ELECTRICAL ENGINEERING DEVELOPMENTS

LITHIUM BATTERIES:
RESEARCH, TECHNOLOGY
AND APPLICATIONS

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 ELECTRICAL ENGINEERING DEVELOPMENTS

LITHIUM BATTERIES:
RESEARCH, TECHNOLOGY
AND APPLICATIONS

GREGER R. DAHLIN
AND KALLE E. STROM
EDITORS

Nova Science Publishers, Inc.

New York
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Lithium batteries : research, technology, and applications / editors, Greger

R. Dahlin and Kalle E. Strxm.
p. cm.
Includes index.
ISBN 978-1-61668-517-1 (eBook)
1. Lithium cells. I. Dahlin, Greger R. II. Strxm, Kalle E.
TK2945.L58L5535 2009
621.31'2423--dc22
ISBN: 9781607417224 2009051579

Published by Nova Science Publishers, Inc.  New York

 CONTENTS

Preface vii
Chapter 1 LiFePO4 Cathode Materials for Lithium-Ion Batteries 1
B. Jin and Q. Jiang
Chapter 2 Inorganic Cathode Materials
for Lithium Ion Batteries 31
Zhicong Shi , Hansan Liu and Jiujun Zhang
Chapter 3 Analysis of Cell Impedance for the Design
of a High-Power Lithium-Ion Battery 73
Hyung-Man Cho and Heon-Cheol Shin
Chapter 4 Chemical Overcharge Protection
of Lithium-Ion Cells 119
Zonghai Chen, Yan Qin and Khalil Amine
Chapter 5 Thermal Stability and Electrochemical Performance
of LiCoO2 and LiCo0.2Ni0.8O2
in Lithium-Ion Batteries 147
George Ting-Kuo Fey and T. Prem Kumar
Chapter 6 Compositional and Structural Evolution of Cathode
Particles of the Cycled Lithium Batteries
Investigated by Analytical High Resolution
Transmission Electron Microscopy (AHRTEM) 165
Yuewu Zeng , Shaofeng Chen, Jinhua He and Z.C.
Kang ,
vi Contents

Chapter 7 Soft Solution Processing of Nanoscaled Lithium

Vanadium Oxides as Cathode Materials
for Rechargeable Lithium Ion Batteries 181
Hao Wang, HaiYan Xu and Hui Yan
Chapter 8 Advanced Lithium-Ion Batteries
for Plug-in Hybrid-Electric Vehicles 203
Paul Nelsonα and Khalil Amineβ
Index 223
 PREFACE

Lithium ion batteries, a class of chemical power sources that use an

electrochemical process of lithium ion intercalation into or de-intercalation
from host materials, are gaining dominance in mobile electronic applications,
and are also showing promise for an upcoming new generation of electric
vehicle applications. Since SONY Corporation commercialized rechargeable
lithium-ion batteries, the batteries have been widely utilized as the power
sources in a wide range of applications, such as mobile phones, laptop
computers, digital cameras, electrical vehicles, and hybrid electrical vehicles.
This book is concerned with the recent developments in and research of
LiFePo4 cathode materials with an emphasis on the synthesis method and how
to improve electrochemical performance. Moreover, the efforts made to
develop other new inorganic cathode materials for a new generation of lithium
ion batteries are reviewed. A systematic semi-empirical way to analyze the
constituents of total cell impedance in lithium-ion battery is also presented. In
addition, overcharge protection is not only critical for preventing the thermal
runaway of lithium-ion batteries during operation, but also important for
automatic capacity during battery manufacturing and repair. This book
compares three overcharge protection strategies - external circuit protection,
inactivation agents, and redox shuttles - to highlight the advantage of redox
shuttles for overcharge protection. The safety of lithium-ion battery packs are
also discussed, as well as techniques for studying thermal stability, such as
differential scanning calorimetry and accelerating rate calorimetry.
Chapter 1-Since SONY Corporation commercialized rechargeable
lithium-ion batteries 18 years ago [1], the batteries have been widely utilized
as the power sources in a wide range of applications, such as mobile phones,
laptop computers, digital cameras, electrical vehicles, and hybrid electrical
viii GREGER R. DAHLIN AND KALLE E. STROM

vehicles. In rechargeable lithium-ion batteries, cathode materials are one of the

key components, and mainly devoted to the performance of the batteries.
Among the known cathode materials, layered LiCoO2, LiMnO2, and LiNiO2,
spinel LiMn2O4, and other cathode materials such as elemental sulfur have
been studied extensively [2-15] while LiCoO2 has been used as the cathode
material for commercial lithium-ion batteries. However, due to the toxicity and
the high cost of Co, novel cathode materials must be developed not only in
relation to battery performance but also in relation to safety and cost.
Chapter 2- Lithium ion batteries, a class of chemical power sources that
use an electrochemical process of lithium ion intercalation into or de-
intercalation from host materials, are gaining dominance in mobile electronic
applications, and also showing promise for an upcoming new generation of
electric vehicle applications. Currently, the most successful active electrode
materials used in lithium ion batteries are graphite (anode material with a
specific capacity of 350 mA h g-1) and LiCoO2 (cathode material with a
specific capacity of 135 mA h g-1). Under the driving force of safety issues, a
new cathode material, LiFePO4, has been developed in recent years as the
most promising cathode material for next-generation lithium ion batteries.
However, this new material can deliver a specific capacity of only 150 mA h
g-1, which is far less than that of anode materials (Figure 1) [ 1 ]. The low
specific capacity of cathode materials has been identified as the factor
preventing lithium ion batteries from meeting the high capacity and high
power demands of automobiles and electronic devices. Therefore, finding
cathode materials with higher specific capacities has become the key priority
in lithium ion battery research and development (R&D).
Chapter 3- This work presents a systematic semi-empirical way to analyze
the constituents of total cell impedance in a lithium-ion battery, and their time-
dependent contributions to total direct current (dc) polarization. The approach
includes the differentiation of internal resistive elements, followed by
theoretical calculations of their contributions to total polarization using circuit
analysis. Our method provides a fast and reliable way to design a high-power
battery with the instantaneous input/output power that best fits the user’s
specific needs. It also provides insight into the design of high-power with long
shelf life and calendar life. We begin with an overview of high-power cell
design. Methodology to differentiate and quantify the time-dependent
contribution of elementary resistances to total polarization is given, and
applications to power aging in battery use, and power decline at low operating
temperature, are suggested. A strategy for the design of materials to meet
power requirements is discussed for each case.
 Preface ix

Chapter 4- Overcharge protection is not only critical for preventing the

thermal runaway of lithium-ion batteries, but also important for automatic
capacity balancing. This chapter compares three overcharge protection
strategies—external circuit protection, inactivation agents, and redox
shuttles—to highlight the advantage of redox shuttles for overcharge
protection. Then the redox shuttle history and mechanism are introduced and
the latest advances on redox shuttles are described. Fundamental studies for
designing stable redox shuttles for use in lithium-ion batteries are also
discussed.
Chapter 5- Parallel to the rising market for lithium-ion power packs, more
incidents of severely debilitating and sometimes fatal tragedies, as a result of
battery hazards are being reported. Some of the safety risks of lithium-ion
batteries are inherent in the fact that they combine highly energetic materials
that are in contact with a flammable electrolyte based on organic solvents.
Moreover, the potential ranges experienced by these cells are beyond the
thermodynamic stability windows of the electrolytes, which can decompose
upon contact with the charged active materials. The interface between the
cathode and electrolyte is of special concern since partial dissolution of the
active material can create further complications. This chapter discusses
processes at the positive electrode that can lead to thermal runaway, especially
at those based on the most popular cathode materials, LiCoO2 and
LiNi0.8Co0.2O2. Measures such as coating cathode particles with inert oxides
have been shown to improve cell safety by increasing the onset temperature of
electrode-electrolyte reactions and lowering the exothermicity of such
reactions. Additionally, coatings also bestow improved cyclability to the
cathodes. Reactivity of cathode active materials is also related to electrolyte
composition. Electrolyte additives and non-flammable electrolytes are a case
in point. Techniques for studying thermal stability such as differential
scanning calorimetry and accelerating rate calorimetry are also discussed.
Chapter 6- As is well known [1-3], the lithium battery is a rechargeable
battery and its lithium comes from the cathode electrode materials such as
lithium intercalated transition metal oxides, for example, LiCoO2, LiNiO2,
LiMnO2, Li(Co1-x-yNixMny)O2, and LiMn2O4. During the charging process, the
Li+ ions pull out from the lithium intercalated oxides by electric field and are
expelled into the carbon layers of graphite anode through an electrolyte.
Therefore, the graphite anode acts as Li+ ions sink. However, during the
discharging process, the Li+ ions stored in the graphite anode act as Li+ source
and will flow out from the graphite anode intercalating into the oxygen closed
packed layers of the dioxide cathode through an electrolyte. So, the cathode is
x GREGER R. DAHLIN AND KALLE E. STROM

a sink of the flowing Li+ ions. The anode and cathode both act as Li+ ion
source and sink. The capacity of the lithium battery is dominated by the Li+
ion source storage capacity and the sink volume. The rate of Li+ ions flow is
also related to the source and sink capability. The cathode and anode,
especially the cathode, are very important for the lithium battery.
Chapter 7- Lithium vanadium oxides have been extensively studied
because of their possible application as a cathode material for rechargeable
lithium batteries. Due to their low cost, they are one of the promising
substitutes for the expensive LiCoO2 cathode presently commercially used.
Lithium vanadium oxides including γ-LiV2O5 and LiV3O8 have been prepared
by soft solution methods in this study. In the first part of this work, γ-LiV2O5
nanorods have been prepared directly by a simple solvothermal method using
ethanol as a solvent, which also serves as a reducing agent. The γ-LiV2O5
nanorods with diameters of 30-40 nm obtained at 160 oC shows a larger
capacity of 259 mAh/g in the range of 1.5 - 4.2 V, and its capacity remained
199 mAh/g after 20 cycles. In the second part, LiV3O8 nanorods have been
obtained by a novel hydrothermal-based two-step method. The LiV3O8 sample
treated at 300 oC shows a poor crystallinity while a specific capacity of 302
mAh/g in the range of 1.8 - 4.0 V, and its capacity remained 278 mAh/g after
30 cycles. It indicates that the lithium vanadium oxide nanorods prepared by
the above methods have potentiality to be used as cathode material in
rechargeable lithium ion batteries.
Chapter 8- In this study, electric-drive vehicles with series powertrains
were configured to utilize a lithium- ion battery of very high power and
achieve sport-sedan performance and excellent fuel economy. The battery
electrode materials are LiMn2O4 and Li4Ti5O12, which provide a cell area-specific
impedance of about 40% of that of the commonly available lithium-ion
batteries. Data provided by EnerDel Corp. for this system demonstrate this
low impedance and also a long cycle life at 55oC. The batteries for these
vehicles were designed to deliver 100 kW of power at 90% open- circuit
voltage to provide high battery efficiency (97-98%) during vehicle
operation. This results in battery heating of only 1.6oC per hour of travel on
the urban dynamometer driving schedule (UDDS) cycle, which essentially
eliminates the need for battery cooling. Three vehicles were designed, each
with series powertrains and simulation test weights between 1575 and 1633 kg:
a hybrid electric vehicle (HEV) with a 45-kg battery, a plug-in HEV with a 10-
mile electric range (PHEV10) with a 60-kg battery, and a PHEV20 with a 100-
kg battery. Vehicle simulation tests on the Argonne National Laboratory’s
simulation software, the Powertrain System Analysis Toolkit (PSAT), which
 Preface xi

was developed with MATLAB/Simulink, showed that these vehicles could

accelerate to 60 mph in 6.2 to 6.3 seconds and achieve fuel economies of
50 to 54 mpg on the UDDS and highway fuel economy test (HWFET) cycles.
This type of vehicle shows promise of having a moderate cost if it is mass
produced, because there is no transmission, the engine and generator may be less
expensive since they are designed to operate at only one speed, and the
battery electrode materials are inexpensive.
In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 1

LIFEPO4 CATHODE MATERIALS

FOR LITHIUM-ION BATTERIES

B. Jin∗ and Q. Jiang

Key Laboratory of Automobile Materials (Jilin University),
Ministry of Education, and School of Materials Science and Engineering,
Jilin University, Changchun 130025, China.

1. INTRODUCTION
Since SONY Corporation commercialized rechargeable lithium-ion
batteries 18 years ago [1], the batteries have been widely utilized as the power
sources in a wide range of applications, such as mobile phones, laptop
computers, digital cameras, electrical vehicles, and hybrid electrical vehicles.
In rechargeable lithium-ion batteries, cathode materials are one of the key
components, and mainly devoted to the performance of the batteries. Among
the known cathode materials, layered LiCoO2, LiMnO2, and LiNiO2, spinel
LiMn2O4, and other cathode materials such as elemental sulfur have been
studied extensively [2-15] while LiCoO2 has been used as the cathode material
for commercial lithium-ion batteries. However, due to the toxicity and the high
cost of Co, novel cathode materials must be developed not only in relation to
battery performance but also in relation to safety and cost.

∗ Corresponding author: Tel.: +86-431-85095170; E-mail: [email protected] (B. Jin)

2 Zhicong Shi , Hansan Liu and Jiujun Zhang

Figure 1. The schematic representation of the crystal structure of LiMPO4 (M=Fe, Mn,
Co, and Ni) compounds showing the HCP oxygen array with MO6 and PO4 groups.

Recently, LiMPO4 (M = Fe, Mn, Ni, and Co) proposed by Goodenough et

al. with an ordered olivine-type structure has attracted an extensive attention
due to a high theoretical specific capacity (~170 mAh g-1) [16-35]. As shown
in Figure 1, LiMPO4 (M = Fe, Mn, Co, and Ni) adopts an olivine-related
structure, which consists of a hexagonal closed-packing (HCP) of oxygen
atoms with Li+ and M2+ cations located in half of the octahedral sites and P5+
cations in 1/8 of tetrahedral sites. This structure may be described as chains
(along the c direction) of edge-sharing MO6 octahedra that are cross-linked by
the PO4 groups forming a three-dimensional network. Tunnels perpendicular
to the [010] and [001] directions contain octahedrally coordinated Li+ cations
(along the b axis), which are mobile in these cavities. Among these
phosphates, LiFePO4 is the most attractive because of its high stability, low
cost and high compatibility with environments [36-37]. However, it is difficult
to attain the full capacity because the electronic conductivity is very low,
which leads to initial capacity loss and poor rate capability, and diffusion of
Li+ ion across the LiFePO4/FePO4 boundary is slow due to its intrinsic
character [16]. The electronic conductivity of LiFePO4 is only 10-9-10-10 S cm-
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 3

1
[38], being much lower than those of LiCoO2 (~10-3 S cm-1) and LiMn2O4
(2×10-5-5×10-5 S cm-1) [39-40]. Many researchers have suggested solutions to
this problem as follows: (i) coating with a conductive layer around the
particles [41-42]; (ii) ionic substitution to enhance the electrochemical
properties [38]; and (iii) synthesis of particles with well-defined morphology
[43-44]. The most researches focus on synthesis method and developing the
simple preparation procedure to improve low electronic conductivity and
cycling performance of LiFePO4.
This review will be concerned with the recent development and research
of LiFePO4 cathode materials with emphasis on synthesis method and how to
improve electrochemical performance. Here we will also draw the cathode
performance from examples taken from our own work. This contribution
consists of five sections. Section 1 is entitled Introduction. The following
section (Section 2) describes the synthesis method. Section 3 focuses on how
to improve electrochemical performance. Section 4 provides summary and
future prospects. Section 5 is acknowledgments.

2. SYNTHESIS METHOD OF LIFEPO4 CATHODE

MATERIALS

2.1. Solid-State Reaction

Many research groups have tried to use solid-state reactions to synthesize

LiFePO4 [16, 45-49]. The solid-state reaction is a conventional synthesis
method, which usually needs a two-step heating treatment including the first
firing in a temperature range of 300-400 °C and subsequent one between 600
and 800 °C. These repeated heat-treatments result in a large particle size due to
crystal growths in the final product [43, 45]. Goodenough et al. [16]
synthesize LiFePO4 by direct solid-state reaction of stoichiometric amounts of
Fe(II)-acetates, ammonium phosphate, and Li carbonate. The intimately
ground stoichiometric mixture of the starting materials is first decomposed at
300 to 350 °C to drive away the gases. The mixture is then reground and
returned to the furnace at 800 °C for 24 h before being cooled slowly to room
temperature. The X-ray diffraction (XRD) testing shows the emergence and
growth of a second phase at the expense of LiFePO4 synthesized by the above
solid-state reaction as more and more Li ions are extracted. With total
chemical delithiation, the second phase could be identified by both chemical
4 Zhicong Shi , Hansan Liu and Jiujun Zhang

analysis and Rietveld refinement to XRD data to be FePO4. The XRD testing
for chemical lithiation of FePO4 shows the emergence and growth of LiFePO4
at the expense of FePO4 on more lithiation. Both LiFePO4 and FePO4 have the
same space group. There are contractions of a and b constants on chemical
extraction of Li from LiFePO4, but a small increase in c constant. The volume
decreases by 6.81% and the density increases by 2.59%. Electrochemical
charge and discharge testing results indicate that approximately 0.6 Li atoms
per formula unit can be extracted at a closed-circuit voltage of 3.5 V vs. Li and
the same amount can be reversibly inserted back into the structure on
discharge. The extraction and insertion of Li ions into the structure of LiFePO4
is not only reversible on repeated cycling; the capacity actually increases
slightly with cycling.
Kim et al. [49] synthesize LixFePO4 (X = 0.7-1.1) by a solid-state
reaction. Li2CO3, FeC2O4·2H2O and NH4·H2PO4 as starting materials are
milled with ZrO2 ball in acetone for 24 h. After acetone is removed, the
mixture is then decomposed at 350 °C for 10 h in flowing N2 gas to avoid
oxidation of Fe2+. The powder is ground again using mortar and pestle, then it
is pelletized. Finally the samples are heated at 700 °C for 24 h in flowing N2
gas. The lattice parameters calculations of LixFePO4 synthesized via the above
solid-state reaction process with different Li contents demonstrate that lattice
constants of these samples are approximately similar. Comparison of discharge
capacities of LiXFePO4 with various current densities presents that Li0.9FePO4
has more capacity and better rate capability than the other two samples.

2.2. Hydrothermal Method

The hydrothermal synthesis is a useful method to prepare fine particles,

and has some advantages such as simple synthesis process, and low energy
consumption, compared to high firing temperature and long firing time during
solid-state reaction used conventionally [50-56]. We also report the synthesis
of LiFePO4 by the hydrothermal synthesis [57-60]. Although LiFePO4 can be
easily synthesized hydrothermally at 150-220 °C and its XRD pattern looks
good, it gives poor cycling performance; The HR-TEM image of LiFePO4
heat-treated at 170 °C and subsequent at 500 °C in Figure 2 displays that
amorphous layers with a thickness of about 1-3 nm are coated on the particle
surfaces due to generation of carbon on the particle surfaces through
decomposition of ascorbic acid as a reducing agent during the hydrothermal
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 5

reaction, which results in an increase in the discharge capacity as demonstrated

in Figure 3.
Whittingham et al. [52] also demonstrate hydrothermal synthesis of
LiFePO4 where the used starting materials are FeSO4·7H2O, H3PO4 and LiOH.
The molar ratio of the Li:Fe:P is 3:1:1, and a typical concentration of FeSO4 is
22 g/liter of water. Sugar and/or L-ascorbic acid are added as an in situ
reducing agent to minimize the oxidation of ferrous to ferric. Multi-wall
carbon nanotubes are also added to improve electronic conductivity of
LiFePO4. The resulting grayish blue gel is transferred into a 125 ml capacity
Teflon-lined stainless steel autoclave, which is sealed and heated at 150-220
°C for 5 h. Precipitates are collected by suction filtration and dried at 60 °C for
3 h in the vacuum oven. The XRD results demonstrate that the only phase
observed is LiFePO4. The lattice constants obtained from Rietveld refinement
are: a = 10.332(2) Å, b = 6.005(1) Å, c = 4.6939(6) Å, V = 291.2 Å3.
Charge/discharge tests results in the first cycle show that for LiFePO4
synthesized by the above hydrothermal synthesis, close to 160 mAh g-1
capacity is obtained on the charging cycle, and the capacity is over 145 mAh
g-1 on discharge which is maintained over subsequent cycling.

2.3. Co-Precipitation

The co-precipitation procedure, a commercially feasible process, can

prepare a fine, chemically uniform and more homogenous powder size
distribution of LiFePO4. Yang et al. [61] prepare LiFePO4 with co-
precipitation from aqueous solution containing trivalent iron ion. The aqueous
precursor mixture of Fe(NO3)3, LiNO3, (NH4)2HPO4, ascorbic acid and
appropriate amount of ammonia is used. The purpose of ascorbic acid has
reduced Fe3+ to Fe2+ in the aqueous precursor. The amount of sugar added into
the precursor solution is 20 wt % of LiFePO4 to be formed. The co-
precipitated powder can be easily separated in a centrifuge and then the co-
precipitated powder is dispersed in the hydrolyzed sugar solution, followed by
drying and heating. The sugar-coated powder is calcined at 350 °C for 10 h
and subsequently sintered at 600 °C for 16 h in N2 atmosphere. The sugar will
be converted to carbon and distributed evenly on the LiFePO4 powders. The
particle size distribution result of LiFePO4 synthesized via the above co-
precipitation process shows that the particle distribution is bimodal, the
population peak around smaller particle size is LiFePO4 powder (about 1.51
μm) and another population peak at larger particle size (about 8.04 μm) can be
6 Zhicong Shi , Hansan Liu and Jiujun Zhang

attributed to the LiFePO4/C particles composed porous carbon structure with

LiFePO4 embedded. The charge/discharge test results demonstrate that
LiFePO4/C synthesized via the above co-precipitation process can exhibit
good capacity retention with slow charge/discharge rate (C/10-C/3), 85% of
theory capacity of 169 mAh g-1.
Park [62], Arnold [63], Ni [64], Park [65] and Prosini [66] et al. also
improve the electrochemical performance of LiFePO4 by co-precipitation
method.

2.4. Emulsion-Drying Method

LiFePO4 can be prepared via a hydrothermal method as mentioned above,

but encounters the problem that some Fe ions reside on the Li sites and
therefore deteriorates cell properties [67]. In such a liquid-phase synthesis, a
solid phase is usually formed through a chemical reaction in the liquid phase.
Hence, compared with solid-state reaction methods, some advantages are
expected for the resultant powders, such as homogeneous mixing, lower
heating temperature and smaller particle sizes. Emulsion-drying method as a
new liquid-phase synthesis route is also used to prepare olivine-type LiFePO4.
Myung et al. [37] prepare LiFePO4/C composite by emulsion-drying method.
Stoichiometric amounts of LiNO3, Fe(NO3)3·9H2O and (NH4)2HPO4 are
dissolved in distilled water. The aqueous solution is then vigorously mixed
with a mixture of an oily phase, Kerosene : Tween 85 (surfactant) = 7 : 3 in
volume, to prepare a homogeneous water-in-oil (W/O) type emulsion, in
which cations are distributed very uniformly on an atomic scale. Finally, the
prepared W/O type emulsion consisting of LiNO3, Fe(NO3)3·9H2O, and
(NH4)2HPO4 is mainly composed of an oil phase (aqueous : oil phases = 2 : 8
in volume). The emulsion-dried precursor is burned out at 300 or 400 °C with
a certain time in an air-limited box furnace. The obtained powders are then
calcined at the desired temperatures for a specific time in a tube furnace with
an Ar atmosphere. The charge/discharge testing results of LiFePO4/C
composite synthesized via the above emulsion-drying process and cycled at 50
°C indicate that a higher capacity of about 140 mAh g-1 is obviously observed
at 50 °C and the capacity retention during cycling is over 98%.
Chung et al. synthesize LiFePO4 by direct heating of a dried emulsion
precursor [68]. LiNO3, Fe(NO3)3·9H2O and (NH4)2HPO4 are used as the
starting materials. The dried emulsion precursor powders are heated under Ar
flow at a heating rate of 5 °C/min to different temperatures. The cycle
performance of LiFePO4 synthesized at various temperatures and at 750 °C
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 7

with 40 wt % carbon black as a conductive agent via the above emulsion-

drying process demonstrate that the capacity obtained from the compound
heated at 750 °C is higher than that obtained at 850 °C due to the particle-size
effect, and the initial discharge capacity of LiFePO4 synthesized at 750 °C
with 40 wt % carbon black is 132.5 mAh g-1, and increases to 151 mAh g-1 at
the 10th cycle due to an enhancement in electronic conductivity through the
use of a large amount of carbon black.

Figure 2. The HR-TEM image of LiFePO4 heat-treated at 170 °C and subsequent 500
°C.

5.0
4.5
4.0
Voltage (V)

3.5
3.0
2.5 a b

2.0 5th 1st 5th1st

1.5
1.0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170
Capacity (mAh g-1)

Figure 3. The discharge curves of LiFePO4 synthesized at (a) 170 °C and (b) 170 °C
and subsequent 500 °C.
8 Zhicong Shi , Hansan Liu and Jiujun Zhang

2.5. Sol-Gel Method

There has been much interest recently in LiFePO4 made by a sol-gel

process [69-76]. Gaberscek et al. [73] synthesize LiFePO4-based composite
materials via a sol-gel method. 0.01 mol of Li3PO4 and 0.02 mol of H3PO4 are
dissolved in 200 mL water by stirring at 70 °C for 1 h separately. 0.03 mol of
iron (III) citrate is dissolved in 300 mL of water by stirring at 60 °C for 1 h.
The two solutions are mixed together and dried at 60 °C for 24 h. After
thorough grinding with a mortar and pestle, the obtained material is fired in
inert (Ar) or reductive (5 % of H2 in Ar) atmosphere at 500-700 °C for 15 min-
72 h. The resulting LiFePO4/C consists of micrometer-sized particles
containing pores with wide distribution of sizes. When filled with electrolyte,
the pores are responsible for supply of ions while the distance between the
pores (30-150 nm) determines the solid-state diffusion kinetics. The walls of
pores are covered with a carbon layer, which serves as an electron conductor
and is thin enough (2-3 nm) to allow penetration of Li ions. The
electrochemical test data demonstrate that LiFePO4/C synthesized via the
above sol-gel process at lower rates can recover towards the nominal capacity
even after 50 cycles of the very high rate operation of 3400 mA/g.
Choi et al. [71] also report the synthesis of olivine-type LiFePO4 by a sol-
gel route using lauric acid as the surfactant while CH3CO2Li·2H2O,
FeCl2·4H2O and P2O5 are used as the starting materials. Each precursor is
dissolved separately in ethanol to yield a 1 M solution. Fe and P solutions are
first mixed in the desired stoichiometric ratio and stirred for 3 h followed by
the addition of stoichiometric amount of the Li solution. Equal molar ratio of
lauric acid surfactant is added to the solution after 3 h of stirring. After 4 h, the
reaction is presumed to be complete and the ethanol is evaporated under
continuous flow of ultra high purity-Ar followed by heat-treatment under
H2/Ar = 10%/90% atmosphere at 500 °C for 5 h to prevent the possible
formation of Fe3+ impurities. LiFePO4 synthesized with lauric acid surfactant
via the above sol-gel process can deliver a specific capacity of 125 and 157
mAh g-1 at discharge rates of 10 and 1C with less than 0.08% fade per cycle,
respectively. The major advantage of the current sol-gel approach is the
formation of a porous network structure with uniform particle size by utilizing
a carboxylic acid surfactant, which acts as a capping agent preventing and
minimizing the agglomeration of the phosphate particles.
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 9

2.6. Mechanical Alloying

Recent studies have shown that mechanical alloying or mechanical

activation (MA) is a promising method for synthesis of LiFePO4 [77-87], in
which the powder particles undergo repeated welding, fracturing and re-
welding in a dry high-energy ball-milling vessel. This process results in
pulverization and intimate powder mixing. It has been found that a ball-milling
step alone is insufficient to obtain a single-phase olivine product. On the other
hand, the time and temperature of the thermal treatment necessary for final
crystallization of the compound can be decreased substantially by this process
[80, 85].
Kim et al. [77] prepare olivine LiFePO4 cathode materials by mechanical
alloying using iron (Ш) raw material. LiOH·H2O, Fe2O3, (NH4)2H·PO4, and
acetylene black powders are used as starting materials. The MA process is
carried out for 4 h under argon atmosphere using a shaker type ball miller
rotating at around 1000 rpm. The mechanical-alloyed powders are then fired
from 500 to 900 °C for 30 min in a tube-type vacuum furnace at a pressure 10-
6
Torr. LiFePO4 synthesized by the above mechanical alloying exhibits
excellent cell performance with a discharge capacity of 160 mAh g-1.
Kim et al. [79] also report the synthesis of nano-sized LiFePO4 and
carbon-coated LiFePO4 (LiFePO4/C) cathode materials by a mechanical
activation process. LiFePO4 is synthesized from Li2CO3, FeC2O4·2H2O and
NH4H2PO4 taken in stoichiometric quantities. The mechanical activation
process consists of the following steps: (i) high-energy ball milling of the
powder in a hardened steel vial with zirconia balls at room temperature for
different periods in an argon atmosphere using a SPEX mill at 1000 rpm; (ii)
conversion of the powder into pellets by mechanical pressing; (iii) thermal
treatment of the pellets at temperatures ranging from 500 to 700 °C for
different time intervals in a nitrogen atmosphere; (iv) slow cooling to room
temperature. LiFePO4/C with 7.8 wt % acetylene black is prepared by the
same processing steps. LiFePO4/C synthesized by the above mechanical
activation process exhibits excellent electrochemical performance, with low
capacity fading even at the high current density of 2C.

2.7. Microwave Processing

Microwave processing can achieve very fast and uniform heating through
a self-heating process that arises from direct absorption of microwave energy
10 Zhicong Shi , Hansan Liu and Jiujun Zhang

into materials within a short period of time, and at temperatures lower than
that required for furnace heating. This processing has been applied in the
synthesis of LiFePO4 as a novel heating method [88-93].
Higuchi et al. [88] report a novel synthetic method of microwave
processing with a domestic microwave oven to prepare LiFePO4 cathode
materials. The used starting materials are Li2CO3, NH4H2PO4, and
Fe(CH3COO)2 or Fe(CH3CHOHCOO)2·2H2O. These materials are weighed in
stoichiometric ratios, dispersed into ethanol, and thoroughly mixed using an
agate mortar. The mixed powder is dried at 60 °C and pressed at a pressure of
98 MPa into pellets. Each pellet is covered with glass wool and then placed in
an alumina crucible with a lid. The microwave irradiation to the crucible is
conducted with a domestic microwave oven that operated at 2.45 GHz, with a
maximum power level of 500 W. The charge/discharge result demonstrates
that the initial discharge capacity of LiFePO4 synthesized quickly and easily
by the above microwave processing is about 125 mAh g-1 at 60 °C.
Song et al. [89] also demonstrate the synthesis of LiFePO4-C by ball-
milling and subsequent microwave heating. Li3PO4 and Fe3(PO4)2·8H2O are
used as precursor materials. Stoichiometric amounts of Li3PO4 and
Fe3(PO4)2·8H2O (1:1, molar ratio) are weighed and placed in a ball-milling jar
with 5 wt % acetylene black. Ball-milling at various ball-to-powder ratios
(weight ratios) is carried out under an Ar atmosphere for 30 min using a
vibrant type mill. The ball-milled mixture is pressed into a pellet and then put
inside a quartz crucible that is filled with activated carbon. The quartz crucible
is put in the middle of a domestic microwave oven (750 W) and microwaves
are irradiated for several minutes (2-5 min). During that treatment, carbon
generates heat through the direct absorption of microwave energy and thereby
makes a reductive atmosphere by carbothermal reaction. The cycling
performance demonstrates that LiFePO4-C synthesized by the above ball-
milling and subsequent microwave heating can deliver a high initial discharge
capacity of 161 mAh g-1 at C/10 and exhibit very stable cycling behavior.

2.8. Other Synthesis Methods

Takeuchi et al. [94] prepare LiFePO4/C with 20 wt % acetylene black by

spark-plasma-sintering process at 600 °C. It is found that LiFePO4 particles are
covered with fine carbon particles and they form agglomerates with the size of
about 10 μm. The charge/discharge tests for the cell using LiFePO4/C
composite positive electrodes show superior cycle performance at the rates of
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 11

17-850 mA g-1 (1/10-5C) compared with the cell using conventionally blended
LiFePO4+C composite positive electrodes. The improvement in the cell
performance is attributed to strong binding between LiFePO4 and carbon
powders.
Kim et al. [95] use Fe(CH3COO)2, NH4H2PO4 and LiCH3COO as the
starting materials to synthesize LiFePO4 by polyol process without any further
heating as a post-processing step. The LiFePO4 nanoparticles show a
reversible capacity of 166 mAh g-1, which amounts to a utilization efficiency
of 98%, with an excellent reversibility in extended cycles.
Wu et al. [96] report the synthesis of LiFePO4 by precipitation method.
According to the stoichiometry, iron metal, LiNO3, and (NH4)2HPO4 are
mixed in an aqueous acidic solution. After the starting materials are dissolved,
adequate amount of sucrose is added to the solution then heated at 150 °C to
evaporate water. The solid residue is calcined at 350 °C for 8 h and then heat-
treated at temperatures between 400 and 800 °C for 12 h in N2. Among the
prepared composite cathode materials, the sample heat-treated at 700 °C for 12
h shows better cycling performance than those of others. It shows initial
specific discharge capacities of 165 and 130 mAh g-1 at 30 °C with C rates of
C/10 and 1C, respectively.
Yang et al. [97] synthesize small crystallites LiFePO4 powders with
conducting carbon coating by ultrasonic spray pyrolysis. The precursor
solution for atomization is an aqueous mixing solution of LiNO3,
Fe(NO3)3·9H2O, H3PO4, and ascorbic acid (C6H8O6) in the de-ionized water at
the molar ratio 1:1:1 of Li:Fe:PO4. The amount of white sugar added into the
precursor solution is 60 wt % of LiFePO4 to be formed. The as-sprayed fine
powders pyrolysis-synthesized at 450, 550, and 650 °C are heat-treated at 650
°C for 4 h in a tube furnace under a nitrogen atmosphere, and then furnace-
cooled to room temperature. The carbon coating on the LiFePO4 surface is
critical to the electrochemical performance of LiFePO4 cathode materials of
the Li secondary battery, since the carbon coating does not only increase the
electronic conductivity via carbon on the surface of particles, but also
enhances the ion mobility of Li ion due to prohibiting the grain growth during
post-heat-treatment. The carbon of 15 wt % evenly distributed on the final
LiFePO4 powders can get the highest initial discharge capacity of 150 mAh g-1
at C/10 and 50 °C. Konstantinov et al. [98] report the preparation of carbon-
mixed LiFePO4 cathode materials by spray solution technology. Ni et al. [99]
synthesize well-crystallized LiFePO4 by the KCl molten salt method. Lee et al.
[100, 101] also report the synthesis of LiFePO4 nanoparticles in supercritical
12 Zhicong Shi , Hansan Liu and Jiujun Zhang

water. Carbothermal reduction method [102] and vapor deposition [103] are
also utilized to synthesize LiFePO4.

3. HOW TO IMPROVE ELECTROCHEMICAL PERFORMANCE

OF LIFEPO4 CATHODE MATERIALS

3.1. Effect of Particle Size and Morphology on Electrochemical

Performance of LiFePO4

For LiFePO4, small particle size and well-shaped crystal are important for
enhancing the electrochemical properties [16]. In particles with a small
diameter, the Li ions may diffuse over smaller distances between the surfaces
and center during Li intercalation and de-intercalation, and LiFePO4 on the
particle surfaces contributes mostly to the charge/discharge reaction [45]. This
is helpful to enhance the electrochemical properties of LiFePO4/Li batteries
because of an increase in the quantity of LiFePO4 particles that can be used.
Many researchers have tried to improve the electrochemical performance
by controlling particle size and morphology of LiFePO4 [43-44, 53, 71, 76, 93,
104-115]. Gaberscek et al. [107] suggest that based on analysis of nine papers
by different authors, the discharge capacity of LiFePO4 drops approximately
linearly with average particle size d, regardless of the presence/absence of a
native carbon coating. Furthermore, the electrode resistance, Rm, as a function
of d, follows almost exactly the square law: Rm ∝ dn (n = 1.994). Based on
theoretical derivation of the same dependence for different contact topologies
of interest, they also suggest that the power law with n = 2 is generally valid if
the low-conductivity species in bulk active particle (LiFePO4) are ions. In
particular, to achieve a high-rate capability of LiFePO4, more emphasis should
be placed on minimization of d, while it is sufficient that the carbon phase or
other electronic conductor has only point contacts each individual active
particle if the electron-conducting phase also percolates the whole electrode
material. In conclusion, they claim that particle size minimization is more
important than carbon coating for achieving excellent electrochemical
performance.
Liu et al. [111] prepare nanocomposites of LiFePO4 with carbon by a
solid-state route. Li2CO3, FeC2O4·2H2O, NH4H2PO4, and acetylene black as
the used starting materials are mixed in ratio of Li : Fe : PO4 = 1 : 1 : 1 in a
planet mixer for 24 h. The mixtures are sintered in a tube furnace at 750 °C for
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 13

15 h in an inert atmosphere. The LiFePO4/C nanocomposites with 5 wt %

carbon synthesized by the above solid-state route display d = 100 nm with
spherical particle morphology. They suggest that the unique morphology and
size are due to admixing of carbon in the starting material, which protects
LiFePO4 from oxidation and agglomeration. The cyclic voltammetry results
demonstrate that kinetics of Li intercalation and de-intercalation is greatly
improved by adding carbon. This amelioration can improve the rate capability
of LiFePO4/C.
Ellis et al. [53] add the organic additives ascorbic acid and citric acid to
the starting materials as carbon sources and reducing agents in the course of
LiFePO4 hydrothermal synthesis. They suggest that the size of the crystallites
in the absence of organic additives is controlled by the reaction temperature
and concentration of the precursors. At 190 °C, typical low concentrations of
precursors (7 mmol of (NH4)2Fe(SO4)2·6H2O in 28 ml of water-or 0.25 M in
Fe-along with stoichiometric amounts of H3PO4 and LiOH·H2O) produce
diamond-shaped platelets that are about 250 nm thick. These have large basal
dimensions of 1-5 μm. Increasing the reactant concentration by threefold
creates more nucleation sites and therefore produces much smaller particles,
whose basal size distribution peaks at 250 nm.
The SEM observations of LiFePO4 prepared at low concentration of
precursors (0.25 M in Fe) and at 190 °C and subsequent 600 °C confirm that
the presence of a reducing agent strongly affects the morphology. The particle
size of LiFePO4 prepared from the ascorbic acid is obviously smaller (250-1.5
μm) than that without the reducing agent. Conversely, LiFePO4 prepared from
the citric acid contains a wide distribution of particle sizes (500 nm-3 μm),
with particle thicknesses remarkably greater than those without additives. The
Raman spectrum identifies the deposition of significant quantities of carbon
(about 5 wt %) for LiFePO4 prepared from the ascorbic acid. This is possibly
because ascorbic acid decomposes near 200 °C under typical conditions. The
more stable citric acid does not decompose during the hydrothermal reaction
and as a result minimal carbon is detected. These discrepancies in particle size
and carbon content are evident in a comparison of the charge/discharge
performance of the two materials. With substantially more carbon and smaller
average particle size, the LiFePO4 with the ascorbic acid exhibits 70%
reversibility on the first cycle, as compared to 35% for the LiFePO4 prepared
from citric acid when cycled at a rate of C/10.
Wang et al. [105] report the preparation of LiFePO4 via firing amorphous
LiFePO4 obtained by chemical reduction and lithiation of FePO4 using
Vitamin C (VC) as a reducing agent and Li acetate as Li source in alcohol
14 Zhicong Shi , Hansan Liu and Jiujun Zhang

solution. A solution of precursors is prepared by dissolving 0.06 mol VC and

0.12 mol Li acetate in alcohol, and then 0.1 mol prepared amorphous FePO4 is
suspended in the solution. After stirring the suspension at 60 °C for 5 h, the
alcohol insoluble amorphous LiFePO4 forms. Crystalline grey LiFePO4
powder is obtained by sintering the amorphous LiFePO4 in furnace at 600 °C
for 2 h under Ar (95%) + H2 atmosphere.
The cycling performance of LiFePO4 prepared by the above non-aqueous
method at various charge/discharge rates shows that LiFePO4 exhibits good
cycling stability and high reversible capacity. Capacity attenuation is
neglectable on cycling. The capacity of LiFePO4 decreases from about 159
mAh g-1 at C/10 in the first 45 cycles to about 154 mAh g-1at C/2 rate in the
next 10 cycles, and to about 144 mAh g-1 at 1C in another 10 cycles and
finally recovers to 157 mAh g-1 when the discharge rate changes back to C/10.
Shortening the diffusion path by synthesizing fine particles is an effective way
for improving the high-rate performance of LiFePO4. The ultrafine spherical
particles and the conductive carbon between the particles of LiFePO4 are the
reasons for its excellent high rate capability.
In addition, Meligrana et al. [104] report that C19H42BrN as carbon source
and reducing agent can lead to the synthesis of LiFePO4 with finely dispersed
nanocrystalline grains. Zaghib et al. [113] synthesize LiFePO4 nanoparticles
where the size of the particles is small enough that surface effects become
important but large enough that their core region is not affected.

3.2. Substitution of Li+ or Fe2+ with Cations

It is known that it is difficult to attain the full capacity because the

electronic conductivity of LiFePO4 is very low, which leads to initial capacity
loss and poor rate capability, and diffusion of Li+ ion across the
LiFePO4/FePO4 boundary is slow due to its intrinsic character [16]. Therefore,
to improve electrochemical performance of LiFePO4, we should control
particle sizes and morphology [43-44, 53, 71, 76, 93, 104-115], as mentioned
in section 3.1. Recently, it is found that ionic substitution is another feasible
way to enhance the intrinsic electronic conductivity [116-131].
Yamada et al. [116-119] report the preparation of Mn-doped
LiMn0.6Fe0.4PO4 by solid-state reaction of FeC2O4, MnCO3, NH4H2PO4, and
Li2CO3. The used starting materials are dispersed into acetone, then
thoroughly mixed, and reground by ball-milling. The mixture is first
decomposed at 280 °C and reground again, then heated at 600 °C in purified
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 15

N2 gas flow. The charge/discharge results demonstrate that LiMn0.6Fe0.4PO4

can deliver a discharge capacity of greater than 160 mAh g-1, and
LiMn0.6Fe0.4PO4 exhibits two pairs of voltage plateaus, one at 4.1 V
(Mn3+/Mn2+) and another at 3.5 V (Fe3+/Fe2+). This is obviously different from
the LiFePO4, in which the whole Fe3+/Fe2+ reaction proceeds in a two-phase
way (LiFePO4-FePO4) with a voltage plateau at 3.4 V [16].
Liu et al. [120] synthesize Zn-doped LiZn0.01Fe0.99PO4 by a solid-state
reaction. They suggest that the Zn doping promotes the formation of crystal
structures, expands the lattice volume and provides more space for lithium-ion
intercalation/de-intercalation. In addition, they also claim that the doping
decreases the charge transfer resistance, improves the reversibility of lithium-
ion intercalation/ de-intercalation, and increases the diffusion of Li ions due to
the pillar effect of the doped Zn atoms. The Li ion diffusion coefficient of Zn-
doped LiFePO4 increases from 9.98×10-14 to 1.58×10-13 cm2 s-1. As results,
both discharge capacity and rate capability are greatly ameliorated. After Zn
doping, the discharge capacity increases from 88 to 133 mAh g-1 at the current
density of 0.2 mA cm-2 (C/10) in the first cycle.
Wang et al. [121] report the preparation of a series of Co-doped LiFe1-
xCo xPO4 solid solutions by solid-state reactions. They suggest that the
formation of a solid solution lowers the oxidation potential of the Co2+ ions
and makes the Co2+→Co3+ reaction complete at a lower voltage.
Consequently, this reaction makes more contribution of capacity in the solid
solution than in LiCoPO4. The cycling performance of LiFe1-xCoxPO4 cycled
at a current density of 10 mA g-1 demonstrate that both LiFePO4 and LiCoPO4
display the poor cycling performance, only 76.2% and 58.2% the capacity of
the first cycle can be retained after 20 cycles for LiFePO4 and LiCoPO4,
respectively. Oppositely, LiFe1-xCoxPO4 solid solutions keep a rather high
capacity during 20 cycles, retaining 88.4% of the original capacity for
LiFe0.8Co0.2PO4, 86.3% for LiFe0.5Co0.5PO4, and 88.1% for LiFe0.2Co0.8PO4.
They claim that electrolyte decomposition should be a reason for the capacity
fading of LiFe1-xCoxPO4 solid solutions as well as for that of LiCoPO4.
Wang et al. [122] synthesize LiFePO4 and Ti-doped LiTi0.01Fe0.99PO4 by a
sol-gel route. Both LiFePO4 and LiTi0.01Fe0.99PO4 display very flat charge and
discharge plateaus. LiFePO4 and LiTi0.01Fe0.99PO4 display initial discharge
capacity of 157 and 160 mAh g-1 (close to the theoretical capacity of 170 mAh
g-1), respectively. They suggest that LiTi0.01Fe0.99PO4 exhibits a slightly higher
capacity due to the enhanced electronic conductivity induced by increased p-
type semiconductivity through the dopant effect, and a variation of Fe valence
16 Zhicong Shi , Hansan Liu and Jiujun Zhang

during the charging and discharging processes without changing of Fe

octahedral coordination symmetry.
Cho et al. [123] have examined the effects of La doping on the
charge/discharge performance of LiFe0.99La0.01PO4/C composite cathode
materials synthesized by a solid-state reaction. The La doping does not affect
the structure of LiFePO4, but remarkably improves its rate capacity
performance and cycling stability. They demonstrate that LiFe0.99La0.01PO4/C
can deliver a discharge capacity of 156 mAh g-1 cycled in a voltage range of
2.8-4.0 V at C/5, compared to 104 mAh g-1 for pure LiFePO4, and sustain 497
cycles based 80% charge retention. They suggest that such a considerable
improvement is mainly attributed to enhanced conductivity (from 5.88×10-6 to
2.82×10-3 S cm-1) and high Li+ mobility in La-doped LiFe0.99La0.01PO4/C.
Zhang et al. [124] report the preparation of Li0.99Mo0.01FePO4/C
composite cathode materials by a solution method followed by calcining at
different temperatures. The mix-doping method does not affect the structure of
Li0.99Mo0.01FePO4/C but evidently improves its capacity delivery and cycling
performance. They demonstrate that Li0.99Mo0.01FePO4/C synthesized at 700
°C for 12 h can deliver the initial discharge capacities of 161 and 124 mAh g-1
at C/5 and 2C, respectively, which is attributed to the enhanced electronic
conductivity by Mo doping and carbon coating. The lower electrochemical
polarization of Li0.99Mo0.01FePO4/C suggests that the enhanced conductivity is
induced by the doping method. They claim that two possible conducting
mechanisms may be involved. The first probable mechanism, as Chung et al.
assumed [38], is p-type conduction by the holes generated at the top of the
bulk valence Fe–O bands by the activation of the electrons to the empty
impurity Mo states. The second probable mechanism is that the doped Mo6+,
the vacancies on Li sites, and their neighboring Fe and O ion form a
conducting cluster [133]. In addition, the residual carbon resulted from the
decomposition of sucrose acts as nucleation site for the formation of
Li0.99Mo0.01FePO4 crystals, helping in obtaining samples with uniform sizes.
The dispersed carbon particles also promote the electrochemical reaction by
enhancing the surface electronic conduction.
According to Ying et al. [125], the spherical Li0.97Cr0.01FePO4/C
composites have been synthesized by a controlled crystallization-carbothermal
reduction method. They demonstrate that at 0.005, 0.05, 0.1, 0.25 and 1C,
Li0.97Cr0.01FePO4/C can achieve the initial discharge capacity of 163, 151, 142,
131 and 110 mAh g-1, respectively, and also shows excellent cycling
performance due to the enhanced electronic conductivity by the Cr3+
substitution and carbon coating. The tap-density of the spherical
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 17

Li0.97Cr0.01FePO4/C powders is as high as 1.8 g cm-3, which is greatly higher

than the non-spherical LiFePO4 powders reported. They claim that the high-
density spherical Li0.97Cr0.01FePO4/C cathode materials can provide significant
incentive for battery manufactures to consider it as a very promising candidate
to be utilized in the lithium-ion batteries with high power density.
Hong et al. [126] synthesize LiFe0.9Mg0.1PO4 by mechanical alloying
method followed by heat treatments. The prepared LiFe0.9Mg0.1PO4 shows an
equilibrium potential plateau in two-phase region with a potential hysteresis of
18 mV between Li insertion and extraction, and has a high rate capability. Due
to the fast charge-transfer reaction, high electronic and ionic diffusivity, the
phase transformation between LiFe0.9Mg0.1PO4 and Fe0.9Mg0.1PO4 begins to
play an important role in the charge/discharge process.
In addition, the improved electrochemical performances of LiMxFe1-xPO4
and Li1-xMxFePO4 (Ti, Zr, Mg) [127], Li0.98Al0.02FePO4/C [128],
Li0.99Ti0.01FePO4/C [129], LiFe0.9M0.1PO4 (M = Ni, Co, Mg) [130-131], and
Li0.99Al0.01FePO4/C [132] are also reported.

3.3. Effect of Carbon Coating and Metal or Metal Oxide Mixing

on Charge/Discharge Performance of LiFePO4

It is well-known that carbon as a reducing agent can not only prevent the
formation of Fe3+ impurity and the agglomeration of particles during the
preparation of LiFePO4, but also increase the electronic conductivity.
Ravet et al. [134] are the first to show that carbon-coated LiFePO4 with 1
wt % carbon can deliver a discharge capacity of 160 mAh g-1 at 80 °C at a
discharge rate of C/10 using a polymer electrolyte.
Huang et al. [135] have made a systematic study of nanocomposites of
LiFePO4 and conductive carbon by two different methods. Method A employs
a composite of LiFePO4 with a carbon xerogel formed from a resorcinol-
formaldehyde precursor; method B uses surface-oxidized carbon particles to
act as a nucleating agent for LiFePO4 growth. Both particle size minimization
and intimate carbon contact are necessary to optimize electrochemical
performance. The resultant LiFePO4/C composite using method A can deliver
90% theoretical capacity at C/2, with very good rate capability and excellent
stability.
Prosini et al. [136] synthesize LiFePO4 by the solid-state reaction of
Li2CO3, FeC2O4·H2O and (NH4)2HPO4 in the presence of high-surface area
carbon-black. The SEM observations demonstrate that the adding of the fine
18 Zhicong Shi , Hansan Liu and Jiujun Zhang

carbon powders reduces LiFePO4 grain size. The carbon is evenly dispersed
among grains, ensuring a good electric contact. LiFePO4 composite cathode
materials are conductive and no additional carbon-black has to be added
during the electrode preparation. Thus, the electrochemical properties of
LiFePO4 are greatly improved. LiFePO4 composite cathode materials can
achieve a discharge capacity of 125 mAh g-1 at a discharge rate of C/10. The
discharge capacity increases with temperatures and the full discharge capacity
can be obtained at 80 °C and C/10 discharge rate. LiFePO4 composite cathode
materials may be cycled 230 times at C/2 discharge rate and room
temperature, delivering an average discharge capacity of 95 mAh g-1, with a
very satisfactory discharge capacity retention.
Shin et al. [83] have investigated the electrochemical performance of
carbon-coated LiFePO4 using three different carbon sources such as graphite,
carbon black, and acetylene black. The SEM observations reveal that the
carbon-coated LiFePO4 consists of non-uniform fine particles with the size
range of 100-300 nm, which are much smaller than the pure LiFePO4 particles.
This implies that the presence of carbon in the mixture retards the particle
growth during calcining. The electronic conductivities of the carbon-coated
LiFePO4 are 10-2-10-4 S cm-1, which are much higher than 10-9-10-10 S cm-1 of
LiFePO4. They suggest that this improvement is attributed to the excellent
electrical contacts between LiFePO4 particles by the carbon layer. Thus, the
electrochemical performance of the carbon-coated LiFePO4 shows higher
discharge capacity and better capacity retention compared to LiFePO4.
LiFePO4 coated with graphite exhibits better electrochemical performance than
others. The carbon-coated LiFePO4 can deliver a discharge capacity of 120
mAh g-1 at 2C and room temperature. Equivalent circuit analysis from
impedance measurement confirms that the improved electrochemical
performance of the carbon-coated LiFePO4 using graphite is induced by the
low charge transfer resistance and low Li-ion migration resistance.
Thorat et al. [137] describe the preparation and testing of LiFePO4
cathodes for hybrid vehicle application. LiFePO4 cathodes contain
combinations of three different carbon conductivity additives: vapor-grown
carbon fibers (CF), carbon black (CB) and graphite (GR). SEM observations
reveal that LiFePO4 cathodes containing carbon fibers (CB+CF and CF only)
show the fibers quite clearly. The fibers appear to be in good contact with
other particles. The fibers are believed to improve the electrical conduction
and contact throughout the cathode and also provide mechanical strength to
the solid matrix. They suggest that the combination of fibers and carbon black
can provide a highly conductive network that connects well to the active
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 19

material particles and the current collector. LiFePO4 cathodes with a mixture
of CF+CB exhibits the best power-performance, followed by cells containing
CF only and then by CB+GR. The improved electrode performance due to the
fibers also allows an increase in energy density while still meeting power
goals. The best specific-power performance for each of the compositions
investigated occurs around an active material loading of 1 mAh cm-2. The
maximum discharge rate that leads to 2.2 V at the end of the pulse is about
20.6C, obtained by interpolation. The specific power corresponding to the
maximum rate is 3882 W kg-1 cathode, again obtained by interpolation.
With the exclusion of carbon black, graphite, acetylene black and vapor-
grown carbon fibers as carbon conductive additives, multiwalled carbon
nanotubes (MWCNTs) are also used as a carbon conductive additive.
MWCNTs have many merits over amorphous acetylene black, such as high
conductivity, small specific surface area and tubular shape. Thess et al. [138]
report that electronic conductivity of MWCNTs thin film is about (1-4)×102 S
cm-1 along the nanotube axis and 5-25 S cm-1 perpendicular to the axis,
respectively.
Li et al. [139] have studied LiFePO4/MWCNTs novel network composite
cathode compared to LiFePO4/acetylene black cathode. The SEM observations
reveal that a piece of MWCNTs connect LiFePO4 particles in series and
countless MWCNTs interlace all particles together to form a three-
dimensional network wiring, the electron conducting on the interface between
cathode particles and current collector is greatly improved when MWCNTs act
as a conducting bridge. The charge/discharge testing results demonstrate that
MWCNTs can improve cycling efficiency and rate capability more effectively
on the same conditions than carbon black. A variety of oxo-functional groups
may exist on the surface of acetylene black. These external functional groups
and micropores on the surface contribute to the irreversible reactions with
electrolytes [140]. However, MWCNTs can prevent these irreversible
reactions and improve cycling efficiency due to deletion of oxides groups and
reduction of specific surface area. LiFePO4/MWCNTs composite cathode
materials can achieve the initial discharge capacities of 155 mAh g-1 at C/10
and 146 mAh g-1 at 1C rate.
We also study the electrochemical performance of LiFePO4/MWCNTs
composite cathode materials synthesized by a hydrothermal method in lithium
polymer batteries. The SEM observations show that the MWCNTs intertwine
with LiFePO4 particles together to form a three-dimensional network. The
dispersed MWCNTs provide pathways for electron transference. Therefore,
the electronic conductivity of LiFePO4-MWCNTs composites is improved.
20 Zhicong Shi , Hansan Liu and Jiujun Zhang

The electronic conductivities are 5.86×10-9 S cm-1 for pure LiFePO4, 1.08×10-1
S cm-1 for LiFePO4-MWCNTs with 5 wt % MWCNTs. Figure 4 shows the
cyclic voltammograms of LiFePO4-MWCNTs with different MWCNTs
contents at a scan rate of 0.1 mV s-1. It can be seen that the redox peak profile
of LiFePO4-MWCNTs with 5 wt % MWCNTs is more symmetric and
spiculate than that of LiFePO4, demonstrating that the reversibility and
reactivity of LiFePO4-MWCNTs with 5 wt % MWCNTs are enhanced due to
improvement of electronic conductivity and the fast ionic diffusion kinetics
resulting from a decrease in the crystallite size by MWCNTs. As shown in
Figure 5, the discharge rate capability of LiFePO4-MWCNTs with 5 wt %
MWCNTs is obviously ameliorated by MWCNTs. LiFePO4-MWCNTs with 5
wt % MWCNTs can deliver the discharge capacities of 123 mAh g-1 at C/10,
110 mAh g-1 at 3C/10, 106 mAh g-1 at C/2, 97 mAh g-1 at 1C and 53 mAh g-1
at 3C.
Spong et al. [141] report the preparation of carbon-coated LiFePO4 by a
novel, one-step, low-cost synthesis method from aqueous precursor solutions
of Fe(NO3)3, LiCH3COO, H3PO4 and sucrose. Sucrose additions up to a mole
fraction of 25% are found to suppress crystallization of the salts during the
first stages of pyrolysis, thereby reducing elemental segregation and
facilitating the formation of the olivine structure below 500 °C in a single
heating step. Sucrose also acts as a reducing agent and a source of carbon to
form a conductive network in the active material during synthesis, leading to a
higher capacity than materials in which sucrose is substituted with acetylene
black. After additional treatment with sucrose at 700 °C, carbon-coated
LiFePO4 can achieve the discharge capacities of 162 mAh g-1 at C/14 rate and
158 mAh g-1 at C/3.5 in the voltage range of 2.0-4.5 V.
Yun et al. [41] use poly(vinyl alcohol) (PVA) as a carbon source to
prepare LiFePO4/C composite cathode materials by a conventional solid-state
reaction with one-step heat treatment at 800 °C. They show that carbon
coating can control particle growth, provide improved electrical contact
between particles, and enhance the surface electronic conductivity⎯all of
which improve electrochemical performance, especially rate capacity. The
charge/discharge testing results indicate that LiFePO4/C composite cathode
material with 5 wt % PVA exhibits the best electrochemical performance, and
can deliver a discharge capacity of 153 mAh g-1 at C/10 with excellent
capacity retention.
In addition to the above carbon sources, there are still
naphthalenetetracarboxylic dianhydride [142], hydroxyethyl-cellulose [70],
white table sugar [143], polypropylene [144], propylene [103], glycol [145],
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 21

Figure 4. The cyclic voltammograms of LiFePO4-MWCNTs with: (a) 0 wt %, and (b)

5 wt % MWCNTs at a scan rate of 0.1 mV s-1.

citric acid monohydrate [146] and kitchen oils (olive, soybean and butter)
[147] for the preparation of LiFePO4/C composite cathode materials.
Croce et al. [148] report the preparation and electrochemical performance
of kinetically improved Cu-added or Ag-added LiFePO4 composite cathode
materials. The added Cu or Ag metal powders do not affect the structure of
LiFePO4 but clearly improve its kinetics in terms of capacity delivery and
cycling life due to a reduction of the particle size and an increase of the bulk
intra- and inter-particle electronic conductivity of LiFePO4. The obvious
22 Zhicong Shi , Hansan Liu and Jiujun Zhang

capacity improvement of Ag-added LiFePO4 both at medium (C/5) and

particularly at high (1C) rates is maintained for many cycles, demonstrating
the stability of Ag-added LiFePO4.
According to Liu et al. [149], ZrO2 nanolayer coated LiFePO4 particles
have been successfully synthesized by a chemical precipitation method. The
HR-TEM observations reveal that nanolayer structured ZrO2 with a thickness
of 2-3 nm exists on the surface of LiFePO4 particles. The ZrO2 nanolayer
increases the mechanical toughness of the core particles and decreases the
interface charge transfer resistance. It does not affect the crystal structure of
LiFePO4 core but considerably improves the electrochemical properties at high
charge/discharge rate due to the amelioration of the electrochemical dynamics
on the LiFePO4 electrode/electrolyte interface. Furthermore, the ZrO2
nanolayer is favorable to increasing the thermal stability by forming a more
stable solid electrolyte interface layer and covering the over-reactive sites on
the particle surface to avoid probable electrolyte decomposition. In addition,
the ZrO2 surface coating can also provide a protective layer for LiFePO4 core
particles to shield them from direct contact with the acidic electrolyte. ZrO2
nanolayer coated LiFePO4 can deliver the initial discharge capacities of 146
mAh g-1 at C/10 and 97 mAh g-1 at 1C with excellent capacity retention.
In addition, the enhanced electrochemical properties of ZnO-coated
LiFePO4 [150], LiFePO4-Ag composite thin films [151] and polypyrrole-
added LiFePO4 composites [152] are also reported.

Figure 5. The rate capability of LiFePO4-MWCNTs with: (a) 0 wt %, and (b) 5 wt %

MWCNTs at various C rates ranging from C/10 to 3C rate at room temperature.
 LiFePO4 Cathode Materials for Lithium-Ion Batteries 23

4. SUMMARY AND FUTURE PROSPECT

LiFePO4 cathode materials have been reviewed focusing mainly on the
synthesis method and how to improve the electrochemical performance. For
LiFePO4, small particle size and well-shaped crystals are important for
enhancing the electrochemical properties [16]. In particles with a small
diameter, the Li ions may diffuse over shorter distances between the surfaces
and center during Li intercalation and de-intercalation, and the LiFePO4 on the
particle surfaces contributes mostly to the charge/discharge reaction [45]. This
is helpful to enhance the electrochemical properties of LiFePO4/Li batteries
because of an increase in the quantity of LiFePO4 particles that can be used.
Among the various synthesis methods as mentioned above, the hydrothermal
synthesis is a useful method to prepare fine particles, and has some advantages
such as simple synthesis process, and low energy consumption, compared to
high firing temperature and long firing time during solid-state reaction used
conventionally.
Although LiFePO4 possesses high stability, low cost and high
compatibility with environment, it suffers from the limitations of poor
electronic conductivity and slow Li-ion diffusion, and therefore operates
unsatisfactorily at lower temperatures and/or higher current densities. Coating
LiFePO4 active particles with conductive carbon [83], carbon mixing as a
powder initially [136] and in-situ generation by organic compounds during the
preparation [145] is a feasible method to overcome its insulating nature and
make the cell operate at high current densities.
These continuous effects to improve the synthesis method and the
electrochemical performance of LiFePO4 will result in Li-ion batteries with
higher energy density and lower price, and larger scale applications including
low current density applications, such as mobile phones, laptop computers and
digital cameras, and high current density applications, such as electrical
vehicles and hybrid electrical vehicles.

5. ACKNOWLEDGMENTS
The authors acknowledge the financial supports from National Key Basic
Research and Development Program of China (Grant No. 2010CB631001) and
the China Postdoctoral Science Foundation Funded Project (Grant No.
20090451124).
24 Zhicong Shi , Hansan Liu and Jiujun Zhang

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In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 2

INORGANIC CATHODE MATERIALS

FOR LITHIUM ION BATTERIES

Zhicong Shi a, Hansan Liu b and Jiujun Zhang b

a. State Key Laboratory of Fine Chemicals, Dalian University of
Technology P.O. BOX 132, 158-Zhongshan Road,
Dalian, Liaoning, 116012, China
b. Institute for Fuel Cell Innovation, National Research
Council of Canada 4250 Wesbrook Mall,
Vancouver, BC, V6T 1W5, Canada

1. INTRODUCTION
Lithium ion batteries, a class of chemical power sources that use an
electrochemical process of lithium ion intercalation into or de-intercalation
from host materials, are gaining dominance in mobile electronic applications,
and also showing promise for an upcoming new generation of electric vehicle
applications. Currently, the most successful active electrode materials used in
lithium ion batteries are graphite (anode material with a specific capacity of
350 mA h g-1) and LiCoO2 (cathode material with a specific capacity of 135
mA h g-1). Under the driving force of safety issues, a new cathode material,
LiFePO4, has been developed in recent years as the most promising cathode
material for next-generation lithium ion batteries. However, this new material
can deliver a specific capacity of only 150 mA h g-1, which is far less than that
of anode materials (Figure 1) [ 2 ]. The low specific capacity of cathode
32 Zhicong Shi , Hansan Liu and Jiujun Zhang

materials has been identified as the factor preventing lithium ion batteries from
meeting the high capacity and high power demands of automobiles and
electronic devices. Therefore, finding cathode materials with higher specific
capacities has become the key priority in lithium ion battery research and
development (R&D).
In general, a cathode material for lithium ion batteries needs to meet the
following requirements [3]:

(1) The material can react with lithium reversibly and remain a stable
structure during the process of intercalation/de-intercalation. This
requirement is essential for extending the lifetime of lithium ion
batteries.
(2) The reaction free energy of the cathode material with lithium must be
high enough to achieve a battery with high energy density.
(3) The material must have high electronic conductivity and high lithium
ion conductivity to facilitate fast charge transferring and then deliver a
high power density.
(4) The material does not chemically react with the electrolyte during
cycling. This is a basic safety requirement.
(5) The material is low-cost and environmentally friendly.

Figure 1. Voltage versus capacity for cathode and anode materials presently used or
under serious considerations for next generation of rechargeable Li-based batteries.
Note the big difference in capacity between cathode and anode materials, which is the
reason why cathode material is the bottle-neck of capacity density of lithium ion
batteries.[1]
 Inorganic Cathode Materials for Lithium Ion Batteries 33

(A) (B)

Figure 2. (A) Ball-stick structure model of hexagonal layered structure LiMO2 (M =

Mn, Co, or Ni) and (B) unit cell of LiMO2 (M = Mn, Co, or Ni).

Two general classes of cathode material are candidates for lithium ion
batteries: inorganic compounds and organic polymers. The most popular
inorganic cathode materials can be divided into three kinds of inorganic metal
compounds. The first consists of the lithium transition metal oxides with a
layered α-NaFeO2 structure (such as LiCoO2, LiNiO2, and LiMnO2); the
second comprises the lithium transition metal oxides with a spinel structure
(such as LiMn2O4); and the third is the group of lithium transition metal
phosphates (polyanionic compounds) with an olivine structure (such as
LiFePO4 and LiMnPO4) or with a NASICON structure (such as Li3V2(PO4)3).
Three decades ago, Goodenough and his team [4] found that LiCoO2 had a
layered α-NaFeO2 structure and could electrochemically release lithium ions
during a battery reaction, suggesting that this material could be used as a
cathode material for lithium ion batteries. In 1991, SONY successfully
employed this kind of material as the cathode in their first commercialized
lithium ion batteries, and opened a new era of rechargeable batteries [5]. The
layered α-NaFeO2 structure of LiCoO2 has a cubic close-packed (ccp) oxygen
lattice. Complete removal of lithium ions from the interslab can result in a
rearrangement of the oxygen lattice into a hexagonal close-packed (hcp) frame
[ 6 ]. A stable delithiated structure can only be obtained by 50% lithium
removal, which limits the maximum practical specific capacity of LiCoO2 to
135 mA h g-1. Besides this moderate specific capacity, LiCoO2 also has the
disadvantages of being unsafe, toxic, and costly. Although lattice doping and
34 Zhicong Shi , Hansan Liu and Jiujun Zhang

surface coating may improve its lifetime and safety [ 7 ] [ 8 ], LiCoO2 is

considered a less than ideal lithium ion battery cathode material for large-scale
applications such as power sources in hybrid electric vehicles (HEV) and
electric vehicles (EV). An alternative cathode is expected to replace LiCoO2.
In this chapter, we review most of the efforts made to develop new
inorganic cathode materials for a new generation of lithium ion batteries. We
focus primarily on layered LiNiO2 and LiMnO2, spinel LiMn2O4, as well as
olivine LiFePO4, presenting in detail their crystal structures, intercalation
mechanisms, synthesis methods, and performance. Future R&D directions and
potential applications of these cathode materials are also discussed.

2. LAYERED LITHIUM METAL OXIDES

2.1 Introduction

An ideal lithium metal oxide LiMO2 (M = Mn, Co, or Ni) has an α-

NaFeO2 rock-salt structure with a space group of R-3m (No. 166), as shown in
Figure 2. The atomic coordinates are regulated as M at the 3a site (0,0,0), Li at
the 3b site (0,0,0.5), and O at the 6c site (0,0,z) (0,0,-z). The value of z is
around 0.25, with small deviations dependent on the property of the transition
metal M. The oxygen sub-lattice in the rock-salt structure takes an
ABCABCABC... stacking sequence. The cations occupy the octahedral sites
of alternating layers parallel to the crystal plane (111), thus yielding a structure
of AγBaCβAcBαC (Greek letters denote transition metal layers and small
Latin letters denote Li layers) (Figure 2). Therefore, a two-dimensional path
on an a×b panel can facilitate the diffusion of lithium ions during intercalation
or extraction.
Structural changes in the cathode material during battery reactions can
affect battery lifetime. For example, it has been recognized that removal of Li
ions during the charging process may change the phase structure of Li1-xMO2
due to distortion of the ccp oxygen lattice. In particular, layered metal oxides
might be partially changed to an energetically favorable spinel structure when
a composition of Li0.5MO2 is reached. The deterioration of crystal structure
from layered to spinel during electrochemical cycling was previously observed
for both LiCoO2 and LiMnO2, using transmission electron microscopy (TEM)
[ 9 ] [ 10 ], micro-Raman [ 11 ], and neutron diffraction coupled with nuclear
magnetic resonance (NMR) [ 12 ]. This structural transfer could change both
 Inorganic Cathode Materials for Lithium Ion Batteries 35

electrochemical activity and cathode lifetime [13]. Therefore, to achieve deep

removal and re-insertion of lithium ions for higher energy density and longer
battery lifetime, improved structural stabilization of layered LiMO2 is
necessary.

2.2 LiNiO2

2.2.1 Problems with LiNiO2

LiNiO2 has an α-NaFeO2 structure with a space group of R-3m (No. 166),
which is the same as that in LiCoO2 (Figure 2). The theoretical specific
capacity of LiNiO2 is as high as 276 mA h g-1, and the material structure can
remain stable even when the Li is removed at a Li/Ni ratio of 0.65 when the
battery is electrochemically cycling between 2.5 V and 4.1 V. This can result
in LiNiO2 having a practical specific capacity of 180 mA h g-1, which is higher
than LiCoO2 (135 mA h g-1) [14]. However, LiNiO2 has some limitations as a
cathode material in lithium ion batteries, despite nickel being more readily
available than cobalt [3]. Firstly, enough excess nickel exists in the lithium
layer to form a non-stoichiometric [Li+1-zNi2+z]3b[Ni3+1-zNi2+z]3a[O2]6c, which
could block the lithium diffusion route and thus reduce the lithium diffusion
coefficient. The non-stoichiometric [Li+1-zNi2+z]3b[Ni3+1-zNi2+z]3a[O2]6c can also
seriously limit the power capability of the LiNiO2. Unfortunately, it is difficult
to eliminate this undesired excess nickel from the material synthesis process.
Secondly, phase transformation of LiNiO2 during lithium extraction/re-
insertion cycles can cause an irreversible change in crystal structure, leading to
a short cycling lifetime. Finally, the delithiated LixNiO2 has high oxidization
potential for reaction with the organic solvent electrolyte, causing battery
safety issues. These three challenges must be overcome before LiNiO2-based
materials can be used as cathodes in commercial lithium ion batteries.

2.2.2 Synthesis of stoichiometric LiNiO2-based materials

Some general difficulties arise in the synthesis of stoichiometric LiNiO2
using the traditional solid-state method. This is due to: (1) defects on lithium
sites when lithium is evaporated at high temperatures [15]; (2) the large energy
barrier for the oxidation of Ni2+ to Ni3+ [16]; and (3) the decomposition and
phase transformation of LiNiO2 at high temperatures [17]. Nickel on lithium
sites in non-stoichiometric [Li+1-zNi2+z]3b[Ni3+1-zNi2+z]3a[O2]6c can cause a large
capacity loss in the first charge/discharge cycle, followed by poor capacity
upon further cycling [18].
36 Zhicong Shi , Hansan Liu and Jiujun Zhang

Figure 3. Specific discharge capacities during charge-discharge cycling of LiNi1-

-1
yCoyO2 (y＝0, 0.1, 0.2, 0.3, 0.5, 1.0) with a discharge current density of 18mA g
(0.1C) between 3.0V and 4.2V. [Hansan Liu’s unpublished result]

In terms of mitigation, three strategies can improve the synthesis of a

near-stoichiometric LiNiO2- based material: (1) using excess lithium salt in the
reaction precursor to compensate for lithium evaporation at high temperatures;
(2) using a low-temperature method, such as sol-gel or co-precipitation, in
place of the conventional solid-state method; and (3) doping with a second
metal, such as LiNi1-yCoyO2(0 ≤ y ≤ 1) solid solution, to reduce atomic
displacement and then enhance the ordering of the hexagonal layered structure
[19].
In our previous work [26, 27, 37], we studied the synthesis, structures, and
performance of LiNi1-yCoyO2 (y = 0, 0.1, 0.2, 0.3, 0.5, 1.0) as cathode
materials. A sol-gel method using citric acid as a chelating reagent was
developed for preparing the materials at a relative low temperature (725 °C)
and in a short time (24 hrs). All of the above three strategies were adopted in
this synthesis. The crystal structures of the materials were analyzed by the
Rietveld refinement method based on their X-ray diffraction data. The result
indicated that the ordering of the hexagonal layered structure was enhanced by
cobalt content. For pure LiNiO2, 7.3% of the Li 3b sites were occupied by
nickel. The non-stoichiometric number was decreased to 2.4% after 20% of
 Inorganic Cathode Materials for Lithium Ion Batteries 37

the nickel was replaced by cobalt, and almost no nickel could be found on Li
3a sites when the cobalt doping level was increased to 30%. Cobalt doping
also had significant effect on cathode performance. As presented in Figure 3,
pure LiNiO2 showed an initial specific discharge capacity of 143 mA h g-1,
higher than that of LiCoO2 (125 mA h g-1), under a discharge current density
of 18 mA g-1 (0.1 C) between 3.0 V and 4.2 V. Unfortunately, its capacity
retention was far poorer than that of LiCoO2; only 68% of the initial capacity
was retained after 50 cycles. With cobalt doping, the specific capacity of
LiNi0.8Co0.2O2 increased to 185 mA h g-1, and 82% of the initial specific
capacity was retained after 50 cycles. However, when the cobalt doping level
exceeded 20%, the excess doping suppressed removal of lithium from the
layered structure, resulting in a lower reversible capacity. The optimal doping
content was determined to be ~20% cobalt.

2.2.3 Structural stability of delithiated LiNiO2-based materials

Irreversible crystal structure change is the main reason for capacity fading
during charge/discharge cycling of LiNiO2-based materials. An ideal host
material has a stable crystal structure or undergoes reversible structural change
during charge/discharge cycling. It is well known that most oxides are formed
by electrovalent bonding and interaction between ions, and their crystal
structures therefore must change during ion insertion or extraction. Ohzuku et
al. [20] and Delmas et al. [21] carried out in-depth studies of structural changes
in LiNiO2 during the charge/discharge processes. After the removal of lithium
ions, the crystal structure of LixNiO2 was transformed from a rhombohedral
phase (R1, 1.00>x>0.75) to a monoclinic phase (M, 0.75>x>0.45), then a new
rhombohedral phase (R2, 0.45>x>0.25), followed by a third rhombohedral
phase (R3, 0.25>x>0.00), and finally a hexagonal phase (H4, x = 0) (Figure
4a). This successive phase transformation was believed to be due to the Jahn-
Teller effect of the NiO6 octahedron, and the rearrangement of the super
crystal structure formed by lithium/vacancy ordering during lithium ion
removal and hole generation [22].
The transformation of multiple phases of LiNiO2 during lithium
intercalation and extraction can cause serious capacity fading. The partial
irreversible phase transformation and the crystal cell volume change results in
the cracking and break-off of active materials. Moreover, the high oxidation
state of nickel in LixNiO2 can also lead to a reaction with the ethyl carbonate
(EC) in the organic electrolyte when the charging voltage reaches 4.3 V
(Figure 4a), which could result in a large irreversible capacity and cause
serious safety problems [23]. Therefore, enhancing structural stability during
38 Zhicong Shi , Hansan Liu and Jiujun Zhang

cycling is one of the major challenges in the commercialization of LiNiO2-

based cathode materials.

Figure 4. Differential capacity (dQ/dE) against voltage curves derived from the second
charge-discharge cycle (0.2C, 2.7-4.5V) of LiNiO2(a), LiNi0.8Co0.2O2(b) and LiNi0.8-
yTiyCo0.2O2 (y＝0.025(c), 0.050(d), 0.075(e), 0.100(f)). [Hansan Liu’s unpublished
result]

Figure 5. The (003) diffraction peaks of ex-situ XRD patterns for the delithiated
pristine, 5% Ti-doped and 3% TiO2-coated Li1-xNi0.8Co0.2O2 at different lithium content
during charge/discharge process. [37]
 Inorganic Cathode Materials for Lithium Ion Batteries 39

Doping with other metal elements is a demonstrated successful strategy to

improve the structural stability of LiNiO2-based cathode materials. Many
studies have deployed this doping strategy by replacing part of the nickel with
other metal elements such as cobalt, magnesium, aluminum, or titanium [24]
[25] [26] [27]. It is well known that cobalt doping in LiNiO2 can reduce disorder
in the interslab and improve its structure stability. The weaker redox peak at
high voltage in Figure 4b supports this assertion. When LiNiO2 is doped by
redox inactive metal ions, such as the titanium in LiNi0.8-yTiyCo0.2O2, complete
removal of the lithium can be avoided, thereby stabilizing the crystal structure
and suppressing the irreversible phase changes that occur with very low
lithium content (Figure 4c–f). This doping effect can be demonstrated by ex-
situ X-ray diffraction (XRD) of delithiated cathode materials Li1-xNi0.8-
28
yTiyCo0.2O2, as shown in Figure 5 [ ]. A series of enlarged (003) diffraction
peaks, which reflect the interslab distances, are extracted from the ex-situ
XRD patterns of the delithiated cathode materials, including Li1-xNi0.8-
yTiyCo0.2O2. For a delithiated pristine material, the (003) peak shifts slightly
toward the lower diffraction angles when the lithium content x increases to 0.5
(Figure 5, left pattern). Further lithium extraction can make the (003) peak
shift slightly back to higher diffraction angles. The (003) peak shift
corresponds to the reciprocating changes in interslab distance, i.e., structural
instability during the delithiation process. Compared to pristine materials, the
materials doped with 5% Ti show better structure stability during the
delithiation process. As shown in the central pattern of Figure 5, before x =
0.5, there is no significant shift for the (003) peak. Even when x > 0.5, only a
slight shift to higher angles is observed.
Coating is another strategy for improving structural stability. Figure 5 can
be used to compare the doping effect and the coating effect. Figure 5 (right
pattern) shows the structural change of a 3% TiO2-coated Li1-xNi0.8Co0.2O2
material after delithiation. It can be seen that a similar change in the (003)
peak as that of pristine material occurred in the coated materials, indicating
that there still were obvious structural changes during cycling for the coated
material. Therefore, the doping strategy is better than the coating strategy in
terms of improving structural stability.
The effect of doping on structural stability can also lead to better capacity
retention and longer cycling lifetime for LiNi0.8-yTiyCo0.2O2 cathode materials.
For example, LiNi0.7Ti0.1Co0.2O2 can give an initial specific discharge capacity
of 188 mA h g-1 in the range of 2.7–4.5 V and fade from 188 to 148 mA h g-1
after 100 cycles with a high capacity retention of 80%, which is much better
than the 58% retention for LiNi0.8Co0.2O2 cathode material (Figure 6) [27]. If
40 Zhicong Shi , Hansan Liu and Jiujun Zhang

another metal element was doped to form a quaternary lithium metal oxide, the
cyclicability of the lithium ion battery could be further improved. For
example, additional Mg-doping, yielding LiNi0.7Co0.2Ti0.05Mg0.05O2, could
result in an improved capacity retention of up to 91% after 100 cycles [29].

2.2.4 Thermal stability of delithiated LiNiO2-based materials

Poor thermal stability of LixNiO2 materials in a charged state, caused by
self-decomposition of nickel oxide and the high oxidization ability of Ni4+
with an organic solvent electrolyte, is another major factor that degrades
capacity during charge/discharge cycling. This poor thermal stability also
makes LiNiO2-based batteries unsafe. Generally speaking, cathode materials
show good thermal stability at full lithiation, but would decompose at low
temperature and low lithium content state. Differential scanning calorimetry
(DSC) showed the thermal stability order of three oxide cathodes when
charged to 4.2 V in the same electrolyte (PC/EC/DMC(1/1/3)+LiPF6(1M)) to
be as follows: LiMn2O4 > LiCoO2 > LiNiO2 [30]. LiNiO2 could decompose to
NiO at 850 °C [31], while Li0.3NiO2 could decompose at 200 °C with a specific
thermal capacity of 1600 J g-1 [32] [33]. Cathode decomposition releases large
quantities of heat and gas, causing a fatal blast during the lithium ion battery
operation.

Figure 6. Plots of discharge-specific capacity vs. cycle number for LiNi0.8-yTiyCo0.2O2

(y = 0, 0.025, 0.050, 0.075, 0.100) cathode materials. Cycling was carried out with a
current rate of 0. 2C for 1-5 cycles, 0.5C for 6–10 cycles and 1C for 11-100 cycles.
[26]
 Inorganic Cathode Materials for Lithium Ion Batteries 41

Figure 7. DSC scans of the bare and AlPO4-coated cathodes at 4.2 and 4.6 V vs.
carbon (~4.3 and ~4.7 V vs. lithium, respectively). The cathodes were extracted from
the Li-ion cells, and the scan rate was 3 °C min-1. [36]

Figure 8. Cycling stability curves of (a) pristine, (b) 5% Ti-doped and (c) 3% TiO2-
coated LiNi0.8Co0.2O2 at 0.2C current density between 2.7V and 4.5V. [37]
42 Zhicong Shi , Hansan Liu and Jiujun Zhang

Figure 9. Crystal structures of a) R-3m layered LiMO2, b) Pmnm o- LiMnO2, c) Fd3m

spinel LiMn2O4. Small white spheres: Li. Small black spheres: Transition metal. Large
gray spheres: Oxygen. Note the similar oxygen sublattices in all the structure. Layered
LiMO2 has alternating layers of Li and M. o- LiMO2 shows zig-zag layering. Spinel
has alternating layers filled 3/4 and 1/4 by Mn, resulting in three-dimensional channels
with Li in tetrahedral sites. [38]

Two strategies exist to mitigate the effect of thermal instability: (1) doping
with other metal elements, and (2) coating with thermally stable oxides or
phosphates. As shown in section 2.2.3, doping with cobalt and titanium can
improve the thermal stability of LiNiO2 cathode materials, as demonstrated by
the shift in the electrolyte’s anodic peak from 4.35 V in pure LiNiO2 to a
higher voltage in the doped samples (Figure 4). On the other hand, surface
coating using chemically stable metal oxides or metal phosphates has been
demonstrated to be effective in preventing a direct reaction between the
oxidative component and the organic electrolyte, and then in reducing the
thermal effect on lithium ion batteries during cycling [34] [35] [36] [37]. For
example, coating AlPO4 on LixNi0.8Co0.1Mn0.1O2 could lead to a significantly
reduced exothermic heat, just one-quarter of the heat released by bare LiNiO2
at charged states (Figure 7) [37]. It has been found that if LiNi0.8Co0.2O2 was
coated with a 15-nm layer of TiO2, the anodic peak of electrolyte oxidation on
the cyclic voltammetry (CV) curves was also suppressed [38]. As shown in
Figure 5, the ex-situ XRD pattern shows no difference in crystal structure
evolution between pristine and TiO2-coated LiNi0.8Co0.2O2 during the
charge/discharge process. This means that surface coating has no effect on the
structural stability of the cathode material during cycling. However, the
discharge capacity retention can be improved, as shown in Figure 8, resulting
in extended lithium ion battery lifetime. This positive effect should be
 Inorganic Cathode Materials for Lithium Ion Batteries 43

attributed to the enhanced thermal stability of LiNi0.8Co0.2O2 in the delithiated

state.

Figure 10. Discharge voltage profiles for (a) o-LiMnO2 (b) 5% Al-doped m-LiMnO2,
and (c) 3% Cr-doped m-LiMnO2 during extended cycling of Li cells at 55 °C. Current
rate is 30 mA g-1. [46]

Figure 11. Discharge voltage profiles for orthorhombic LiMnO2 prepared at high
temperature in a Li cell discharged at C/5, C/2,C, and 2C rates, ambient temperature. It
shows the typical discharge behavior of spinel phase with 4V and 2.8V plateaus. [38]
44 Zhicong Shi , Hansan Liu and Jiujun Zhang

2.3 LiMnO2

2.3.1 Challenges of LiMnO2

Mn-based cathodes, primarily layered LiMnO2 and spinel LiMn2O4, are
very interesting in their application to large batteries, because they are superior
to lithium cobalt or nickel oxides in terms of safety, cost, and toxicity. LiMnO2
has a high theoretical discharge capacity of 285 mA h g-1, about twice that of
LiMn2O4. In comparison with both hexagonal LiCoO2 and LiNiO2, LiMnO2
does not have a perfect α-NaFeO2 structure (Figure 9a) [39]. The trivalent Mn
ions can cause a cooperative distortion of the MnO6 octahedra due to Jahn-
Teller stabilization, leading to a metastable monoclinic unit cell (space group
C2/m), denoted as m-LiMnO2. This new structure shows a lower symmetry
with different angles and lattice constants, compared to higher rhombohedral
symmetry. The thermodynamically stable LiMnO2 has an orthorhombic
symmetry, denoted as o-LiMnO2 (Figure 9b). However, both m-LiMnO2 and
o-LiMnO2 have the cation ordering of a layered α-NaFeO2 structure, which
tends to gradually transform into a spinel structure (Figure 9c) during lithium
intercalation/de-intercalation. Phase transformation often happens among the
orthorhombic, the layered O3, and the spinel structures due to the same close-
packed oxygen sub-lattice and only minor differences in cation occupation
(Figure 9). Energetically, the spinel structure is preferable over the layered O3
or orthorhombic structure for most Li0.5MO2 [ 40 ]. A recent study using ab
initio calculations showed that the delithiated LixMnO2 layered materials could
transform to a spinel structure in a two-stage process [41] [42]. In the first stage,
part of the Mn and Li ions rapidly migrated into tetrahedral sites surrounded
by Li vacancies. The activation barrier to the migration of Mn into a
tetrahedral site was low, partly because of the charge disproportionation of
Mn3+ into Mn2+ (tetrahedral) and Mn4+ (octahedral). In the second stage, the
structural transformation involved a more difficult coordinated rearrangement
of Mn and Li ions to form spinels, which took place more slowly due to its
complexity and higher activation barriers. This phase transformation could
cause fast capacity fading and reduce the lifetime of layered LiMnO2 cathodes.
Therefore, the challenge for practical application of LiMnO2 cathodes is how
to prepare and stabilize the structure of LiMnO2 during cycling.

2.3.2 Development of monoclinic LiMnO2 cathode materials

Much effort has been put into developing the commercial and scientific
potential of layered LiMnO2. Layered LiMnO2 materials do not crystallize in
 Inorganic Cathode Materials for Lithium Ion Batteries 45

the R-3m space group, but show a monoclinic distortion of the lattice (space
group C2/m) due to the cooperative ordering of Jahn-Teller distorted [Mn3+O6]
octahedra. Although m-LiMnO2 is thermodynamically metastable when
compared to both orthorhombic and spinel phases, it has been successfully
synthesized by soft chemical methods such as ion exchange and hydrothermal
synthesis.
The exchange of Na+ ions in layered NaMnO2 with Li+ ions was carried
out to form m-LiMnO2 [42-44]. An earlier attempt at Li-Na exchange in
molten salts failed when the layered structure collapsed [43]. Using a modified
ion exchange strategy, a m-LiMnO2 material was successfully prepared [44]
[45]. m-LiMnO2 was first achieved by ion exchange of layered NaMnO2 in
methanol with LiCl at 90 °C. However, the ion-exchange kinetics was so poor
that the process took approximately a month [44]. The ion exchange process
was then accelerated by refluxing layered NaMnO2 in n-hexanol with LiBr at
150 °C [45]. Unfortunately, the m-LiMnO2 material did not exhibit good
electrochemical performance. A large amount of lithium could be extracted on
the first charge, but the ions could not be totally re-intercalated into the host on
subsequent discharge, and showed poor capacity retention as well. To gain a
fundamental understanding for further improvement, neutron diffraction and
electron microscopy were applied to investigate the causes of this phenomenon
[46]. It was found that the layered structure had been transformed to a highly
disordered spinel after just a few cycles. In the first charge process, Li ions
were initially removed by a two-phase mechanism involving the original
monoclinic layered phase and a hexagonal phase. Then a single hexagonal
phase was observed between 30% and 100% of the Li ions in the original
materials being removed. Finally, a dramatic collapse of the interlayer spacing
was observed at the very end of the first charge process. Subsequent cycling
raised the amount of spinel phase in the material, indicated by an increased
capacity at the potential region of 4 V (Figure 10b) [47]. However, the rate of
this transformation could be significantly decreased if a non-stoichiometric
layered LixMnyO2 was used. After 100 cycles, both neutron diffraction and
NMR analysis indicated that only 25% of the spinel structure was formed [48]
[49]. Additional Co or Ni doping in the NaMnO2 precursor could also slow the
transformation from layered structure to spinel structure. The doped LiMyMn1-
yO2 (M = Co or Ni) materials showed improved capacity, rate capability, and
cycling stability when compared with non-substituted LiMnO2 [ 50 ] [ 51 ].
Although these results look promising, the preparation process presents
problems for large-scale manufacturing.
46 Zhicong Shi , Hansan Liu and Jiujun Zhang

An alternative approach to synthesizing layered m-LiMnO2 at low

temperatures is the hydrothermal method using permanganates and a lithium
source as precursors [52]. The resulting LixMnO2•nH2O is dehydrated under
mild conditions to give the desired layered LixMnO2. The analogs doped by
cobalt, iron, or nickel, LixMn1-y(Co, Fe, or Ni)yO2, could also be synthesized
by this method to obtain the same layered structure [53]. LixMn0.99Co0.01O2 has
shown a capacity between 0.7 and 0.8 Li/Mn, with good reversibility at a rate
of 0.1 mA cm-2 for charging/discharging. However, cycling at high current
densities, such as 1 mA cm-2, could initiate a conversion from the layered
phase to the spinel-like phase. Layered LiMnO2 materials prepared at low
temperatures often show much better capacities and rate capabilities when
compared to those prepared at high temperatures. This is due to the shorter
solid diffusion lengths for Li ions within these materials, which have lower
crystallinity, smaller particle sizes, and higher surface areas. However, these
materials often have low volumetric densities and therefore low energy
densities. Furthermore, large surface areas have the potential to accelerate side
reactions in the cathode/electrolyte interface, thereby lowering both safety and
cycling stability.
Layered m-LiMnO2 can also be prepared at high temperatures with an
appropriate doping process. This kind of approach was first reported in 1995
by Davidson et al. [54]. Doped with trivalent metal ions, such as Al3+, Ga3+,
and Cr3+, LiMnO2 could crystallize as a layered monoclinic phase (space
group C2/m) by a simple solid-state reaction at 900-1000 °C under inert gas
[47] [55] [56] [57] [58]. Although doping with Al or Ga improved the capacity
retention of m-LiMnO2, mainly through slowing the rate of crystal
transformation from a layered to a spinel structure, complete prevention of this
crystal transformation was not observed (Figure 10b). However, if the material
was doped with 3% Cr, a large improvement in capacity retention was
observed, as shown in Figure 10c [47]. A slight additional capacity can be
achieved at 4 V even after 200 cycles, indicating almost no formation of
spinel-type intercalation sites for Li ions. X-ray diffraction spectra taken from
cycled Cr-substituted materials showed peaks for the hexagonal phase, with an
unknown structure confirming the absence of the spinel phase. This might be
interpreted as indicating that Cr3+, with a strong stabilization energy for
octahedral sites, could hinder the second stage of transformation from layer to
spinel structures, as predicted by Ceder at el. [42].
In summary, layered m-LiMnO2 materials with or without doping of other
metal elements can be prepared at high temperatures using a solid-state
reaction, or at low temperatures using an ion exchange or hydrothermal route.
 Inorganic Cathode Materials for Lithium Ion Batteries 47

However, most of the materials undergo structural transformation during

battery cycling, forming defective spinel-type structures. Only Cr3+-doping
effectively inhibits the full transformation of the layered structure to the spinel
structure, by hindering the second transformation stage.

Figure 12. Charge (closed circles) and discharge (open circles) capacity fading upon
cycling of Li/LiNi0.5Mn0.5O2 cell operated between 2.5-4.5 V at a rate of 0.17 mA cm-2.
[73]

2.3.3 Development of orthorhombic LiMnO2 cathode materials

In the structure of thermodynamically stable o-LiMnO2 (space group
Pmmn), illustrated in Figure 8b, Li and Mn ions are located in the octahedral
sites in an alternating zig-zag configuration, with edge-sharing between [LiO6]
and [MnO6] octahedra. o-LiMnO2 materials with special electrochemical
properties have been intensively investigated over the last decade. They can be
prepared by several synthesis methods, using either low-temperature or high-
temperature routes.
Low-temperature o-LiMnO2 materials have been prepared by several
synthesis methods. o-LiMnO2 was first reported by Ohzuku et al. [59] with a
relatively high capacity of 190 mA h g-1 over a voltage range of 2.0–4.25 V.
This material was synthesized by heating mixed stoichiometric γ-MnOOH and
LiOH at 300–450 °C under dry nitrogen. Reimers et al. [60] also reported a
48 Zhicong Shi , Hansan Liu and Jiujun Zhang

high-capacity o-LiMnO2 synthesized by ion-exchanging of γ-MnOOH in

boiling LiOH solution, with subsequent drying at 105 °C in air or heating at
200 °C under argon. However, the orthorhombic structure of the materials was
found to gradually transform into a spinel structure. As a result, low-
temperature o-LiMnO2 materials showed poor capacity retention with
extended cycling.

Figure 13. The voltage profiles upon capacity during the first charge/discharge process
of the (a) pristine, and (b) AlF3-coated Li(Li0.2Mn0.54Ni0.13Co0.13)O2 at different current
density, 1C = 180 mA g-1. Capacity fades fast with current density, which indicates the
poor kinetic of Li(Li0.2Mn0.54Ni0.13Co0.13)O2 without or with AlF3 coating. The ICL is
successfully reduced from 75 to 47 mA h g-1 at 0.1C rate, and from 88 to 68 mA h g-1 at
2C rate. [91]

High-temperature o-LiMnO2 materials can be synthesized by solid-state

reaction of manganese oxide with lithium salt under an inert atmosphere. The
high-temperature o-LiMnO2 cathodes do have the problem of structural
 Inorganic Cathode Materials for Lithium Ion Batteries 49

transformation during cycling [47], but generally give better capacity retention
than low-temperature o-LiMnO2. High-temperature o-LiMnO2 showed an
improved discharge capacity, from 160 to 200 mA h g-1, when Mn2O3 instead
of MnO2 was used as the precursor [ 61 ] [ 62 ]. The crystallite size of the
electrode materials also played an important role in cell performance. Detailed
investigation into the effect of crystallinity on electrochemical performance
confirmed that crystallite size was the critical parameter in determining the
electrochemical performance of high-temperature o-LiMnO2 phases [63] [64]
[ 65 ]. Despite having good capacity retention, o-LiMnO2 prepared at high
temperatures also shows poor rate capability, as shown in Figure 11.
Meanwhile, the sharp drop in discharge voltage, resulting from the
thermodynamically stable spinel phase, is a problem in practical applications
[39].
As described above, doping and coating of LiMnO2-based cathode
materials with orthorhombic or layered O3 structures still does not prevent
transformation into the spinel structure after extended cycling. This is partially
due to the existence of the same ccp oxygen sub-lattice in all structures. If
LiMnO2-based cathode materials could be synthesized to yield a different
oxygen sub-lattice, the transformation would require a coordinated lattice
rearrangement. However, this rearrangement still could not be achieved at
ambient temperature.

2.4 Mixed Transition Metal Dioxides

Another way to increase the doping level is to form mixed transition metal
dioxides. These are another kind of cathode material with a layered structure.
Ni and/or Co are used as substitutes for Mn to stabilize the structure, and
simultaneously to increase the electronic conductivity of layered LiMnO2 [66].
It has been found that the mixed transition metal dioxides tended to form
LiCoO2 (R-3m) analog with a layered structure, but not in solid solutions of
LiCoO2, LiNiO2, and LiMnO2. The valence states of the ions were Ni2+, Co3+,
and Mn4+. During charge-discharge cycling, the valence state of Mn4+
remained unchanged [67] [68].
Several representative mixed layered compounds will now be discussed:

(1) LiNi0.5Mn0.5O2. Denoted as 550 material (0.5 Ni, 0.5 Mn, 0.0 Co),
LiNi0.5Mn0.5O2 was first reported by Rossen et al. [69] in 1992. Later,
Spahr et al. [ 70 ] used X-ray photoelectron spectroscopy (XPS) and
50 Zhicong Shi , Hansan Liu and Jiujun Zhang

magnetic data to determine that the nickel and manganese in the 550
material were in the forms of Ni2+ and Mn4+ ions rather than Ni3+ and
Mn3+. During electrochemical cycling, nickel was found to be the
only active redox species cycling between the +2 and +4 valence
states, while manganese remained in the +4 valence state, independent
of lithium content. The stable Mn4+ could successfully prevent the
Jahn-Teller effect coming from Mn3+ [71]. This was further confirmed
by the charge-discharge curves, which showed a single-phase reaction
similar to that of LiNiO2 [72]. Layered LiNi0.5Mn0.5O2 with optimum
electrochemical performance was also synthesized by sintering nickel
manganese double hydroxide precursors with lithium hydroxide at
1000 °C [73]. This yielded an initial discharge capacity of ca. 190 mA
h g-1 between 2.5 V and 4.5 V at 0.17 mA cm-2, and almost no
deterioration in capacity was detected in the first 30 cycles (Figure 12)
[74]. The rate capacity approached 190 mA h g-1 at 0.17 mA cm-2, and
-1
declined to 135 mA h g at 6 mA cm-2. It is believed that pulse
discharge rates over 10 mA cm-2 should be achievable according to
the declining tendency indicated by the measurements [3]. Aluminum
was also used as a doping metal [74]. Al doping on the Ni and Mn
sites of the 550 materials reduced cation mixing and initial
irreversibility, thus improving structural stability and capacity
retention [75]. Moreover, Wang et al. [76] and Zhou et al. [77] proved
that 10% Al-doped 550 materials had a better thermal stability than
LiCoO2, LiMn2O4, and LiNi1/3Mn1/3Co1/3O2, and a higher
volumetric energy density than both LiMn2O4 and LiFePO4 materials.
Therefore, Al-doped LiNi0.5−zMn0.5−zAl2zO2 may be candidates for
cathode materials in large-size lithium ion cells for EV/HEV, where
low cost, excellent safety, and high energy density are required.
(2) LiNi1/3Mn1/3Co1/3O2. Denoted as 333 material (0.33 Ni, 0.33 Mn,
0.33 Co), LiNi1/3Mn1/3Co1/3O2 was first reported by Liu et al. [78] in
1999. As discussed in section 2.2.3, the addition of cobalt to LiMn1-
yNiyO2 can stabilize the layered structure. It was observed that using
this cobalt-doped material, the volume change was less than 2% as the
lithium ions were removed [ 79 ]. Many synthesis methods for 333
materials have been developed over a wide range of temperatures.
Most of these materials showed similar electrochemical behavior; that
is, the capacity could be increased by increasing the charge cut-off
potential [80] [81]. Ohzuku et al. [82] [83] synthesized 333 material from
 Inorganic Cathode Materials for Lithium Ion Batteries 51

LiOH · H2O and triple hydroxide precursors of cobalt, nickel, and

manganese at 1000 °C, generating a material which could deliver a
capacity of around 150 mA h g-1 when cycling between 2.5 and 4.2 V
with a rate of 0.17 mA cm-2 at 30 °C. Increasing the charge cut-off
potential to 4.6 V yielded a capacity in excessive of 200 mA h g-1. 333
material prepared by the hydrothermal method showed a low capacity.
However, after the material was sintered at 800 °C, enhanced
capacities of 182 mA h g-1 at 0.2 C (30 mA/g), and 124 mA h g-1 at 5
C (750 mA/g) within the potential window of 2.8–4.6 V were
achieved [84]. An increase in synthesis temperature from 800 to 900
°C also resulted in an improved initial capacity, from 173 to 190 mA
h g-1 [ 85 ]. However, the 333 materials showed a large initial
irreversible capacity (up to 20%) and then a marked capacity fading
upon cycling. In addition, the rate capacities of these materials need to
be improved before they will be viable for commercialization [79]
[85].
(3) LiM1-y(Li1/3Mn2/3)yO2. LiM1-y(Li1/3Mn2/3)yO2 represents Li-rich
layered compounds, where M can be Cr, Mn, Fe, Co, Ni, or mixtures
thereof. These materials are solid solutions of layered LiMO2 and
Li(Li1/3Mn2/3)O2. The latter compound can also be treated as
Li2MnO3, where Mn is Mn4+ rather than Mn3; thus, any impact of the
Jahn-Teller effect coming from Mn3+ would be minimized. This is
why the stability of Li-rich 550 material, Li1+x(Ni0.5Mn0.5)1-xO2, can be
increased by the addition of excess lithium [86].
(4) yLiNiO2 ·(1-y)Li[Li1/3Mn2/3]O2. This material can be treated as a
solid solution of LiNiO2-Li2MnO3. The structure and electrochemical
performance of this material were systematically studied by Lu et al.
[87]. The layered degree of this solid solution can be decreased by
increasing the nickel content; the capacity decreases accordingly with
decreasing y value (y = 1/3, 5/12, and 1/2) [87]. The capacity of the y
= 1/3 material can be increased up to 200 mA h g-1 at 30 °C between
2.0 and 4.6 V. Li(Li0.2Ni0.2Mn0.6)O2, described as [LiNi0.5Mn0.5]0.4·
[Li(Li1/3Mn2/3) O2]0.6, has also shown a steady-state capacity of
around 200 mA h g-1 between 2.0 and 4.6 V at 0.1 mA cm-2 after the
first 10 cycles [88]. This anomalously high capacity, far in excess of
the theoretical value, can be obtained in LiNi1/3Co1/3Mn1/3O2 and
Li2MnO3 solid solution [88]. Li(Li0.2Mn0.54Ni0.13Co0.13)O2, described as
[LiNi1/3Co1/3Mn1/3O2]0.4·[Li(Li1/3Mn2/3) O2]0.6, can deliver an initial
52 Zhicong Shi , Hansan Liu and Jiujun Zhang

discharge capacity of 286 mA h g-1 between 4.8 V and 2.0 V at 0.05

mA cm-2 and 50 °C [89] [90]. Moreover, the addition of cobalt to the
solid solution has been found to be helpful in retaining the rate
capacity [91]. However, due to the oxidation of electrolytes at high
potentials and attacks on the electrode/electrolyte interface from trace
acidic species (HF) in the electrolyte, the pristine
Li(Li0.2Mn0.54Ni0.13Co0.13)O2 cathode could suffer from a serious
irreversible capacity loss (ICL) of 75 mA h g-1 at the 0.1 C rate
(Figure 13), a poor rate capacity of 178 mA h g-1 at 2C (Figure 13),
and a low capacity retention of 67.8% at the 0.5 C rate after 80 cycles
(Figure 14) [92] [93]. Therefore, for commercialization of this material,
the large ICL must be reduced and the low conductivity improved.
Zheng et al. [91] [92] reported that AlF3 or TiO2 coating on the
surface of lithium-rich compounds could suppress the side reaction
between the electrolyte and the oxidative cathodes, and thus improve
the electrochemical performance. After AlF3 coating, the ICL was
reduced to 47 mA h g-1 at the 0.1 C rate, and to 68 mA h g-1 from 88
mA h g-1 at the 2 C rate. Moreover, 87.9% of the initial specific
discharge capacity was retained after 80 cycles at the 0.5 C rate at
room temperature, 20.1% higher than that of pristine
Li(Li0.2Mn0.54Ni0.13Co0.13)O2. Results obtained using in-situ
differential electrochemical mass spectrometry revealed that the
activity of oxygen species extracted from the
Li(Li0.2Mn0.54Ni0.13Co0.13)O2 cathode was greatly reduced and the
decomposition of the electrolyte was appreciably suppressed after
AlF3 coating, which could significantly improve the safety of Li cells
when using this kind of cathode. For yLiNiO2·(1-y)Li[Li1/3Mn2/3]O2
to be a viable cathode material for batteries, its rate capability needs
further improvement and its lifetime should be evaluated.

3 SPINEL LITHIUM MANGANESE OXIDES

3.1 Introduction

The A[B2]O4 spinel structure (Figure 15) has a ccp oxygen lattice closely
related to the α-NaFeO2 layer structure, differing only in the distribution of the
cations among the available octahedral and tetrahedral sites [94]. The A cations
 Inorganic Cathode Materials for Lithium Ion Batteries 53

occupy the 8a tetrahedral sites, and the B cations occupy the 16d octahedral
sites. The [B2]O4 array forms a strongly bonded 3D framework in which the 8a
tetrahedral sites and 16c octahedral sites create a 3D interconnected interstitial
space for lithium transportation [95].
Two promising spinel compounds, LiMn2O4 and Li4Ti5O12, have been
developed as electrode materials for lithium ion batteries. LiMn2O4 shows a 4
V plateau during lithium intercalation/de-intercalation, making it a feasible
cathode material. Li4Ti5O12, due to its low lithium intercalation/de-
intercalation voltage (1.5 V), may be more suitable as an anode material.

Figure 14. The specific discharge capacity upon cycling of the pristine (squares), and
AlF3-coated (circles) Li(Li0.2Mn0.54Ni0.13Co0.13)O2 at room temperature over the voltage
range of 2.0-4.8V at room temperature and 0.5C rates, 1C = 180 mA g-1. 67.8% of
initial specific discharge capacity was retained upon 80 cycles at 0.5C rate for the
pristine sample, and increased to 87.9% for AlF3 coated sample. [92]

3.2 LiMn2O4

3.2.1 Problems with LiMn2O4

LiMn2O4 has a spinel structure with cubic symmetry and a space group of
Fd-3m (No. 227), locating Li at the 8a tetrahedral sites and Mn at the 16d
octahedral sites. The 16c octahedral sites are open and face-shared with 8a
tetrahedral sites, affording fast lithium transportation along the 8a-16c-8a path.
The cubic symmetric [Mn2]O4 framework can undergo isotropic expansion
and shrinkage upon lithium intercalation/de-intercalation, resulting in a high
54 Zhicong Shi , Hansan Liu and Jiujun Zhang

intercalating/de-intercalating reversibility [95] [ 96 ]. The theoretical specific

capacity of LiMn2O4 is 148 mA h g-1. However, in practice, only 0.85 Li/Mn
can be removed electrochemically between 3.5 V and 4.3 V, delivering a
specific capacity of 130 mA h g-1 at 4.0 and 4.15 V (Figure 16) [97]. A second
lithium intercalation/de-intercalation in the 16a sites of LiMn2O4 will produce
a 3 V plateau similar to that of layered LiMnO2 after a long cycling, as
discussed in section 2.3.1. However, a second lithium intercalation could cause
severe Jahn-Teller distortion and transformation to a tetragonal phase. Usually
only the 4 V plateau of LiMn2O4 is used in lithium ion batteries.

Figure 15. Two quadrants of the A[B2]O4 spinel structure, with A (Striate balls) at 8a
sites, B (Black alls) at 16d sites, and O (White balls) at 32e sites. For LiMn2O4, Li will
occupy 8a sites and Mn at 16d sites. [93]

First reported by Thackeray et al. [ 98 ], LiMn2O4 is cost-effective,

environmentally friendly, and thermally stable, features which make it a
promising cathode material for high-power lithium ion batteries in HEV/EV
applications. Unfortunately, the rate capacity and capacity retention,
particularly at elevated temperatures, are insufficient and need to be enhanced
prior to commercial use. It has been found that the capacity fading is mainly
caused by (1) dissolution of Mn3+ by disproportional reaction with Mn4+ and
electrolyte-soluble Mn2+, (2) phase transformation from cubic to tetragonal
 Inorganic Cathode Materials for Lithium Ion Batteries 55

symmetry by Jahn-Teller distortion of [MnO6], and (3) the high oxidation

ability of Mn4+ on organic electrolyte [95] [99]. Furthermore, in comparison
with the rate capability of LiCoO2, that of LiMn2O4 is inferior due to its low
electric conductivity (10−6 S/cm).

Figure 16. Charge and discharge voltage profiles for nano-LiMn2O4 at 0.5C rate
between 3.5-4.3 V for the first and second cycles at 30 °C. [96]

Figure 17. Rate performance of nano-LiMn2O4 compared with sol-gel LiMn2O4. The
rate capability is expressed as the percentage of the capacity obtained at a specific
discharge rate compared to that obtained at 0.2C rate (30 mA g-1; around 0.15 mA cm-
2
). (b) The discharge voltage profile for nano-LiMn2O4 at different C-rates. [96]
56 Zhicong Shi , Hansan Liu and Jiujun Zhang

3.2.2 Modification of LiMn2O4

The insufficient cycle life of LiMn2O4-based cathodes is believed to be
caused by the dissolution of divalent manganese ions formed by the
disproportional reaction of trivalent manganese. Therefore, it is very important
to minimize the amount of trivalent manganese formed during cycling.
Tarascon et al. [100] found that the value of the cubic lattice parameter (a0) in
LiMn2O4 was directly related to the average valence state of the manganese,
which was critical for obtaining high performance. When the oxidation state of
the manganese was 3.58 or higher, such as in lithium-rich Li1+xMn2-xO4 with a0
= 8.23 Å or less, the dissolution of manganese could be minimized and the
effect of the Jahn-Teller distortion associated with the Mn3+ ion was reduced
as well [101] [102]. On the other hand, storage performance also needs to be
seriously considered for lithium batteries using spinel LiMn2O4 as the cathode
material. In addition, LiMn2O4 also suffers from severe self-discharge in its
fully charged state, particularly at elevated temperatures, due to the redox
reaction between tetravalent manganese and organic electrolyte solvent [103]
[ 104 ]. It has also been determined that the presence of trace moisture in
fluoride-containing electrolyte can generate HF, which then dissolves the
spinel oxides. This problem can be solved using electrolyte containing a non-
fluoride lithium salt, such as LiBOB, rather than LiPF6 [105].

Figure 18. Crystal structure of olivine LiMPO4,where M is either Mn, Fe, Co, or Ni,
constructed by [MO6] (octahedra), [PO4] (tetrahedral), and the Li atoms (ball). [116]
 Inorganic Cathode Materials for Lithium Ion Batteries 57

Figure 19. SEM images of (A) an Fe(II) phosphate and lithium phosphate, co-
precipitated from aqueous solutions, and of (B) lithium iron phosphate, synthesized
thereof by heat treatment in nitrogen. [127]

Co-doping is an effective way to improve the performance of LiMn2O4-

based cathode materials. For example, co-doping with aluminum and fluoride
in lithium-rich Li1+xMn1-x-yAlyO4-zFz can enhance the capacity retention at
elevated temperatures [ 106 ]. Hundreds of studies have been published on
LiMn2O4 treated with various kinds of dopants to stabilize its structure, order
its cation distribution, reduce the proportion of trivalent manganese, and
increase its conductivity [3].
Another solution is to coat the LiMn2O4 particle surface with a conductive
or protective material such as Ag [107], MgO [108], Al2O3 [109], ZnO [110], ZrO2
[111], or Li1−xCoO2 (x≥0) [112] [113] [114]. LixCoO2 (0 < x≤1) coating can be
applied to the surface of LiMn2O4 by sol-gel methods [112] or a micro-
emulsion method [113]. Further heat treatment at 800 °C can lead to the
formation of a core-shell structure with a new spinel phase, Li1+xMn2−xCoxO4,
on the surface [112]. In this Li1+xMn2−xCoxO4 coating, cobalt tends to be
divalent, which can reduce the amount of trivalent manganese and therefore
58 Zhicong Shi , Hansan Liu and Jiujun Zhang

prevent manganese from dissolving into the electrolyte solution. In addition,

the Li1+xMn2−xCoxO4 coating layer also exhibited a lower resistance than the
Co-doped spinel material, which was confirmed by electrochemical impedance
spectroscopy (EIS). As a result, the cycling capacity and rate capacity of
coated LiMn2O4 were greatly improved at both room and elevated
temperatures. The capacity retention at a 20 C rate could be increased from
50% to 80% at the maximum capacity.

Figure 20. Doped olivines of stoichiometry Li1-xMxFePO4 show electrical conductivity

at room temperature that is a factor of ca. 108 greater than in undoped LiFePO4, and
absolute values > 10-3 S cm-1 over the temperature range -20 °C to +150 °C of interest
for battery applications. Results are for polycrystals fired at 700-850 °C and measured
by two-point d.c. and four-point van der Pauw methods. Inset shows expanded plot for
series of dense, single-phase samples fired at 800 °C, showing lower activation energy
of the doped compositions. [122]
 Inorganic Cathode Materials for Lithium Ion Batteries 59

Figure 21. Cycling performance of the Li/C-LixMnPO4 cell at 0.28 mA cm-2 at room
temperature. [144]

Recently, Shaju et al. [97] reported a stoichiometric nano-LiMn2O4

prepared by the sol-gel method using RF resin, followed by calcination at 750
°C for 15 h. As shown in Figure 17, the material exhibits a high initial capacity
(131 mA h g-1) and retains 118 mA h g-1 after 200 cycles at a 0.5 C rate. It also
exhibits an excellent rate capability (retaining 90% of its capacity at 40 C and
85% at 60 C), a nearly 100% power retention rate (5840 W kg-1 dropping to
5828 W kg-1 at 10 C after 1000 cycles), and a high volumetric energy density
(around 750 Wh L-1 at 10 C). The excellent performance of nano-LiMn2O4
may be due to its stable carbonized surface that inhibits dissolution.
Spinel LiMn2O4 is therefore one of the most promising cathode candidates
for high-power lithium batteries in terms of cost, toxicity, and safety.
However, considering its low gravimetric energy density, spinel LiMn2O4 may
not be suitable as a cathode material in portable batteries.

4 OLIVINE LITHIUM METAL PHOSPHATES

4.1 Introduction

Padhi et al. [115] [116] [117] first reported the polyanionic compounds with
an olivine or NASICON structure as insertion materials for lithium ion
batteries in 1996. Olivine LiFePO4 and NASICON Li3Fe2(PO4)3 are two
typical compounds in this category [118].
60 Zhicong Shi , Hansan Liu and Jiujun Zhang

Olivine lithium metal phosphates (LiMPO4, where M is either Mn, Fe, Co,
or Ni) have an orthorhombic symmetry with the space group Pmna (No. 52),
as shown in Figure 18 [116]. The olivine structure consists of a slightly
distorted hexagonal close-packed (hcp) framework, with Li and M in the
octahedral 4a and 4c sites, and P in the tetrahedral 4c sites, respectively. The
octahedral 4a sites form linear chains of edge-sharing [LiO6] octahedra along
the b axis, which can produce a 1D channel for lithium ion transportation. The
octahedral 4c sites form staggered lines of corner-sharing [MO6] octahedra
along the b axis. The strong P-O covalency can stabilize the anti-bonding
M3+/M2+ state through the M-O-P inductive effect, generating a higher redox
potential. Moreover, the MPO4 3D framework with strong P-O covalency is
stable not only at high temperatures, but also during lithium intercalation/de-
intercalation cycling.
Olivine LiMPO4 sustains its orthorhombic structure after removal of one
lithium ion, exhibiting only a 6.81% shrinkage in volume, which means it
offers a good cycle life and excellent safety when used as the cathode in
lithium ion batteries. However, separation of the [MO6] octahedra by [PO4]
tetrashedra can dramatically reduce the material’s electronic conductivity,
leading to a poor rate capacity [119 ]. Great efforts have thus been made to
improve the conductivity and hence the capacity of olivine phosphates. These
cathode materials include LiFePO4, LiMnPO4, and LiCoPO4. The electronic
conductivity of LiMPO4 olivines could be effectively improved by various
techniques, such as carbon coating, cation doping, and synthesis of
nanocrystalline grains [120] [121] [122] [123] [124] [125].

4.2 LiFePO4

4.2.1 Problems with LiFePO4

Phospho-olivines as lithium intercalation materials were reported early in
1997. Unfortunately, researchers did not pay much attention to them because
olivine phosphates with low electronic conductivity did not allow most of the
lithium ions to intercalate/de-intercalate reversibly. This low reversibility
could lead to low capacity, particularly at high current densities. Under the
strong driving force of safety requirements when lithium ion batteries are used
commercially for both portable devices and EV/HEV applications, olivine
phosphate cathode materials, especially LiFePO4, have been revisited globally
by researchers since the beginning of the 21st century. Attractive features are
 Inorganic Cathode Materials for Lithium Ion Batteries 61

their low cost, low toxicity, excellent thermal stability, and promising
electrochemical performance.
Olivine LiFePO4 has an orthorhombic symmetry with the space group
Pmna and cell parameters a = 10.333 Å, b = 6.011 Å, and c = 4.696 Å [126]. It
can reversibly intercalate/de-intercalate almost all of the lithium ions at around
3.4 V vs. Li/Li+, delivering a theoretical specific capacity 170 mA h g-1 and a
theoretical energy density of 550Wh/kg. Due to the inductive effect from
strong P-O covalency, olivine phosphates can maintain their structure during
the lithium intercalation/de-intercalation process in coexistence with LiFePO4
and FePO4 [ 127 ]. Delithiated FePO4 shows an olivine structure with a very
slight deviation in cell parameters from that of LiFePO4, which guarantees
excellent stability of the crystal structure and thus excellent cycling
performance [128]. The reversible capacity of LiFePO4 can reach 170 mA h g-1,
with no obvious fading apparent even after several hundred cycles. Moreover,
LiFePO4 shows high thermal stability and low oxidative ability with the
electrolyte [ 129 ] [ 130 ]. Unfortunately, the electronic conductivity of pure
LiFePO4 (ca. 10-9 S cm-1) at room temperature [123] [125] was found to be far
lower than that of LiCoO2 (ca. 10-3 S cm-1) [131] and of LiMn2O4 (ca. 10-4 S
cm-1) [132]. The poor kinetics of lithium intercalation in LiFePO4, caused by a
low lithium diffusion coefficient [133] and low electronic conductivity [134],
could also restrict its practical capacity at high current densities, particularly
limiting its use in high-power lithium ion batteries for EV/HEV applications.
The other problem with LiFePO4 is the difficulty of preventing Fe2+ from
being oxidized to Fe3+ during preparation. Many studies of LiFePO4 have thus
been focused on preparation methods and on enhancing its electrochemical
performance through doping and/or coating.

4.2.2 Synthesis methods for LiFePO4

LiFePO4 can be prepared by high-temperature solid-state reactions, or by
low-temperature liquid methods. The first reported LiFePO4 was synthesized
by a high-temperature reaction of solid-state precursors, including ferrous salt,
in an inert atmosphere [113] [125] [ 135 ]. Solid-state reactions can readily
produce aggregative particles and some impurities due to incomplete mixing
of reactants as well as lithium evaporation at high temperatures. The intimate
grinding of starting materials can be attained by the mechanochemical
activation method, resulting in pure LiFePO4 with smaller particle sizes [134].
LiFePO4 with small particle sizes can also be prepared at a lower temperature
and in a shorter time period by a microwave method [136]. In addition, a novel
carbothermal reduction method was also developed to synthesize LiFePO4
62 Zhicong Shi , Hansan Liu and Jiujun Zhang

using a low-cost ferric salt [137]. It was found that carbon resources in the
starting materials not only acted as reductive reagents for the transition of Fe3+
to Fe2+ at high temperatures, but also prevented the final products from
aggregating. Furthermore, the residual carbon film on the surface of LiFePO4
could significantly increase its electronic conductivity.
Normally, low-temperature liquid methods consume less energy than
high-temperature solid-state methods. LiFePO4 could be synthesized by many
low-temperature methods, such as the hydrothermal [123] [ 138 ] [ 139 ], co-
precipitation [127] [134], or sol-gel method [134] [ 140 ]. Although the
hydrothermal method is easy to operate, the synthesized olivine LiFePO4 has
shown poor electrochemical properties, as about 7% of the iron atoms
occupied the lithium sites and blocked the diffusion of lithium ions [138]. Heat
treatment of hydrothermal material at 700 °C ordered the lithium and iron
atoms. Using the co-precipitation method, a finely dispersed precursor
containing a stoichiometric composite of Fe(II) phosphate and lithium
phosphate can be obtained. Sintering of this precursor can produce finely
dispersed, rhombus shaped LiFePO4 sheets (Figure 19). This material, when
added with 20 wt% conductive carbon and 10 wt% PTFE, can deliver a
constant capacity of 150 mA h g-1 at a 0.05 C rate in the first 40 cycles [127].
However, the amount of additives in the electrode composite needs to be
reduced to further improve the specific capacity.

4.2.3 Electrochemical performance upgrading of LiFePO4

As pure LiFePO4 has a very low electronic conductivity (ca. 10-9 S cm-1)
at room temperature [122], the theoretical capacity (170 mA h g-1) can only be
observed at either a very low current density [120] or elevated temperatures
[128]. Two strategies, carbon coating and cation doping, are generally adopted
to improve the electronic conductivity and thereby the electrochemical
performance of LiFePO4.
Huang et al. [141] reported a LiFePO4/C (15 wt% of carbon) composite and
obtained capacities of 162 mA h g-1 at a 0.1 C rate and 110 mA h g-1 after 800
cycles at a 5 C rate, even with a low cathode loading (5 mg/cm2) and rather
high carbon content (20 wt%, including 5 wt% additive carbon). Such a large
amount of carbon could significantly decrease the tap density and energy
density of LiFePO4/C composites. Chen at al. [142] proposed a LiFePO4/C (3.5
wt% of carbon) composite using sugar as a carbon precursor, achieving a rate
capability comparable to that of LiFePO4/C (15 wt%) reported by Huang et al.
[140].
 Inorganic Cathode Materials for Lithium Ion Batteries 63

Chuang et al. [122] at MIT reported an impressive electrochemical

performance for LiFePO4 doped by cations, including Mg2+ and Nb5+. The
doped material showed an electronic conductivity increased by 8 orders of
magnitude (Figure 20). At low rates (C/10 to C/30), this material gives a
capacity of ~150 mA h g-1, corresponding to ~90% of the theoretical value.
The capacity is reduced to 100 mA h g-1 at 4.3 C, in the voltage range of 2.8–
4.2 V at room temperature. Power and energy densities for a complete cell
could be estimated as 1,300-2,200 W kg-1 and 32-53 W h kg-1 at a 20 C rate,
and 2,800-4,670 W kg-1 and 18-30 Wh kg-1 at a 40 C rate, respectively. This
result makes these low-cost and ultra-safe olivine materials very attractive for
EV/HEV applications.

4.3 LiMPO4 (M = Mn, Co, Ni)

Besides iron, the transition metal in olivine LiMPO4 may also be

manganese, nickel, or cobalt. However, no reports have been published on
these materials that indicate an electrochemical performance superior to that of
LiFePO4, even though the materials have higher discharge potentials, as shown
by experimental [143] [144] [145] and theoretical results [146]. The open-
circuit voltages are calculated as 3.5 V for LiFePO4, 4.1 V for LiMnPO4, 4.8 V
for LiCoPO4, and 5.1 V for LiNiPO4. Because no appropriate organic
electrolyte can be sustained at a potential over 5 V, LiNiPO4 is still not
suitable to use as a cathode material for lithium ion batteries, at this current
stage in our technology.
Olivine LiCoPO4 can give a high lithium intercalation voltage plateau at
4.8 V with a capacity of 100 mA h g-1 at 0.2 mA cm-2 [142], which is about
60% of the theoretical capacity (167 mA h g-1). Unfortunately, cobalt salts are
costly, resulting in LiCoPO4 being expensive as well and making it a less than
ideal cathode candidate for practical applications despite its high lithium
intercalation plateau. With respect to cost, spinel LiNi0.5Mn1.5O4 material,
which also has a lithium intercalation plateau of 4.8 V, may be more
interesting than LiCoPO4 [147].
Low-cost LiMnPO4, with a lithium intercalation plateau of 4.1 V, is an
attractive cathode candidate for lithium ion batteries. An earlier report on
LiMnPO4 indicated a very low capacity, which might be attributed to its low
electronic conductivity or lithium ion conductivity [148]. LiMnPO4 synthesized
by both the direct precipitation method [149] and the hydrothermal method [150]
did not show a favorable capacity, either. In this kind of material, Mn2+ is
64 Zhicong Shi , Hansan Liu and Jiujun Zhang

disordered on the Li+ sites, which hinders lithium diffusion within the
structure, similar to the case of hydrothermally prepared LiFePO4. Carbon
coating, reported by Li et al. [145], could improve the capacity of olivine
LiMnPO4 up to about 140 mA h g-1 with a current density of 0.28 mA cm-2 at
room temperature (Figure 21). However, carbon-coated LiMnPO4 showed a
poor rate capacity of about 50 mA h g-1 at a 2 C rate [151], which was far lower
than that of carbon-coated LFePO4. Therefore, it is necessary to further
improve the performance of manganese olivine when it is used as a cathode
material for lithium ion batteries, even though it has a high lithium
intercalation voltage and needs mild synthetic conditions.

5 CONCLUSION
Lithium ion battery technology still faces some challenges, including
safety issues and insufficient energy density for modern electronic devices,
although these batteries have been commercially available for many years. The
emerging market of electric vehicles, hybrid electric vehicles, and plug-in
hybrid electric vehicles (PHEV) is a strong driving force to overcome these
challenges and stimulate the development of a new generation of lithium ion
batteries with high energy density and high power density. In order to address
these issues, cathode materials in lithium ion batteries are the primary targets
of research and development. In previous decades, layered LiCoO2 was the
cathode material for the first generation of lithium ion batteries, and even
today it is still used in most of commercially available lithium ion batteries.
But because of its poor thermal stability and low specific capacity, alternative
new inorganic cathode materials are urgently needed to replace LiCoO2. With
rapid research and development, several kinds of materials have been
explored, including LiNiO2, LiMnO2, LiMn2O4, and LiFePO4.
Compared with LiCoO2, layered LiNiO2-based compounds show higher
specific capacity but poorer thermal stability. Although lattice doping and
surface coating can further improve performance, these materials can only be
used in limited fields and are not suitable for completely replacing LiCoO2 in
the main lithium ion battery market. Layered LiMnO2-based compounds are
not considered practical cathode materials because of their structural
instability. Fortunately, layered mixed transition metal oxides, particularly the
550 and 333 materials, display higher specific capacity and better thermal
 Inorganic Cathode Materials for Lithium Ion Batteries 65

stability than LiCoO2, and should be able to gradually replace LiCoO2 in

lithium ion batteries for portable electronic devices.
Compared with LiCoO2, spinel LiMn2O4 is another promising cathode
material, being low-cost, environmentally benign, and thermally stable.
Unfortunately, its low rate capability and poor capacity retention at elevated
temperatures compromise this material’s suitability. Efforts to improve the
electrochemical performance of spinel LiMn2O4 through material
modifications have recently intensified.
Olivine LiFePO4 is another good cathode material candidate because of its
low cost, low toxicity, and excellent thermal stability, its major drawback
being low electronic conductivity. With respect to this, great progress has been
made using lattice doping and surface coating technologies. Because of its
affordability and safety, LiFePO4 has emerged as a commercially available
new cathode material for the next generation of lithium ion batteries,
particuraly in EV/HEV/PHEV applications.

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In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 3

ANALYSIS OF CELL IMPEDANCE

FOR THE DESIGNOF A HIGH-POWER
LITHIUM-ION BATTERY

Hyung-Man Cho and Heon-Cheol Shin∗

School of Materials Science and Engineering,
Pusan National University, Busan, Korea.

ABSTRACT
This work presents a systematic semi-empirical way to analyze the
constituents of total cell impedance in a lithium-ion battery, and their
time-dependent contributions to total direct current (dc) polarization. The
approach includes the differentiation of internal resistive elements,
followed by theoretical calculations of their contributions to total
polarization using circuit analysis. Our method provides a fast and
reliable way to design a high-power battery with the instantaneous
input/output power that best fits the user’s specific needs. It also provides
insight into the design of high-power with long shelf life and calendar life.
We begin with an overview of high-power cell design. Methodology to
differentiate and quantify the time-dependent contribution of elementary
resistances to total polarization is given, and applications to power aging
in battery use, and power decline at low operating temperature, are

∗
Corresponding author: E-mail: [email protected]
74 Hyung-Man Cho and Heon-Cheol Shin

suggested. A strategy for the design of materials to meet power

requirements is discussed for each case.

I. INTRODUCTION
High power batteries have been widely studied as an energy source for
eco-friendly transportation systems including hybrid electric vehicles, electric
motors, ships, and aircraft that can be operated with little or no oil
consumption and carbon dioxide emissions, as compared to conventional
systems with an internal combustion engine [1-3]. The lithium-ion battery
(LIB) has been one of the most promising substitutes for the nickel metal
hydride battery used in most of the hybrid electric vehicles (HEVs)
commercially available today [4].
A successful design of a high-power LIB at both ambient and low
operating temperatures, the diagnosis of the battery with degraded power, and
the subsequent redesign of the battery with long shelf/calendar life rests
entirely on an in-depth understanding of factors related to battery power. This
chapter presents a systematic semi-empirical way to analyze the time-
dependent contribution to total polarization of each reaction step involved in
battery operation. For this purpose, electrical signals from the cathode and
anode are separated using a three-electrode electrochemical cell configuration.
Then, they are further differentiated on the grounds of mechanism-based or
phenomenological equivalent circuits. Next, the variation in elementary
polarization caused by each reaction step with time is calculated using a
theoretical analysis of an equivalent circuit. This gives the proportional
contribution of each reaction step to the total polarization during a pulse
discharging or regenerative (charging) process.
In this article, the main impedance factors affecting the power
performance of a LIB are proposed as functions of operating temperatures and
degrees of cell power degradation. In Section II, high power cell design is
introduced with an emphasis on design factors of the constituents. In Section
III, we suggested the methodology to quantitatively analyze the time-
dependent contribution of elementary resistances to total polarization. In
Section IV, an in-depth diagnosis of the battery with degraded power is
considered. In particular, analyses based on two- and three-electrode
electrochemical cell configurations are compared. Finally, Section V describes
the temperature dependence of battery power and related critical factors,
together with a prediction of the low temperature performance of a hybrid
 Analysis of Cell Impedance for the Design of a High-Power… 75

electrode consisting of typical insertion materials and electrical double layer

capacitor (EDLC) materials.

(a)

(b)

Figure 1. Schematic representations of (a) battery pack and (b) the inside of unit cell.

II. OVERVIEW OF HIGH POWER CELL DESIGN

The main role of a LIB in transportation systems such as a HEV depends
on the type of electric vehicle. Power density is particularly important when
76 Hyung-Man Cho and Heon-Cheol Shin

the battery is used as an auxiliary power source for a strong (full) or plug-in
HEV [5]. Here, the engine might be operated at the most efficient speed and
additional power is supplied by the battery as required. That is, the battery
provides additional power in the case of uphill driving and accelerating, and
absorbs regenerative power during downhill/normal driving and braking.
Accordingly, the battery, as an assisting power source, needs superior
capability for charge (or power) release and gain.
The successful development of a LIB with high power density depends on
minimizing the ionic and electronic resistances related to battery operation.
Thus, it is imperative to understand the pathways of electrons and lithium ions.
The resistance of the battery or unit cell (hereafter called “cell resistance”) is
only a part of the total resistance responsible for battery power. The design
must take into consideration battery pack resistance; this consists of cell
resistance, the bulk resistance of jigs, the connection (or contact) resistance
between cell and jig, the resistance caused by the battery management systems
(BMS), etc., as shown in Figure 1(a). Among these resistance sources, cell
resistance is of prime importance because the consistency in cell resistance
during and after repetitive use (or long time storage), and its temperature
dependence especially at very low temperatures, are decisive factors in the
performance of the whole battery pack.
A simplified schematic view inside a LIB is shown in Figure 1(b). The
internal cell resistance in the LIB can be roughly classified as follows [6-8]: 1)
a series resistance RΩ due to lithium ion transport through the porous separator
wetted with the electrolyte, and electron transport through numerous pathways
including the conducting chains (e.g., carbon black in the composite
electrode); 2) a film resistance Rf due to lithium ion transport through the solid
electrolyte interphase (SEI) on the active materials; 3) a charge transfer
resistance Rct at the interface between the electrolyte (or SEI) and active
materials; and 4) a diffusion impedance Zdiff against solid-state bulk diffusion
of lithium ions through active materials.
The design to decrease RΩ is straightforward in that the electronic or ion
conductivity of the components has a direct influence on the value of RΩ. For
instance, separators with different porosity and pore tortuosity lead to different
values of apparent electrolyte resistance, since these two factors play a critical
role in the polarization inside the separator. (In fact, air permeability and the
Gurley number are more frequently used in industry to evaluate the degree of
penetrability of active species through the separator than the terminologies
such as porosity, tortuosity, and polarization [9].) The separators with more
porous and less tortuous pore structure result in smaller RΩ (or polarization),
 Analysis of Cell Impedance for the Design of a High-Power… 77

yielding higher power density of the battery. However, an excessively open

separator pore structure is usually not adequate for practical use due primarily
to safety issues and a strong possibility of micro-shorts between the cathode
and anode [10].
Although the chemical composition of the SEI has been extensively
studied for two decades, a systematic analysis of the lithium ion transport
through it has not been performed in spite of its relevance. This is because the
unique structure of the SEI, consisting of a compact LixPFy/Li2CO3-based
inner layer and porous polycarbonate-based outer layer, complicates the
situation. The control of the SEI formation (or activation) process immediately
after battery assembly, and the appropriate design of an electrolyte with
specific additives that are decomposed ahead of the conventional SEI-forming
solvent such as ethylene carbonate may affect SEI properties, but a study of
the design parameters of the SEI is still a great challenge [11].
Energetically, interfacial charge transfer and solid-state lithium diffusion
through the active materials are usually the most difficult reaction steps in the
lithium intercalation/deintercalation process. In particular, Rct is thought to be
critical in battery performance at very low temperatures although there is still
controversy regarding the dominant low temperature rate-determining
mechanism [12-14]. Design of the composition of active materials and surface
modification would be promising ways to elevate electrochemical activity at
the interface, thereby dropping off the charge transfer barrier. Nano-structured
active materials with nano-pores and/or particles are an alternative with great
potential for significantly lowering the value of Rct. However, the difficulty of
uniform dispersion, and the irreversible charge consumption during the initial
SEI formation process due to their extremely large surface area, needs to be
resolved for their practical use [15-17].
The solid-state diffusion process is particularly important when interfacial
charge transfer is relatively facile and thus the total intercalation reaction is
governed by the chemical diffusion of lithium through the active materials.
Basically, the activation energy for lithium diffusion closely relates to the size
of the lithium diffusion path and the electrostatic interaction between lithium
ions and the cations around it. Hence, much work has been done to reduce the
activation energy for lithium diffusion by compositional and/or structural
adjustment at the atomic scale on the basis of ab initio calculation [18, 19]. At
the microscale, the modification of microstructure such as grain size (or grain
boundary) is expected to considerably affect lithium diffusivity. In general, the
oxides with larger primary particle sizes show higher lithium diffusivity since
the inter-particle transport of lithium across grain boundaries is reduced [20].
78 Hyung-Man Cho and Heon-Cheol Shin

III. TIME-DEPENDENT CONTRIBUTION OF REACTION

STEPS TO TOTAL POLARIZATION

1. Overview of the Approach

Our goal is to quantify the time-dependent proportional contribution of

individual reaction steps to total polarization during battery operation, and
then set the redesign strategy of the cell components of a high-power LIB. The
differentiation and quantification of the elementary impedances are the first
step in this approach. Here, the electrochemical impedance spectra are
obtained at a specific state-of-charge (SOC) and battery operating temperature.
Then, the lithium intercalation is modeled to construct a mechanism-based
equivalent circuit, and its electrical parameters are estimated using a complex
nonlinear least squares (CNLS) fitting method [21, 22]. If the reliable
identification of an impedance model and its electrical parameters is unlikely
due to ambiguity of the measured impedance spectra, impedance diagnosis
methods such as discrete Fourier transformation (DFT) [23-26] and
differential impedance analysis (DIA) [27-29] could be used to analyze the
impedance spectra without prior assumption regarding individual reactions.
The next step is the calculation of elementary polarizations due to the
corresponding resistive elements as a function of pulse discharging/charging
time, with the help of theoretical analysis of an equivalent circuit. The
Simulation Program with Integrated Circuit Emphasis (SPICE) software
program is an excellent circuit simulation tool [30-32]. With the help of
SPICE, the variation of instantaneous elementary polarization with battery
operating time is attainable by considering the potential difference between the
nodes of both sides of the resistive elements of concern.
Then, time-dependent proportional contributions of elementary
polarizations (or reaction steps) to total dc polarization are finally determined,
and this gives useful information when we design the battery with the
instantaneous power density that fits our specific needs. For example, if the
HEV to be produced typically undergoes repetitive short time acceleration and
deceleration (braking), cell constituents need to be designed for enhanced
power performance for the initial time period of battery discharging and
charging at high current (or power) density. On the other hand, when the
driving pattern includes extended acceleration or uphill driving, power
performance over a prolonged time period must be considered and the cell
constituents designed accordingly. In addition to cell design according to
 Analysis of Cell Impedance for the Design of a High-Power… 79

driving patterns, this approach can be effectively utilized for diagnosis of a

battery with degraded power, analysis of low temperature power decline, and
prediction of power performance. The application of this approach to a
hypothetical electrochemical cell is given in the next section.

2. Model Case: Analysis on Hypothetical Electrode in LIB

It is generally accepted that the lithium intercalation/deintercalation

process of the LIB consists of Li+ transport through the electrolyte, Li+
transport through the SEI coupled with the charge storing in it, interfacial
charge transfer combined with electrical double layer charging, and solid-state
lithium diffusion into the active material [6-8]. Figure 2 shows a typical
equivalent circuit that models the lithium intercalation/deintercalation process.

Rf Rct
Zdiff

RΩ

Cf Cdl
(a)

r1 r2 r3 rn

c1 c2 c3 cn

(b)

Figure 2. (a) Simplified hypothetic equivalent circuit to model the intercalation process
of LIB and (b) the electrical expression of the Warburg or diffusion impedance, Zdiff,
i.e., transmission line (TML).
80 Hyung-Man Cho and Heon-Cheol Shin

120

100

- Imaginary Impedance / Ω
80
10 mHz

60
1.74 Hz

40 794 Hz 0.21 Hz

20

0
0 20 40 60 80 100 120

Real Impedance / Ω
(a)
5
10 -60

4 -50
10

3
-40
10
-30
2
10
Θ / deg
|Z| / Ω

-20
1
10
-10
0
10
0

-1
10 10

-2
10 20
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10

Frequency / Hz
(b)

Figure 3. (a) Nyquist plot and (b) Bode plot, obtained from the equivalent circuit of
Figure 2. The impedance spectra were theoretically determined by arbitrarily taking
RΩ=5 Ω, Rf=20 Ω, Cf=10 μF, Rct=35 Ω, and Cdl=2 mF. The diffusion impedance Zdiff
is expressed as Zdiff=Aω(jω)-0.5tanh[δ(jω)0.5] (where, δ is defined as L/D1/2, ω is the
angular frequency, and Aω is the Warburg coefficient expressed as RD/δ). RD=400 Ω,
L=10 μm, and D=10-9 cm2/s were taken for the calculation of Zdiff. The elemental
resistance rn and capacitance cn in the TML were estimated to be 4×107Ω⋅m-1 and
2.5×105 s⋅Ω-1⋅m-1, respectively.
 Analysis of Cell Impedance for the Design of a High-Power… 81

The electrical parameters related to electrode reaction were arbitrarily

assigned to construct the hypothetical electrode in a LIB. In particular, for the
solid-state diffusion process, finite-length lithium diffusion through the active
materials was assumed. Figure 3 shows the impedance spectra of a
hypothetical electrode in the frequency range of 1 MHz to 1 mHz (for details
on the electrical parameters, see the caption of Figure 3). In particular, the
Nyquist plot shown in Figure 3(a) has two semicircles in the high and
intermediate frequency range, followed by a 45° inclined line at the low
frequency range. The first and second semicircles are ascribed to the reactions
in the SEI and the interfacial charge transfer reaction combined with electrical
double layer charging, respectively, while the inclined line is due to solid-state
lithium diffusion into the active material.

Vtot,L Vtot,R
Vdiff,L Vdiff,R
Vct,L Vct,R
Vf,L Vf,R
VΩ,L VΩ,R
Zdiff(TML)
Rf Rct

RΩ

Cf Cdl Square
current
pulse

Figure 4. Brief description of the circuit analysis, showing the application of the square
current pulse and the estimation of the potential difference, i.e., polarization, due to the
electrical elements. Potential differences between the nodes, VΩ,L / VΩ,R, Vf,L / Vf,R, Vct,L /
Vct,R, Vdiff,L / Vdiff,R, and Vtot,L / Vtot,R represent the polarizations due to the uncompensated
Ohmic resistance (ΔVΩ), resistance to lithium-ion transport through the SEI layer (ΔVf),
interfacial charge-transfer resistance (ΔVct), diffusion resistance (ΔVdiff), and total cell
resistance (ΔVtot), respectively.
82 Hyung-Man Cho and Heon-Cheol Shin

4.2
0.0 0.2C
0.5C

+
Cell Potential / V vs. Li/Li
4.0
1C

Cathodic Polarization / V
0.2
2C
3.8
0.4
4C
3.6
0.6
6C
3.4
0.8
8C 3.2
1.0
10C 3.0
1.2
0 2 4 6 8 10 12

Discharging Time / s
(a)
4.2
0.0 0.2C
0.5C
1C 4.0

+
Cathodic Polarization / V

Cell Potential / V vs. Li/Li

0.2
2C
3.8
0.4
4C
3.6
0.6
6C 3.4
0.8
8C 3.2
1.0

10C 3.0
Stage I Stage II Stage III
1.2
-4 -3 -2 -1 0 1
10 10 10 10 10 10

Discharging Time / s
(b)

Figure 5. (a) Calculated cathodic polarization (or cell potential) transients during
cathodic pulse discharging for 10 s at different rates and (b) the reproduced plot in a
semi-logarithmic scale which shows three-stage behaviour. In order to convert the
current density to the C rate, the mass of the active material and its specific gravimetric
capacity were assumed to be 10 mg and 100 mAhg-1, respectively.
 Analysis of Cell Impedance for the Design of a High-Power… 83

4.2
0.0
ΔVΩ

Cathodic Polarization / V
4.0
0.2 ΔVf

+
Cell Potential / Li/Li
3.8
ΔVct
0.4
3.6
ΔVdiff
0.6
3.4
0.8
3.2
1.0
3.0
Stage I Stage II Stage III ΔVtot
1.2
-4 -3 -2 -1 0 1
10 10 10 10 10 10

Discharging Time / s

Figure 6. Variation of the elementary polarizations with the discharging time at a

discharging rate of 10C on a semi-logarithmic scale, determined from the circuit
analysis (Figure 4).

0.6
Proportional Contribution to ΔVtot / -

a b
0.5
ΔVdiff

0.4

ΔVct
0.3

0.2
ΔVf

0.1

ΔVΩ
0.0
0 2 4 6 8 10 12

Discharging Time / s

Figure 7. Time-dependent proportional contribution of elementary impedances to total

polarization, reproduced from Figure 6. The polarizations due to the charge transfer
and the diffusion make a maximum contribution to total polarization in the regions of a
and b, respectively.
84 Hyung-Man Cho and Heon-Cheol Shin

For a theoretical analysis of an equivalent circuit based on SPICE, the

Warburg or diffusion impedance Zdiff (Figure 2(a)) was expressed using a
combination of the electrical elements. A resistive-capacitive transmission line
might be an excellent electrical analogy of the ideal diffusion process (Figure
2(b)) [33]. The elemental resistance rn and capacitance cn of the transmission
line have a direct relationship with the limiting diffusion resistance RD (RD
=rn⋅L, where L is the diffusion thickness) and diffusion capacitance CD (CD
=cn⋅L=L2/[RD⋅D], where D is the chemical diffusion coefficient), respectively,
in the finite length diffusion process. Since RD is correlated with the Warburg
coefficient Aω (Aω= R D D / L ), which can be experimentally estimated from
the impedance spectrum in the low frequency region, the evaluation of rn and
cn is quite straightforward [33-35].
Now, different current pulses are applied to the reconstructed equivalent
circuit where the Warburg element is substituted for the transmission line, as
shown in Figure 4. The calculation of the potential difference between the
nodes of Vtot,L and Vtot,R as a function of current application time generates the
time-dependent total polarization. We note that the resulting total polarization
is monotonically decreasing on a linear scale (Figure 5(a)), while it shows
three-stage behavior on a semi-logarithmic scale (Figure 5(b)), strongly
indicating the change in the governing factor in the shape of total polarization
transients.
The complicated shape of semi-logarithmic polarization transients can be
readily understood by considering the variations of elementary polarizations
with time. The time-dependent elementary polarizations were obtained for the
nodes of VΩ,L/VΩ,R (for series resistance, including electrolyte resistance),
Vf,L/Vf,R (for SEI film resistance), Vct,L/Vct,R (for interfacial charge transfer
resistance), and Vdiff,L/Vdiff,R (for bulk diffusion resistance). The resulting
elementary polarization transients at a current of 10 mA (Figure 6) proved that
the polarizations due to SEI film resistance (ΔVf), interfacial charge transfer
resistance (ΔVct), and solid-state diffusion resistance (ΔVdiff) are attributable,
consecutively, to three-stage behavior of the total polarization transients.
The contribution of the individual reaction steps to total polarization was
calculated from Figure 6, which gives us the reaction step (or elementary
polarization) corresponding to the maximum contribution to total polarization
at a specific moment of discharging time. In our hypothetical electrode, the
interfacial charge transfer reaction primarily affects total polarization over an
initial period of discharging time, while the solid-state diffusion process makes
a maximum contribution in a later stage of discharging time, as shown in
 Analysis of Cell Impedance for the Design of a High-Power… 85

Figure 7. That is, to enhance the initial power performance of our hypothetical
electrode, the surface design of active materials to elevate the electrochemical
activity must come before all other design of the cell constituents. On the other
hand, when the power performance must not drop off significantly in the later
stage of discharging time and level off throughout the whole discharging time,
the bulk design of active materials to promote solid-state diffusion takes
precedence over all other design factors.
Here, following three factors to additionally affect the cell potential during
discharging process should be mentioned: As a matter of fact, all the
resistances and capacitances except for a series resistance RΩ in the circuit are
basically dependent on lithium content in the active materials. In particular, it
has been well known that Rct and Zdiff are strong functions of lithium content.
This indicates that their variations with lithium content needs to be taken into
account for the calculation of the polarization. Furthermore, the change in the
electrochemical (thermodynamic) potential with lithium content, which relates
to the absorption isotherm of the systems, should be considered for the
calculation. Nevertheless, in the relatively mild operating conditions adopted
in this work, i.e., the maximum discharging current of less than 15C rate and
discharging time for less than 10 s, the variation of lithium content
(stoichiometry) is estimated to be less than 0.02, which is quite small so that
the change in resistance/capacitance/diffusivity and cell potential with lithium
content could be virtually disregarded for the calculation of the potential
transients [31]. In the case of extremely high current drains, however, the
above two factors can’t be neglected. Finally, the difficulty in lithium ion
transport through the porous separator wetted with the electrolyte might raise
the polarization. This additional polarization is usually unavoidable at the
extremely high current drains and get larger as one uses separators with
smaller penetrability, i.e., less porous and more tortuous separators [9].

IV. IN-DEPTH DIAGNOSIS OF THE BATTERY

WITH DEGRADED POWER

1. Cell Configuration and Electrochemical Test Procedures

Two-electrode and three-electrode electrochemical cells used for the

electrochemical measurements are shown in Figures 8(a) and (b), respectively.
In both cell configurations, lithium foil is selected as the counter (auxiliary)
86 Hyung-Man Cho and Heon-Cheol Shin

electrode. Composite materials of 90 wt.% LiCoO2 (Aldrich), 5 wt.% carbon

black, and 5 wt.% polyvinylidene fluoride binder in n-methyl pyrrolidinone
were employed as the working electrode. Details of the drying and pressing
conditions of the composite electrode can be found in [32]. A Celgard 2400
separator was wetted with 1 M solution of lithium hexafluorophosphate
(LiPF6) in a 1:1 volume mixture of ethylene carbonate (EC) and diethyl
carbonate (DEC), and then sandwiched between a composite working
electrode and a counter electrode.
For the reference electrode of a three-electrode electrochemical cell, the
end tip of the Teflon coated copper wire was removed. Lithium titanium oxide
(Li4Ti5O12, Altair) was coated on the bare copper [36, 37]. The reference
electrode was located between two separators, as shown in Figure 8(b). Before
conducting the electrochemical tests, the state of charge of the lithium titanium
oxide was set to 50%, and in this state its potential was approximately 1.57 V
(vs. Li/Li+). All of the cells were assembled in a glove box (MBraun,
Germany) filled with purified argon gas.

Tests of two-electrode electrochemical cell: The as-prepared cell was first

galvanostatically activated five times between 3.0 and 4.2 V (vs. Li/Li+) at a
rate of 0.2 C (24 mAg-1; a gravimetric specific capacity of 120 mAhg−1 was
assumed to convert the current density into the C rate). The cell in this state is
hereafter called the “fresh cell.” After the impedance measurement and a series
of current pulse tests, the cell was further galvanostatically cycled 20 times
under the same conditions that the as-prepared cell was initially cycled (the
cell in this state is hereafter called the “aged cell”). The specific capacity of
the aged cell was reduced to about 80%, as compared to the capacity of the
fresh cell. Finally, impedance measurement and current pulse tests were
performed for the aged cell. For the pulse tests, after equilibrating the cell at
4.2 V (vs. Li/Li+), a variety of cathodic currents were applied until either the
electrode potential reached the low cutoff voltage of 3.0 V (vs. Li/Li+) or the
cell was discharged for 10 s. The impedance measurements were carried out at
a potential of 4.2 V (vs. Li/Li+) by applying an ac amplitude of 5 mVrms over
the frequency range of 10 mHz to 100 kHz.

Tests of three-electrode electrochemical cell: The initial activation of the

as-prepared cell was done in the same way as that of the two-electrode cell.
Then, the fresh cell was further cycled 20 times for cell aging. The
electrochemical impedance spectra at a cell potential of 4.1 V (vs. Li/Li+) were
obtained for the fresh and aged cells for the frequency range of 50 kHz to 5
 Analysis of Cell Impedance for the Design of a High-Power… 87

mHz. Current pulse tests were carried out immediately after the impedance
tests by applying different cathodic currents for 10 s.

Stainless Steel Stainless Steel

Lead :
Stainless Steel

Anode :
Lithium metal

Separator :
Celgard 2400

Cathode : Reference
Lithium cobalt dioxide Electrode :
Current Collector : Teflon-coated
Aluminum lithium titanate
Lead :
Stainless Steel
Stainless Steel Stainless Steel

(a) (b)

Figure 8. Schematic illustrations of (a) two-electrode and (b) three-electrode

electrochemical cell configurations.

0.5C
4.2 0.0
1C
2C
+
Cell Potential / V vs. Li/Li

Cathodic Polarization / V
4.0 3C 0.2

5C
3.8 0.4

8C
3.6 0.6
10.3C

3.4 0.8
13.3C
3.2 1.0
15.3C
3.0 1.2
Fresh cell Aged cell
2.8 1.4
0 2 4 6 8 10 12

Discharging Time / s
Figure 9. Typical potential (or cathodic polarization) transients during the cathodic
pulse discharging for 10 s at different rates, obtained from the fresh cell (solid line) and
the aged cell (dashed line). Figure 1a in D.-K. Kang and H.-C. Shin, “Investigation on
cell impedance for high-power lithium-ion batteries”, Journal of Solid State
Electrochemistry 11 (2007) 1405-1410, Copyright © (2007), with kind permission of
Springer Science and Business.
88 Hyung-Man Cho and Heon-Cheol Shin

60

R1 R2 R3
50
Zω

- Imagenary Impedance / Ω
L1 RΩ CPE1 CPE2 CPE3
40

30 0.01 Hz

20 3.162 Hz
3.981 Hz
Fresh
Aged
10 1 kHz

0.2 Hz
0.316 Hz
0 10 20 30 40 50 60
Real Impedance / Ω

Figure 10. Typical impedance spectra, obtained from the fresh (open circle) and the
aged cell (open square) at the cell potential of 4.2 V (vs. Li/Li+). The inset is the
phenomenological equivalent circuit to model the overall process. Solid lines were
determined from the CNLS fittings of the impedance spectra to the equivalent circuits.
Figure 2 in D.-K. Kang and H.-C. Shin, “Investigation on cell impedance for high-
power lithium-ion batteries”, Journal of Solid State Electrochemistry 11 (2007) 1405-
1410, Copyright © (2007), with kind permission of Springer Science and Business.

A Solartron 1287 electrochemical interface was employed for all of the

galvanostatic experiments. For the electrochemical impedance measurements,
the Solartron 1287 electrochemical interface was coupled with a Solartron
1455A frequency response analyzer.

2. Analysis Based on a Two-Electrode Electrochemical Cell and

its Limitation

Typical potential (or cathodic polarization) transients during constant

current discharging for 10 s at different rates are shown in Figure 9. All the
transients exhibited an abrupt drop in the initial stage of pulse discharging,
followed by a relatively slow decrease in potential with time. The rate of
increase in polarization increased with the discharging rate. In particular, we
note that the maximum rate where continuous discharging for 10 s was
achievable decreased from approximately 15 C in the fresh cell to 13 C in the
aged cell. This strongly indicates that the cell resistance of the aged cell
 Analysis of Cell Impedance for the Design of a High-Power… 89

became larger than that of the fresh cell; i.e., power performance degraded
considerably after cell aging.
To investigate the elementary reaction steps and their contribution to the
total intercalation process, impedance spectra for the fresh and aged cells were
obtained as shown in Figure 10. The impedance spectra consisted of
semicircles and an inclined line. Although a semicircle typically results from
the interfacial reactions and an inclined line is attributable to the solid-state
diffusion process, the overlapping of the time constants of the reactions in the
anode and cathode makes reliable mechanism-based analysis of the impedance
spectra quite unlikely.
Thus, the equivalent circuit for the overall process was
phenomenologically constructed, as shown in the inset of Figure 10. The first
two and the third parallel resistor-constant phase elements (CPEs) stand for the
extremely depressed semicircles in the high frequency range and the third
semicircle in the intermediate frequency range, respectively. The Warburg
element Zω represents an inclined line in the low frequency range. The values
of resistance, capacitance, and the Warburg coefficient were estimated using
CNLS fitting methods. For the theoretical analysis of an equivalent circuit, the
Warburg impedance was modeled by a transmission line, and its elementary
resistance r and capacitance c were evaluated based on the method suggested
in Section III-2. Here, all the CPEs were considered as purely capacitive
components in spite of some discrepancies between the experimental potential
transients and the calculated values. It seems that this simplification is
tolerable in our case, since the capacitive element or CPE has affects the shape
of the transients by less than a couple of hundred milliseconds [31, 32].
It is additionally noted that the changes in resistance/
capacitance/diffusivity and electrochemical or thermodynamic potential with
lithium content were disregarded for the calculation of the polarization. This
seems to be acceptable in the operating conditions adopted in this work due to
small variation of lithium content during the discharging for 10 s. For further
discussion on this topic, see [31].
The dependences of potential (or polarization) on discharging time were
calculated using the SPICE program by applying the different values of square
current to the equivalent circuit. The resulting transients of total cell
polarization are depicted in Figure 11(a). The calculated transients
quantitatively matched the experimental transients (Figure 9). We note that the
semi-logarithmic variation of total cell polarization with discharging time
clearly showed three-stage behavior, as demonstrated at the rate of 8 C in
Figure 11(b). The calculated transients of the elementary polarizations (Figure
90 Hyung-Man Cho and Heon-Cheol Shin

11(b)) tell us that the elementary polarizations due to the R2-C2, R3-C3, and
diffusion impedance are responsible for the three-stage behavior of the total
polarization transient.

0.0 0.5C 4.2

1C
2C
Cathodic Polarization / V

+
0.2 4.0

Cell Potential / V vs. Li/Li

3C

0.4 5C 3.8

0.6 8C 3.6

10.3C
0.8 3.4
13.3C
1.0 3.2
15.3C

1.2 3.0
Fresh cell Aged cell
1.4 2.8
0 2 4 6 8 10 12

Discharging Time / s
(a)

ΔV(RΩ)
0.0 ΔV(R1)
Cathodic Polarization / V

0.1
ΔV(R3)
0.2 ΔV(R2)

ΔV(TML)
0.3

0.4
ΔV(total)
0.5
STAGE I STAGE II STAGE III
0.6
-4 -3 -2 -1 0 1
10 10 10 10 10 10

Discharging Time / s

(b)
Figure 11. (a) Calculated potential (or cathodic polarization) transients during the
cathodic pulse discharging for 10 s at different rates, obtained from the fresh cell (solid
line) and the aged cell (dashed line) and (b) semi-logarithmic variations of the
elementary and total polarizations of the fresh cell with discharging time at 8C rate,
determined from the circuit analysis. Figures 3a and 4 in D.-K. Kang and H.-C. Shin,
“Investigation on cell impedance for high-power lithium-ion batteries”, Journal of
Solid State Electrochemistry 11 (2007) 1405-1410, Copyright © (2007), with kind
permission of Springer Science and Business.
 Analysis of Cell Impedance for the Design of a High-Power… 91

0.0 Δ V(R1)

ΔV(RΩ)

Cathodic Polarization / V
0.1 ΔV(R2)

0.2
ΔV(R3)

0.3 ΔV(TML)
Fresh cell
Aged cell
0.4

0.5

0.6 ΔV(total)

0.7
0 2 4 6 8 10

Discharging Time / s

(a)

0.40 Fresh cell

Aged cell
0.35 ΔV(TML)
Proportional Contribution / -

0.30
ΔV(R3)

0.25

0.20
Δ V(R2)

0.15
Δ V(RΩ)

0.10

Δ V(R1)
0.05

0 2 4 6 8 10 12

Discharging Time / s
(b)

Figure 12. (a) Variations of elementary and total polarizations, obtained from the fresh
cell (solid line) and the aged cell (dashed line), with discharging time at 8C rate and (b)
dependence of proportional contributions of the elements to total polarization,
reproduced from (a). Figures 5a and b in D.-K. Kang and H.-C. Shin, “Investigation on
cell impedance for high-power lithium-ion batteries”, Journal of Solid State
Electrochemistry 11 (2007) 1405-1410, Copyright © (2007), with kind permission of
Springer Science and Business.
92 Hyung-Man Cho and Heon-Cheol Shin

Shown in Figure 12(a) are the calculated transients of elementary and total
polarization at the rate of 8 C for the fresh and aged cells. All the elementary
polarizations for the aged cell exceeded those for the fresh cells, strongly
indicating that the elementary resistances in the cell increased with cell aging.
The proportional contribution of elementary polarization to total polarization
(Figure 12(b)), reproduced from the transients, proved that the reaction
corresponding to the R3 element and the solid-state diffusion process
significantly contributed to the total polarization during the initial and later
stages, respectively, of continuous discharging for 10 s, irrespective of the
fresh and aged cells. Furthermore, the power degradation of the cell after aging
was mainly ascribed to the increase in the R3 value of the cell; i.e., the
contribution of R3 increased after cell aging by more than 5%, which is a
maximum among the increases in contribution of all the elementary
polarizations.
The preceding analysis helps us roughly quantify the contribution of the
individual reactions with different time constants; however, a two-electrode
electrochemical cell places a serious limitation on the reliable differentiation
of the time constants of the real reaction steps. That is, the impedance
spectrum obtained from a two-electrode electrochemical cell is significantly
distorted from the spectrum of the electrode of concern (i.e., the cathode) due
to the overlap of the relaxation times for all the reactions on the anode and
cathode sides. The separation in the contributions of the cathode and anode,
together with setting the design strategy of the materials, will be discussed in a
subsequent section.

3. Analysis Based on a Three-Electrode Electrochemical Cell

Shown in Figure 13 are potential transients during the discharging for 10 s

at different rates, obtained from the fresh and aged cells in a three-electrode
electrochemical cell configuration. With an increasing number of aging cycles,
the transients at the same discharging rate fell faster, indicating that the cell
resistance increased, and thereby the power performance of the cell was
degraded with cycling. To clarify the reaction steps to most affect the total
polarization in the course of the constant-current pulse discharging, and at the
same time explore the main factors in power degradation with cell aging, the
impedance spectra of the cathode and anode were separately measured at
different levels of cell aging.
 Analysis of Cell Impedance for the Design of a High-Power… 93

4.2
0.0
1C

+
4.0

Cell Potential / V vs. Li/Li

Cathodic Polarization / V
0.2
3.8 4C
0.4
3.6

8C 0.6
3.4
0.8
3.2
12C
1.0
3.0
Fresh cell 1.2
2.8
0 2 4 6 8 10 12

Discharging Tim e / s
(a)

4.2
10-Cycle Aged Cell 20-Cycle Aged Cell 0.0
+

4.0
Cell Potential / V vs. Li/Li

1C

Cathodic Polarization / V
0.2
3.8
0.4
4C
3.6
0.6
3.4
0.8
3.2 12C 8C

1.0
3.0
Aged cell 1.2
2.8
0 2 4 6 8 10 12

Discharging Time / s
(b)

Figure 13. Experimental cell potential (or cathodic polarization) transients during the
cathodic pulse discharging for 10 s at different rates, obtained from (a) the fresh cell
and (b) the aged cell.
94 Hyung-Man Cho and Heon-Cheol Shin

The impedance spectra of the cathode clearly exhibited two semicircles

and an inclined line, as shown in Figure 14(a). These are attributable to the
migration/charging of lithium ions in the SEI on the cathode, charge transfer
combined with double layer charging at the interface, and lithium diffusion
through LiCoO2 oxide, respectively. On the other hand, several semicircles
and an intermediate frequency inductive loop were characteristic of the
impedance spectra of the lithium anode (Figure 14(b)), the origin of which is
yet to be determined. The summed spectra of the cathode and anode, denoted
by the open circle in Figure 14(c), revealed a quantitative coincidence with the
impedance spectra measured under a two-electrode electrochemical cell
configuration. This strongly indicates that the impedance spectra of the
cathode and anode were successfully separated using our three-electrode
electrochemical cell.
From the impedance spectra of the full cell (Figure 14(c)), it appeared that
the first semicircle was nearly invariant, whereas the second semicircle
increased with cell aging. Accordingly, a conclusion might be drawn that the
SEI resistance of the cathode was almost constant, but its charge transfer
resistance was significantly raised with cell aging. However, the separated
impedance spectra (Figures. 14(a) and (b)) tell a different story: the SEI
resistance of the cathode in the high-frequency region increased with aging,
while the high-frequency impedance of the anode decreased. That is, the
increase in the SEI resistance of the cathode was offset by the decrease in
high-frequency impedance of the anode, making the high-frequency
impedance of full cell look invariant. Furthermore, the second semicircles of
the full cell impedance spectra of the aged cell reflected the intermediate-
frequency inductive loop of the impedance spectra for the anode. Actually, a
large inductive loop on the anode impedance spectrum considerably lowered
and depressed the second semicircle on the full cell impedance spectra.
Shown in Figures 15(a) and (b) are the equivalent circuits that model the
reactions in the cathode and anode, respectively. In particular, the equivalent
circuit for the lithium anode included the inductive element parallel to three
serial R-CPE elements, which proved to fit the impedance spectra containing
an intermediate-frequency inductive loop (although no physical meaning can
be attached to this at present [31, 38, 39]). The equivalent circuit for the full
cell can be constructed from the combination of the circuits for the cathode
and anode (Figure 15(c)).
For a theoretical analysis of the equivalent circuit, the Warburg impedance
of Figure 15(a) was replaced with a transmission line and all the CPEs were
assumed to be pure capacitors for the sake of simplicity. All of the electrical
 Analysis of Cell Impedance for the Design of a High-Power… 95

parameters of the reconstructed equivalent circuits were determined as

described in Sections III-2 and IV-2, and are summarized in Table 1. Shown in
Figure 16 are the variations of total polarization with discharging time,
determined from the theoretical analysis of the reconstructed equivalent circuit.
The calculated transients of total polarization bore a strong quantitative
resemblance to the experimental transients.

40
12
Fresh cell
- Imaginary Impedance / Ω

3.7 kHz
3.7 kHz 10-cycle aged cell
8 1.26 Hz 20-cycle aged cell
30 7.9 kHz

4 0.52 Hz

20 0
0 5 10 15

magnification 1 Hz

10

5 mHz 5 mHz
0
5 mHz Cathode
0 20 40 60 80

Real Impedance / Ω
2
10 -75

-50

Θ / deg
|Z| / Ω

1
10

-25

0
10 -3 0
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10

Frequency / Hz

(a) (a-2)

3.7 kHz Fresh cell

- Imaginary Impedance / Ω

10 2
10-cycle aged cell
20-cycle aged cell
3.7 kHz
2 kHz 5 mHz
0 5 mHz
5 4 6 8
magnification
5 mHz
3.2 Hz
0
0.7 Hz

1.9 Hz Anode
0 5 10 15 20 25

2
Real Imagianry / Ω
10

10

0
Θ / deg
|Z| / Ω

1
10

-10

-20
0
10 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10

Frequency / Hz

(b) (b-2)
96 Hyung-Man Cho and Heon-Cheol Shin

60
10
Fresh cell (2 electrode)

- Imaginary Impedance / Ω
Fresh cell (3 electrode)
5 10-cycle aged aell (2 electrode)
40 10-cycle aged cell (3 electrode)
0 20-cycle aged cell (2 electrode)
20-Cycle Aged Cell (3 electrode)
-5
0 10 20 30

20 magnification

0
Full Cell
0 20 40 60 80 100 120

Real Impedance / Ω
3
10 -40

-30
2
10

Θ / deg
|Z| / Ω

-20

1
10
-10

0
10 -3 0
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10

Frequency / Hz

(c) (c-2)

Figure 14. Nyquist plots of (a) cathode, (b) anode, and (c) full cell, obtained from the
fresh and aged cells at the cell potential of 4.1 V (vs. Li/Li+). The lines in (a) and (b)
were determined from the CNLS fittings of the impedance spectra to the equivalent
circuits. In (c), the summation of the impedance spectra of cathode and anode obtained
under three-electrode electrochemical cell configuration (lines) were compared with
the spectra measured under two-electrode electrochemical cell configuration (symbols).
(a)-2, (b)-2, and (c)-2 represent the corresponding Bode plots.
 Analysis of Cell Impedance for the Design of a High-Power… 97

RΩ,c CPEf CPEdl

Rf Rct

Zdiff
(a)

L RΩ,a CPE1 CPE2 CPE3 CPE4

R1 R2 R3 R4

R5 L

(b)

CPE4 CPE3 CPE2 CPE1 RΩ CPEf CPEdl

R4 R3 R2 R1 Rf Rct

Zdiff

L R5

(c)

Figure 15. Proposed equivalent circuits to model the reactions in (a) the cathode and
(b) the anode. (c) is the equivalent circuit for full cell, obtained from the combination
of (a) and (b).

The dependence of elementary polarizations on discharging time for the

fresh and aged cells were theoretically separated from the total polarization
(Figure 17), and the time-dependent proportional contributions of the
elementary polarizations to total polarization were calculated accordingly
(Figure 18). The main reason for the power degradation of the aged cell
proved to be a significant increase in polarization due to the charge transfer
resistance of the cathode; i.e., its proportional contribution to total polarization
increased from 30% (for the fresh cell) to 50% (for the 20-cycle aged cell),
which was greater than the increases in contribution caused by any other
elementary polarizations. This strongly indicates that priority in cell design for
the sustained operation of a high-power LIB should be given to surface
stabilization of active materials from, e.g., the addition of structure-stabilizing
elements [40, 41] and/or surface modification [42, 43].
98 Hyung-Man Cho and Heon-Cheol Shin

4.2
0.0
4.0 1C

Cathodic Polarization / V
0.2

Cell Potential / V vs. Li/Li

3.8
4C 0.4
3.6
0.6
3.4
8C 0.8
3.2
1.0
12C
3.0
Fresh cell 1.2
2.8
0 2 4 6 8 10 12

Discharging Time / s
(a)

4.2
10-cycle aged cell 20-cycle aged cell 0.0
4.0
1C
+

Cathodic Polarization / V
0.2
Cell Potentail / V vs. Li/Li

3.8
0.4
3.6 4C
0.6
3.4
0.8
3.2 12C
8C 1.0
3.0
Aged cell 1.2
2.8
0 2 4 6 8 10 12

Discharging Time / s
(b)

Figure 16. Calculated potential (or cathodic polarization) transients of (a) the fresh cell
and (b) the aged cell during the cathodic pulse discharging for 10 s at different rates,
determined from the theoretical analysis of the re-constructed equivalent circuit of
Figure 15.
 Table 1. Electrical parameters of (a) cathode and (b) anode at various levels of aging, determined from the complex
non-linear least squares (CNLS) fitting of impedance spectra to the equivalent circuits. (a) includes the chemical
diffusion coefficient D, diffusion length L and some values calculated therefrom.

(a)
(2)
RΩ (Ω) Rf (Ω) CPEf Rct (Ω) CPEdl(2) Aω D(3) L(4) RD(5) CD(5) r(5) c(5)
C (μF⋅sη-1) η C (mF⋅sη-1) η (Ω⋅s-0.5) (×10- (μm) (Ω) (F) (×10 (×106s⋅
11 2 -1 6
m ⋅s ) Ω⋅m Ω-1⋅m-1)
-1
)
Fresh <0.1(1) 11.86 31 0.71 14.95 7.7 0.98 1.92 5.71 5.0 1.27 0.35 0.25 0.07
10-Cycle Aged “ 17.77 42 0.71 20.81 6.4 0.99 2.34 3.87 5.0 1.88 0.35 0.38 0.07
20-Cycle Aged “ 23.31 50 0.68 44.01 5.5 0.96 2.91 3.88 5.0 2.34 0.30 0.47 0.06
(1)
Fitted values were close to zero due possibly to the artifact of the cell.
(2)
CPE is expressed in the form of C(jω)η
(3)
D at 4.1 V (vs. Li/Li+) was estimated from the galvanostatic intermittent titration technique.
(4)
L was the radius of the particle, determined from the SEM observation.
(5)
RD=Aω⋅L⋅D-1/2, CD=L2⋅RD-1⋅D-1, r=RD⋅L-1, c=CD⋅L-1.
(b)
RΩ (Ω) R1 (Ω) CPE1 R2 (Ω) CPE2 R3 (Ω) CPE3 R4 (Ω) CPE4 R5 L
C η C η C η C η (Ω) (H)
(μF⋅sη-1) (μF⋅sη-1) (mF⋅sη-1) (F⋅sη-1)
Fresh 5.1 3.43 3.95 1 8.57 84.5 0.83 3.31 9.32 0.92 14.82 0.84 0.69 13.41 4.52
10-Cycle Aged 4.2 1.78 0.82 1 3.54 47.4 0.96 10.7 55.6 0.60 8.78 0.90 0.56 6.85 2.09
20-Cycle Aged 4.2 1.67 1.12 1 3.46 83.8 0.93 39.9 51.0 0.71 7.31 2.25 0.70 9.84 3.37
100 Hyung-Man Cho and Heon-Cheol Shin

0.0 ΔVΩ 4.1

Δ V diff
ΔVf
0.1 4.0

+
Cathodic Polarization / V

Cell Potential / V vs. Li/Li

Δ V ct
Δ V anode
0.2 3.9

0.3 3.8

0.4 3.7
Δ V tot
0.5 3.6

0.6 3.5
Fresh cell
0.7 3.4
0 2 4 6 8 10 12

Discharging Tim e / s
(a)

0.0 ΔVΩ 4.1

ΔVdiff

0.1 ΔVanode ΔVf 4.0

+
Cathodic Polarization / V

Cell Potential / V vs. Li/Li

0.2 ΔVct 3.9

0.3 3.8

0.4 3.7

0.5 3.6
ΔVtot

0.6 3.5

10-Cycle Aged Cell

0.7 3.4
0 2 4 6 8 10 12

Discharging Time / s
(b)

Figure 17. (Continued)

 Analysis of Cell Impedance for the Design of a High-Power… 101

0.0 ΔVΩ 4.1

ΔVdiff

0.1 4.0

+
Cathodic Polarization / V
ΔVanode

Cell Potential / V vs. Li/Li

0.2 3.9
ΔVf

0.3 3.8

ΔVct
0.4 3.7

0.5 3.6

0.6 ΔVtot 3.5

20-cycle aged cell
0.7 3.4
0 2 4 6 8 10 12

Discharging Time / s
(c)

Figure 17. Variations of elementary and total polarizations, obtained from (a) the fresh
cell, (b) the aged cell, with discharging time at 4C rate. ΔVanode is the sum of the
contributions of the elementary polarizations in the anode side.

Fresh cell
Proportional Contribution to ΔVtot/-

0.5

0.4

0.3 ΔVanode
ΔVct

ΔVf
0.2

ΔVdiff
0.1
ΔVΩ

0.0
0 2 4 6 8 10 12
Discharging Time / s
(a)

Figure 18. (Continued)

102 Hyung-Man Cho and Heon-Cheol Shin

10-cycle aged cell

Proportional Contribution to ΔVtot/-

0.5

0.4

ΔVct
0.3
ΔVf

0.2
ΔVanode
ΔVdiff
0.1
ΔVΩ

0.0
0 2 4 6 8 10 12

Discharging Time / s
(b)
Proportional Contribution to ΔVtot/-

0.5 20-cycle aged cell

ΔVct

0.4

0.3
ΔVf

0.2

ΔVanode
0.1 ΔVdiff

ΔVΩ

0.0
0 2 4 6 8 10 12

Discharging Time / s
(c)

Figure 18. Time-dependent proportional contribution of elementary impedances to total

polarization for (a) the fresh, (b) the 10-cycle aged cell, and (c) the 20-cycle aged cell,
reproduced from Figure 17.
 Analysis of Cell Impedance for the Design of a High-Power… 103

V. CRITICAL FACTORS FOR LOW-TEMPERATURE

POWER DECLINE

1. Brief Description of Electrochemical Test Procedures

A three-electrode electrochemical cell was used to analyze the effect of

temperature on power performance. The components of the cell and its
fabrication procedure are the same as described in Section IV-3. For the
electrochemical tests, the as-prepared cell was initially cycled several times for
activation. Then, the electrochemical impedance spectra at a cell potential of
4.1 V (vs. Li/Li+) were obtained at temperatures ranging from 25 to 5 oC for a
frequency range of 50 kHz to 3 mHz. Current pulse tests were carried out
immediately after the impedance tests at each temperature by applying
different cathodic (discharging) currentsfor 5 s.

2. Effect of Temperature on Total and Elementary Polarizations

Since the reactions associated with battery operation are a thermal

activation process, the power density of the battery is significantly reduced
with decreasing temperature. The polarization transients at different
temperatures manifested the power decline at low operating temperatures, as
shown in Figure 19: at lower temperatures, the transients fell faster.
To investigate the main factors in the low-temperature (LT) power decline,
the impedance spectra were first determined at different temperatures (Figure
20). In the case of the impedance spectra for the cathode, the first and second
semicircles, caused by the reactions in the SEI and the interfacial charge
transfer combined with double layer charging, respectively, increased in size
with lowering temperature while the inclined line due to the solid-state
diffusion process became shorter. From the separated semicircles in the
impedance spectra for the anode measured at the low temperatures, it is proved
that at least four parallel resistive-capacitive elements were needed to properly
model the reactions in the anode during battery operation, the basis for which
is not yet clearly understood.
The equivalent circuits of Figure 15 are still valid to model the impedance
spectra for the cathode and anode. The diffusion impedance was substituted
for the transmission line, and its elementary resistance and capacitance were
evaluated in the same manner as in previous sections. All of the electric
104 Hyung-Man Cho and Heon-Cheol Shin

parameters of the reconstructed equivalent circuits are summarized in Table 2.

We note that the higher temperature sensitivity of the charge transfer
resistance of the cathode means a larger activation energy for it compared to
resistance for Li+ migration through the SEI, as demonstrated in Figure 21.
This further indicates that the low temperature power decline is mainly caused
by difficulty in the interfacial charge transfer reaction at low operating
temperatures, as is consistent with previous works [12, 44].

4.2
0.0
0.5 C
+

4.0
Cell Potential / V vs. Li/Li

2C

Cathodic Polarization / V
0.2
3.8
0.4
3.6 6C
0.6
3.4
0.8
10 C
3.2
1.0
3.0
o
T=25 C 1.2
2.8
0 1 2 3 4 5 6

Discharging Time / s
(a)

4.2
o o
15 C 5 C 0.0
0.5 C
+

4.0
Cell Potential / V vs. Li/Li

Cathodic Polarization / V

0.2
2C
3.8
0.4
3.6
0.6
3.4
6C
0.8
3.2
1.0
10 C
3.0
1.2
2.8
0 1 2 3 4 5 6

Discharging Time / s
(b)

Figure 19. Experimental cell potential (or cathodic polarization) transients during the
cathodic pulse discharging for 5 s at different rates, obtained at the operating
temperatures of (a) 25 and (b) 15 and 5 ℃.
Analysis of Cell Impedance for the Design of a High-Power… 105

25
o
25 C

- Imaginary Impedance / Ω
7.1 kHz o
20 15 C
5
4.6 Hz
o
5 C
15 6.8 kHz 3.1 Hz
6.8 kHz
0
1 Hz 3 mHz
10 0 5 10 15 20
magnification 3 mHz

0 3 mHz cathode
0 10 20 30 40

Real Impedance / Ω
2
10 -40

-30

-20

Θ / deg
|Z| / Ω

1
10

-10

0
0
10 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10

Frequency / Hz

(a) (a-1)

16
o
14 25 C
- Imaginary Impedance / Ω

2 0.3 kHz o
15 C
12 1.4 kHz o
5 C
10
0
8

6 4 5 6 7 8
0.1 kHz
4 magnification
3 mHz
2
3 mHz anode
0 3 mHz

5 10 15 20 25 30

Real Impedance / Ω
2
10 -20

-10
Θ / deg
|Z| / Ω

1
10

0
10 -3 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10

Frequency / Hz
(b) (b-1)
106 Hyung-Man Cho and Heon-Cheol Shin

40
10 o
25 C (2 electrode)

- Imaginary Impedance / :
35
o
25 C (3 electrode)
30 o
5 15 C (2 electrode)
o
25 15 C (3 electrode)
o
5 C (2 electrode)
20 0 o
10 20 30 5 C (3 electrode)
15
magnification
10

0
10 20 30 40 50 60 70 80

Real Impedance / :

(c) (c-1)

Figure 20. Nyquist plots of (a) cathode, (b) anode, and (c) full cell at the cell potential
of 4.1V (vs. Li/Li+) and the temperatures of 25, 15, and 5 ć. The lines in (a) and (b)
were determined from the CNLS fittings of the impedance spectra to the equivalent
circuits. In (c), the summation of the impedance spectra of cathode and anode obtained
under three-electrode electrochemical cell configuration (lines) were compared with
the spectra measured under two-electrode electrochemical cell configuration (symbols).
(a)-2, (b)-2, and (c)-2 represent the corresponding Bode plots.
Table 2. Electrical parameters of (a) cathode and (b) anode at various operating temperatures, determined from
the complex non-linear least squares (CNLS) fitting of impedance spectra to the equivalent circuits. (a) includes
the chemical diffusion coefficient D, diffusion length L and some values calculated therefrom.

(a)
Te RΩ (Ω) Rf (Ω) CPEf Rct (Ω) CPEdl Aω D L RD CD r c
mp. C η C η (Ω⋅s-0.5) (×10- (μm) (Ω) (F) (×106Ω (×106s⋅Ω
(oC) (μF⋅sη-1) (mF⋅sη-1) 11 2 -1
m ⋅s ) ⋅m-1) -1
⋅m-1)
25 3.5 10.57 7.7 0.88 8.48 6.8 0.65 0.76 4.71 5.0 0.55 0.96 0.11 0.19
15 4.0 11.33 6.2 0.91 10.59 8.9 0.74 0.92 4.67 5.0 0.67 0.79 0.13 0.16
5 4.1 12.01 11 0.83 16.66 8.7 0.91 1.13 4.50 5.0 0.84 0.66 0.17 0.13

(b)
Tem RΩ (Ω) R1 (Ω) CPE1 R2 (Ω) CPE2 R3 (Ω) CPE3 R4 CPE4 R5 L
p. (Ω) (Ω) (H)
(oC) C η C η C η C η
(F⋅sη-1) (F⋅sη-1) (mF⋅sη-1) (mF⋅sη-1)
25 4.2 5.1 5.2 0.88 1.4 1.6 0.93 1.7 0.13 0.77 0.98 0.22 1 N/A N/A
15 4.0 7.7 3.4 0.79 4.8 0.26 0.54 2.3 0.41 0.67 2.09 0.25 0.99 N/A N/A
5 4.9 6.3 0.3m 0.94 28 0.31 0.5 3.3 0.73 0.59 4.28 89.3 0.88 N/A N/A
108 Hyung-Man Cho and Heon-Cheol Shin

1
2x10

Ea = 23.339 kJ/mol

Resistance / Ω
Ea = 4.392 kJ/mol
1
10

+
Li migration through SEI
Interfacial charge transfer

3.3 3.4 3.5 3.6

3 -1
Inverse Temperature / 10 xK

Figure 21. Arrhenius plot of the resistance vs. inverse temperature, to determine the
activation energies for Li+ migration through SEI layer and interfacial charge transfer.

The remaining question is the extent to which the charge transfer

resistance affects total polarization in the course of battery discharging. Our
theoretical analysis of the reconstructed circuits led to the dependence of the
elementary polarization transients on operating temperatures (Figure 22), and
the proportional contribution of elementary impedances to total polarization
were, accordingly, estimated as a function of discharging time (Figure 23). At
the operating temperature of 5 oC, the proportional contribution of the
interfacial charge transfer resistance to total dc polarization was up to more
than 30% at the initial stage of discharging and it reached about 22% even at
the later stage of discharging, as shown in Figure 23(c).

3. Power Performance of Hybrid Electrodes

Since the LT power decline of a LIB is intrinsic and unavoidable,

hybridization of the typical battery working concept with the capacitor
working concept has recently been studied in an attempt to dramatically
increase the LT performance of LIBs, due primarily to the superior LT
performance of the capacitor [45]. The combination of insertion materials and
electrochemical double layer capacitor (EDLC) materials can be the case in
point of hybrid electrode. The methodology suggested in this section might be
 Analysis of Cell Impedance for the Design of a High-Power… 109

successfully utilized to gain an insight into LT pulse discharging of the cell

with hybrid electrode(s). We now consider a hypothetical equivalent circuit for
a cell of one hybrid electrode (Figure 24). We note that the electric element for
the EDLC materials, i.e., the capacitor is connected in parallel with those
elements for the insertion materials, because EDLC materials contribute to
charge storing independent of the insertion materials.

4.2

0.0 ΔVdiff
ΔVΩ
ΔVct 4.0
Cathodic Polarization / V

+
Cell Voltage / V vs. Li/Li
0.2 ΔVanode ΔVf
3.8

0.4
ΔVtot 3.6

0.6
3.4

0.8 o 3.2
T=25 C

1.0 3.0
0 1 2 3 4 5 6

Discharging Time / s
(a)

4.2
ΔVdiff
0.0
ΔVΩ
4.0
Cathodic Polarization / V

ΔVct
Cell Voltage / V vs. Li/Li

0.2 ΔVf
ΔVanode 3.8

0.4
3.6

0.6
ΔVtot 3.4

0.8 3.2
o
T=15 C
1.0 3.0
0 1 2 3 4 5 6

Discharging Time / s
(b)

Figure 22. (Continued)

110 Hyung-Man Cho and Heon-Cheol Shin

4.2

0.0 ΔVdiff

ΔVΩ 4.0

Cathodic Polarization / V

+
Cell Voltage / V vs. Li/Li
ΔVf
0.2
ΔVct 3.8

0.4 ΔVanode
3.6

0.6
3.4

0.8 3.2
o
T=5 C
ΔVtot
1.0 3.0
0 1 2 3 4 5 6

Discharging Time / s
(c)

Figure 22. Variations of elementary and total polarizations with discharging time at 4C
rate and at the temperatures of (a) 25, (b) 15 and (c) 5 ℃.

The calculated impedance spectra at different capacitances of the EDLC

materials are shown in Figure 25. As EDLC capacitance increases, the real
impedance that essentially determines the value of dc polarization in the
course of pulse charging/discharging decreases (see the real impedances at 1
Hz, as indicated in the figures). This strongly indicates that the addition of the
EDLC materials to the electrode is beneficial in reducing cell impedance.
Potential or polarization transients of the cell with a hybrid electrode
differ significantly from transients of a cell consisting only of typical insertion
electrodes: Figures 26(a) and (b) show the variations of potential or dc
polarization with discharging time for various EDLC capacitance values,
calculated for the nodes of Vhybrid,L/Vhybrid,R (for a hybrid electrode) and
Vtot,L/Vtot,R (for a full cell), respectively, of Figure 24. It is noted that the
capacitance of the EDLC materials has a strong influence on the polarization
due to the hybrid electrode (Figure 26(a)). That is, a milder decrease in total dc
polarization with larger EDLC capacitance (Figure 26(b)) is totally ascribed to
reduced polarization of the hybrid electrode.
 Analysis of Cell Impedance for the Design of a High-Power… 111

0.5
o
T=25 C

Proportional Contribution ΔVtot/-

0.4

ΔVf
0.3
ΔVct

ΔVΩ
0.2

ΔVanode

0.1
ΔVdiff

0.0
0 1 2 3 4 5 6

Discharging Time / s
(a)

0.5
o
T=15 C
Proportional Contribution to ΔVtot/-

0.4

ΔVanode
0.3

ΔVf
ΔVct
0.2
ΔVΩ

0.1

ΔVdiff

0.0
0 1 2 3 4 5 6

Discharging Time / s
(b)

Figure 23. (Continued)

112 Hyung-Man Cho and Heon-Cheol Shin

0.5

Proportional contribution to ΔVtot/-

o
T=5 C ΔVanode

0.4

0.3

ΔVct
0.2
ΔVf

ΔVΩ
0.1

ΔVdiff

0.0
0 1 2 3 4 5 6

Discharging Time / S
(c)

Figure 23. Time-dependent proportional contributions of elementary impedances to

total polarization at the temperature of (a) 25, (b) 15 and (c) 5 ℃, reproduced from
Figure 22.

Vtot,L Vtot,R

Vhybrid,L Vhybrid,R Vcounter,L Vcounter,R

VΩ,L VΩ,R
Rf,1 Rct,1 Rf,2 Rct,2

RΩ
Cf,1 Cdl,1 Cf,2 Cdl,2

Cedlc

Hybrid electrode Non-hybrid counter electrode

Full cell

Figure 24. Hypothetic equivalent circuit for a cell of one hybrid electrode where the
insertion materials and electrochemical double layer capacitor (EDLC) materials are
conceptually combined.
 Analysis of Cell Impedance for the Design of a High-Power… 113

90
Cedlc=0 F
80
-5
Cedlc=10 F

- Imaginary Impedance / Ω
70 -4
Cedlc=10 F
60

50

40

30

20
1 Hz
10
spectrum for
0 counter electrode

0 20 40 60 80

Real Impedance / Ω
(a)
90
-3
Cedlc=10 F
80 -2
Cedlc=10 F
- Imaginary Impedance / Ω

70 Cedlc=10 F
-1

60

50

40

30
1 Hz
20

10
spectrum for
0 counter electrode

0 20 40 60 80

Real Impedance / Ω
(b)

Figure 25. Calculated impedance spectra at different capacitances of the EDLC

materials. The closed symbols indicate the impedance values at 1 Hz.

When EDLC capacitance is greater than 1 F in this hypothetical system,

there is virtually no contribution of the hybrid electrode to total dc polarization
during the continuous discharging for 5 s, while total polarization depends
entirely on polarization due to the non-hybrid counter electrode. Accordingly,
it is anticipated that LT power decline can be greatly reduced when the
insertion materials, whose reaction impedance is highly temperature-sensitive,
become hybridized with the EDLC materials.
114 Hyung-Man Cho and Heon-Cheol Shin

0.0
1F

Cathodic Polarization / V
ΔV hybrid
0.2 ΔV counter
ΔVΩ

0.4 0.1 F

0.05 F

0.6 0.04 F

0.03 F
-4
10 F
0.02 F

0.8 -3 0.01 F
10 F
Cedlc =0 F

0 1 2 3 4 5

Real Impedance / Ω
(a)

0.0

0.2
Cathodic Polarization / V

0.4
1F

0.6

0.1 F
0.8

0.05 F
1.0
0.04 F
10 F
-4 0.03 F
0.02 F
1.2 -3
10 F 0.01 F

C edlc =0 F
1.4
0 1 2 3 4 5

R ea l Im p ed an ce / Ω
(b)

Figure 26. Variations of potential (or cathodic polarization) transients during the
cathodic pulse discharging for 5 s at various EDLC capacitance values, calculated for
(a) hybrid electrode and (b) full cell. Potential transients obtained for a non-hybrid
counter electrode (ΔVcounter) and an electrolyte (ΔVΩ) were included in (a) for the sake
of comparison.
 Analysis of Cell Impedance for the Design of a High-Power… 115

VI. CONCLUSION
The successful design of a high-power LIB is critically dependent on the
extent to which the effect of cell components on cell polarization is
quantitatively understood during cell operation. This study suggests a viable
way to quantify the time-dependent proportional contribution of elementary
polarizations (or individual reaction steps) during the pulse discharging
process, and provides a good starting point for high power cell design. The
present work can be summarized as follows:

1. Dependence of the contribution of elementary impedances to total dc

polarization on battery discharging time was successfully analyzed
based on a combination of electrochemical impedance spectroscopy
and theoretical analysis of equivalent circuit.
2. Interfacial charge transfer resistance of the cathode proved to be the
most important resistance factor in the course of high-rate battery
discharging at ambient and low operating temperatures. Improvement
of the electrochemical activity of the cathode is the appropriate way to
effectively lower the total dc polarization during battery operation and
enhance battery power. A hybrid electrode for which battery and
capacitor working concepts are combined might significantly elevate
the power density, particularly for low temperature operation.
3. From our comparative analysis on the time-dependent contribution of
elementary polarizations of fresh and aged cells, power degradation
after repeated discharge-charge cycles were attributable to a
significant increase in polarization due to charge transfer resistance of
the cathode. Stabilization of the surface structure of the active
materials would have priority over any other design strategies in order
to secure sustained high-power operation of a LIB.
4. Much caution should be taken regarding the effect of the lithium
anode on impedance spectra and polarization transients when they are
obtained under a two-electrode electrochemical cell configuration.
The impedance and polarization caused by a lithium anode
significantly changes the overall spectra and transients, respectively,
in value and shape.
5. The method suggested in this study gives us a viable way to determine
the critical factors for battery power, thereby enabling us to
systematically design a high-power LIB. Furthermore, this approach
could possibly be applied to the diagnosis of a battery with degraded
116 Hyung-Man Cho and Heon-Cheol Shin

power, and gives insight into the design of a high-power battery with
long shelf and calendar life.
6. The successful application of our method requires the construction of
equivalent circuits to perfectly model the cell reactions and at the
same time needs the information on the correlation between
elementary resistances and design parameters of cell components.
Nevertheless, an in-depth investigation on the discrepancy, after the
redesign of the cell, between calculated (or expected) power
performance and experimental performance, might make our
understanding of the reaction mechanism and the core design
parameters more complete. This leads to the virtuous cycle of
mechanism elucidation, components design, cell preparation, and
diagnosis of high-power LIBs.

ACKNOWLEDGMENTS
This work was supported by a Korea Research Foundation Grant funded
by the Korean Government (MOEHRD) (KRF-2006-331-D00713).
Furthermore, this work was partially supported by a grant-in-aid for the
National Core Research Centre Program from MOST and KOSEF (No. R15-
2006-022-01001-0).

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In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 4

CHEMICAL OVERCHARGE PROTECTION

OF LITHIUM-ION CELLS

Zonghai Chen∗, Yan Qin and Khalil Amine

Chemical Sciences and Engineering Division, Argonne National
Laboratory
9700 South Cass Avenue, Argonne, IL 60439, USA

ABSTRACT
Overcharge protection is not only critical for preventing the thermal
runaway of lithium-ion batteries, but also important for automatic
capacity balancing. This chapter compares three overcharge protection
strategies—external circuit protection, inactivation agents, and redox
shuttles—to highlight the advantage of redox shuttles for overcharge
protection. Then the redox shuttle history and mechanism are introduced
and the latest advances on redox shuttles are described. Fundamental
studies for designing stable redox shuttles for use in lithium-ion batteries
are also discussed.

∗
Corresponding author: E-mail: [email protected]
120 Zonghai Chen, Yan Qin and Khalil Amine

INTRODUCTION
Lithium-ion batteries have been widely used to power portable electronic
devices and they also have demonstrated promise for large-scale applications,
such as hybrid electric vehicles (HEV) [1] and stationary energy backup
systems [2, 3]. Thus, the intrinsic energy storage characteristics of Li-ion
batteries have attracted significant attention from both academic and industrial
communities. When a lithium-ion cell is fully charged, the positive electrode
contains a strong oxidizing transition metal oxide (i.e. Li1-xMO2, M=Ni, Co,
Mn), while the negative electrode contains lithiated carbon, a very strong
reducing material. Sandwiched between the positive electrode and the negative
electrode is a non-aqueous electrolyte that uses an organic carbonate solvent
and a lithium salt. In the cell, this solvent tends to be readily oxidized and
reduced. Thus, the lithium-ion cell itself is thermodynamically unstable and
the compatibility of the cell components is kinetically achieved with the
presence of the surface passivation films on the electrode surface. Therefore,
lithium-ion batteries are very sensitive to thermal and overcharge abuse and
pose significant fire hazards. Overcharge of lithium-ion cells can lead to
chemical and electrochemical reactions in battery components [4, 5], gas
release [4-6], and rapid increase of cell temperature [4-6]. It can also trigger
self-accelerating reactions in the batteries, which can lead to thermal runaway
and possible explosion [7].
Overcharge generally occurs during the charge of a battery pack with
multiple lithium-ion cells connected in series as shown in Figure 1. When a
battery pack is charged, the charger generally continuously monitors the
voltage of the battery pack to roughly estimate the state of charge (SOC) of the
battery pack; it does not monitor each cell and so assumes that each cell in the
pack is identical to the others in terms of capacity and SOC. However, this
assumption is difficult to validate in real operation for the following reasons:

• It is difficult for the manufacturers to assemble truly identical cells for

a specific battery pack; a small variation in cell capacity and cell
performance is normal.
• Some of the cells in the pack might age faster than the others,
resulting in reduced cell capacity.
• Accidents, such as abuses and mechanical damage, can increase the
variation among the cells in the battery pack.
• Finally, after a certain period of operation, the cells in the battery pack
can have different SOC from cell to cell.
 Chemical Overcharge Protection of Lithium-Ion Cells 121

Therefore, there is always chance that one or more cells in the battery
pack has less capacity than the others as shown in Figure 1a, and the cell with
less capacity is called weak cell (the second cell in Figure 1a). When this
battery pack is charged, the weak cell will reach its top SOC first while the
others are still not fully charged (see Figure 1b). At this point, the voltage of
the whole pack is still lower than the expected value and the charger will
continue to charge the pack and overcharge the weak cell. Therefore, the
overcharge protection must operate at the cell level to assure safe operation of
the battery pack. The cell-level overcharge protection can also reduce the need
for costly cell capacity balancing during battery manufacturing, maintenance,
and repair. With the cell-level overcharge protection mechanism, the battery
pack can be charged as a whole. When a cell reaches its top of SOC during
charge, the cell voltage can electrically trigger the overcharge protection
mechanism, and the excess current will be handled by the incorporated
overcharge protection mechanism without causing overcharge to the cell.
Under this mechanism, the charging process of the battery pack can continue
until all the cells are fully charged.

COMPARISON OF AVAILABLE TECHNOLOGIES

Currently, the technologies available for cell-level overcharge protection
include external voltage regulation, inactivation agents, and redox shuttles. A
brief comparison of these three mechanisms is given in Table 1.

Table 1. Comparison of different overcharge protection mechanisms.

External voltage
Characteristic regulation Inactivation agent Redox shuttle
Mechanism Electronic Permanent inactivation of the Active and
regulation overcharged cells by gassing and reversible
Reversible coating of insulator coating.
Irreversible.
Physical device Electric circuit Electrolyte Additive Electrolyte
additive
Weight, volume, Disadvantage Advantage Advantage
and cost
Heat generation Electric work Heat from electrochemical and Electric work
chemical reactions of the dditive.
Thermal Advantage Disadvantage Disadvantage
management
Exemplary Ref. [8, 9] Ref. [10-12] Ref. [13-17]
technologies
122 Zonghai Chen, Yan Qin and Khalil Amine

(a)
Normal Weak Normal Normal
V

~
(b)
Normal Weak Normal Normal
V
~
(a) Fully discharged battery packed; (b) partially charged battery pack with the weak
cell being fully charged. The blue bar indicates the state of charge of each cell.

Figure 1. Schematic of a battery pack with several cells connected in series on

charging.

External voltage regulation [8, 9] is the dominant technology for state-of-

the-art lithium-ion batteries. With this technology, the voltage of each lithium-
ion cell is continuously monitored by an external circuit board. Once the cell
voltage exceeds the regulated value, the external bypassing circuit is activated
and the charging current will flow through the external circuit instead of the
lithium-ion cell. There are several advantages associated with the external
voltage regulation. First of all, the regulated value of circuit board can be fine-
tuned according to the specific chemistry of the lithium-ion cells being
protected. Hence, external voltage regulation can be a universal technology to
provide overcharge protection for a wide range of energy storage devices. In
addition, if the overcharge situation occurs to a given cell, the excess current
passes through the external circuit instead of the cell, and, the heat converted
from the electric current is generated on the external circuit board instead of
the protected cell. This can ease the thermal management of the battery
system. The disadvantage of external voltage regulation is that it adds
complexity, weight, volume, and cost to the battery management system,
which can be a major drawback when the energy or power density of the
battery is highly demanded.
An alternative overcharge protection mechanism is to use inactivation
agents such as 3-thiophenylpropane [11], biphenyl [10] and 3-chlorothiophene
[12], and furan [12]. The advantage of this technology is that only a small
 Chemical Overcharge Protection of Lithium-Ion Cells 123

amount of the inactivation agents will be added to the non-aqueous

electrolytes as additives. Hence, there will be only small or no increase in the
weight and volume of the battery pack. Overcharge of the cell will result in the
polymerization of the additive [10, 12] or an electrochemical reaction that
generates a large amount of gas [11]. The resulted insulating polymer will
cover on the electrode surface and eventually block the pathway of lithium
ions; placing the cell in an open-circuit status. The generated gas can
significantly increase the internal pressure of the lithium-ion cell, to a point
where it activates the venting device built in the cell and permanently
inactivates the cell. Apparently, overcharge of lithium-ion cells incorporating
inactivation agents will permanently disable the cell and lead to the failure of
the whole battery pack.
The redox shuttle [13-15, 17] is an electrolyte additive that can be
reversibly oxidized/reduced at a characteristic potential and provides an
intrinsic overcharge protection for lithium-ion batteries that neither increases
the complexity and weight of control circuitry nor permanently disables the
cell when activated. The redox shuttle molecule (S) has its defined redox
potential, at which it can be oxidized on the positive electrode and form a
radical cation (S•+) (see Equation 1).

S Æ S•+ + e- (1)

The radical cation then travels to the negative electrode through the
electrolyte and is reduced in accordance with Equation 2.

S•+ + e- Æ S (2)

The redox shuttle molecule then diffuses back to the positive electrode for
the next redox cycle, and the electrons move from the positive electrode to the
negative electrode through the external circuit. During normal operation, the
redox potential of the redox shuttle is not reached and the molecules stay
inactive. When the cell is overcharged, the potential of the positive electrode
increases, and the redox cycle of the redox shuttle molecules is activated. The
net reaction of the redox cycle is to shuttle the charge forced by the external
circuit through the lithium-ion cell without also forcing intercalation/
deintercalation of lithium in the electrodes of the cell.
According to above comparison, we can see that redox shuttles have
promising applications for high-energy and high-power lithium batteries,
particularly for transportation applications, to reduce the weight and volume of
124 Zonghai Chen, Yan Qin and Khalil Amine

the battery pack. It is the major focus of this chapter to discuss the stability and
application of redox shuttles for 4V class lithium-ion batteries.

Table 2. Exemplary redox shuttles for overcharge protection

of 3V class lithium-ion batteries.

Redox potential
Redox shuttle Citation V vs. Li+/Li Oxidation reaction
I- [18, 19] 3.2 3I- - 2e Æ I3-
Br- [20] 3.78 3Br- - 2e Æ Br3-
Ferrocene [21] 3.05-3.38 Fc – e Æ Fc+
[22] 3.25 (Fc = ferrocene and
n-butylferrocene [21] 3.18-3.50 its derivatives)
[22] 3.18
N,N- [21] 3.13-3.68
Dimethylaminomethylferrocene
1,1-Dimethylferrocene [21, 23] 3.06-3.34
1-Acetylferrocene [22] 3.509
1-Benzoylferrocene [22] 3.51
Methyl Ferrocenecarboxylate [22] 3.505
Ferrocenecarboxamine [22] 3.486
1-(Dimethylamino)methylferrocene [22] 3.435
Ferrocenemethanol [22] 3.258
Ferrocenecarboxaldehyde [22] 3.541
N,N-Dimethylferrocene [22] 3.128

HISTORICAL REVIEW
The research on redox shuttles for overcharge protection of lithium-ion
batteries can be traced back to the 1980s, when Behl et al. reported that I- has
its first oxidation potential at about 3.25 V vs. Li+/Li and hence is suitable for
overcharge protection of 3V class lithium-ion batteries [18-19]. Table 2 lists
several exemplary 3V class redox shuttles reported in the open literature [18-
23].
The power of redox shuttles lies on the fact that their molecules
continuously move back and forth (“shuttle”) between the positive and
negative electrodes to carry a large amount of charge through the cell in a
short period of time; this mechanism was fully demonstrated by Bard et al.
using a scanning electrochemical microscope (SECM) to achieve single
molecule detection [24]. A small electrolyte droplet containing roughly 1
molecule of [(trimethylammonio)methyl]ferrocene was sandwiched between
 Chemical Overcharge Protection of Lithium-Ion Cells 125

an indium-tin oxide (ITO) glass and a SECM tip with a gap of 10 nm. It has
been demonstrated that the single molecule of [(trimethylammonio)
methyl]ferrocene can carry about 1 pA current from the SECM tip to the ITO
counter electrode with an amplification factor of about 107. This means that
the redox shuttle molecule has to complete 107 oxidation-reduction reaction
cycles every second. If the investigated molecule has a probability of 1 part
per million to undergo irreversible decomposition for each redox cycle, then a
simple calculation shows that the possibility of the redox shuttle to survive
after 1 second of testing is about 45 part per million. Therefore, an ideal redox
shuttle for lithium-ion batteries should be extremely stable to offer hours, or
even hundreds of hours, of overcharge protection. In addition, an ideal redox
shuttle is also expected to have a redox potential about 0.3–0.4 V higher than
the normal operation potential of the positive electrode to minimize the
leakage current, or self-discharge current, described as Equation 3.

⎛ε − Eo ⎞
i = i0 exp⎜⎜ ⎟⎟ (3)
⎝ RT ⎠
In Equation 3,
i = self discharge current density,
i0 = exchange current density that is a characteristic kinetic constant
for a
given electroactive specie,
ε = the potential of the working electrode, and
o
E = the standard redox potential of the electroactive specie.
Finally, a good solubility and high diffusion coefficient of the redox
shuttles in non-aqueous electrolytes are also highly desired to maximize their
mobility through the cell.

STABILITY OF REDOX SHUTTLES

Electronic Stability

After the first commercialization of lithium-ion batteries using LiCoO2 as

the positive electrode material, Adachi et al. proposed that aromatic
126 Zonghai Chen, Yan Qin and Khalil Amine

compounds can be the 4V redox shuttles for applications in state-of-the-art

lithium-ion batteries [25, 26]. They also showed that aromatic compounds with
two methoxyl substitution groups could have a better stability than their
unsubstituted counterparts [25]. Using 1,4-dimethoxybenzene as an example,
the authors believed that the added methoxy-substituted groups at the 1,4
positions helped provide more resonance structures to stabilize the doubly
oxidized cation (see Figure 2). This mechanism can also directly apply to 1,2-
dimethoxybenzene. However, doubly oxidized 1,3-dimethoxybenzene shows
less stable resonance structures and hence the 1,3 substitution configuration is
less favored.
Apparently, the resonance structures can explain the relative stability of
dimethoxybenzene with different substitution configurations. However, it will
be highlighted in the following pages that the redox shuttles for overcharge
protection in general only involve the first oxidation reaction, and the doubly
oxidized dimethoxybenzene generally undergoes a very fast irreversible
decomposition reaction. Therefore, the second oxidation reaction is generally
not involved in a working battery. Moreover, the relative stability of a doubly
oxidized cation might not be a good indicator for the stability of singly
oxidized cations.
It is believed that the need for two methoxyl groups comes from the
aromaticity, or the 4n+2 rule, of unsaturated hydrocarbons [27]. When the
number of electrons in the flat p-π molecular orbital equal 4n+2 (n is an
integer), the molecule possesses aromaticity and the charged structures can be
stabilized by delocalizing the charge in the big π orbital, reducing the net
charge on a single atom. Dimethoxybenzene is a good example for the 4n+2
rule with 6 π electrons in the benzene ring and one pair of p-electrons from
each conjugated O atom.
Figure 3 shows the molecular configurations of 1,4-dimethoxybenzene
and its corresponding radical cation, which is generated after 1,4-
dimethoxybenzene is oxidized (losing one electron). Both configurations are
presented according to the full geometry optimization using ab initio
calculations. The most significant difference between these configurations is
the tetrahedral angle between the methoxyl groups and the aromatic plane. At
its reduced state, 1,4-dimethoxybenzene has its methoxyl groups pointing out
of the aromatic plane (see Figure 3a). However, the methoxyl groups stay in
the aromatic plane when the molecule is oxidized to form a radical cation (see
Figure 3b). Figure 3b also shows a slight increase of the bond order between
the carbon atom (on the aromatic ring) and the oxygen atom.
 Chemical Overcharge Protection of Lithium-Ion Cells 127

O O O O

-2e

O O O O

Figure 2. Canonical structures of 1,4-dimethoxybenzene after two-electron oxidation.

(a)

(b)

Figure 3. Optimized geometry of 1,4-dimethoxybenzene in its (a) reduced state and (b)
oxidized state.

The above evidence indicates some sort of interaction between the

aromatic ring and the oxygen atom, and the significance of the interaction
needs to be verified. Thus, the geometry of the transition state of both the
reduced state and the radical cation was also optimized by fixing one of the
methoxyl groups in or out of the aromatic plane. The transition state
mentioned above is for the rotation of the methoxyl group with the C-O bond.
The energy of each state was determined by density function theory. The
energy differences between the in-plane configuration and the out-of-plane
configuration are listed in Table 3. Apparently, the energy difference is the
energy barrier needed to rotate the C(ph)-O σ bond from an out-of-plane
configuration to an in-plane configuration. The energy barrier for the reduced
128 Zonghai Chen, Yan Qin and Khalil Amine

state is about -11.2 kJ/mol, which is acceptable for the rotation of the σ bond.
When the molecule is oxidized, the energy barrier jumps to about 52.7 kJ/mol,
which is unusually high for the simple rotation of the σ bond.

Table 3. Energy barriers for C-X bond rotation.

Chemical Name Chemical Structure Energy Barrier Energy Barrier

for Reduced for Oxidized
State (kJ/mol) State (kJ/mol)
1,4- -11.2 52.7
dimethoxybenzene
O O
(X=O)

1,4-dimethyl 0.2 3.1

benzene (X=C)
H3C CH3

1,4-dimethylthio 2.3 71.2

benzene (X=S)
S S

(Reproduced from J. Electrochem. Soc., 153: A2215, Copyright (2006), with

permission from the Electrochemical Society.)

(a) π−π
π−π

(b) π−π

(Reprinted from J. Electrochem. Soc., 153: A2215, Copyright (2006), with permission
from the Electrochemical Society.)

Figure 4. Schematic illustration of π-π interaction between the aromatic ring and the
substitution groups.
 Chemical Overcharge Protection of Lithium-Ion Cells 129

Figure 4a schematically shows the highest occupied molecular orbital

(HOMO) configuration of the oxidized 1,4-dimethoxybenzene. The oxygen
atom in Figure 4a adopts an sp2 hybrid configuration with one O-C σ bond,
one full sp2 orbital staying in the aromatic plane, and one full p-orbital rotating
perpendicular to the aromatic plane. Obviously, the p-orbital of the oxygen
atom cannot receive more electrons, but it can partially donate its electrons to
the aromatic ring through the π-π interaction, as shown in Figure 4a. When the
molecule is not oxidized, there is no formal charge bearing on the aromatic
ring, so that the electron donation seems insignificant and the π-π interaction
is weak. Thus, the C(ph)-O bond has more σ characteristics and has a small
energy barrier for rotation. When the molecule is oxidized, the donation of an
electron from the oxygen atom to the aromatic ring becomes significant
because the aromatic ring bears a +1 formal charge. If one of the methoxyl
groups rotates by 90°, as shown in Figure 4b, the p-orbital of the oxygen atom
will stay in the aromatic plane and the π-π interaction will be deconstructed,
which is believed to contribute to the high rotation energy barrier of the radical
cation.
Table 3 also lists the rotation energy barriers of 1,4-dimethyl benzene,
which lacks π-π interaction between the aromatic ring and the substitution
groups because of the sp3 configuration of carbon atoms in the substitution
groups. As expected, the rotation energy barrier for both reduced and oxidized
1,4-dimethybenzene is very small because of the lack of π electrons in the
substitution groups. Another typical example is 1,4-dimethythio benzene,
which has very similar electronic structure to 1,4-dimethoxybenzene. The 3p
electrons on S can interact with the aromatic ring as the 2p electrons on O do.
Therefore, a high rotation energy barrier is also predicted by the theoretical
calculation for the oxidized state of 1,4-dimethythio benzene, as shown in
Table 3.
Given the significance of the lone p electrons on the substitution groups,
there is a question about the stability of V-group-based (such as N) substituted
aromatic compounds. In order to answer this question, we tested some
commercially available aromatic compounds comprising N in the full cell
configuration. Such compounds proved to be very unstable as redox shuttles.
A reasonable explanation is that the amine group, a Lewis base, is susceptible
to attacking by the Lewis acid like Li+. Once the amine group is attacked, the
N atom is forced to adopt a sp3 configuration and lose the π-π interaction with
the aromatic ring. (Note: –OCH3 can also be attacked by H+ or Li+.) Group VI
elements, such as O or S, have two lone pairs of electrons and can maintain the
130 Zonghai Chen, Yan Qin and Khalil Amine

sp2 configuration even after being attacked by the Lewis acid (i.e., H+ or Li+),
presuming that the possibility of accepting more than one Lewis acid can be
ignored. Therefore, some S-based aromatic compounds were also reported as
redox shuttles for overcharge protection [28-30].

Structural Stability

Although stabilized by two methoxyl groups, 1,4-dimethoxybenzene has

been reported undergoing a radical polymerization reaction when being
oxidized [31], as shown in Equation 4.

O O
-2ne
n + 2nH+
n
O O (4)

It is speculated that the polymerization mechanism in Eq. 4 involves two

steps. Once 1,4-dimethoxybenzene is oxidized, a radical cation will be formed,
and the radical cation can be further stabilized by losing a proton with no
charge bearing on the aromatic ring (see Equation 5). The resulted radical can
attack other 1,4-dimethoxybenzene molecule as shown in Equation 6. After the
polymerization reaction, 1,4-dimethoxybenzene will be converted into a
polymer and lose shuttle capability. Hence, 1,4-dimethoxybenzene cannot be a
reversible redox shuttle for lithium-ion batteries.

O O O
-e
+ H+

O O O (5)

O O O O O O

+ -e + H+

O O O O O O (6)
 Chemical Overcharge Protection of Lithium-Ion Cells 131

Adachi et al. proposed that halogenated dimethoxybenzene could be a

stable redox shuttle for overcharge protection of 4V class lithium-ion batteries
[25, 26], with 1-bromo-2,5-dimethoxybenzene identified as most stable [25].
However, Dahn et al. reported that 1-bromo-2,5-dimethoxybenzen is not stable
at all [14]. Figure 5 shows the voltage profile of a LiFePO4/graphite lithium-
ion cell during the overcharge test. The electrolyte used was 0.08 M 1-bromo-
2,5-dimethoxybenzene and 0.7 M lithium bis(oxalato)borate (LiBOB) in a
mixture solvent of propylene carbonate (PC) and dimethyl carbonate (DMC)
with a volume ratio of 1:2. When the cell was initially charged, its voltage
increased normally with the charge time. The cell voltage surged up sharply
after the cell was fully charged at about 3.7 V until the cell voltage reached
about 4.3 V, at which point the redox shuttle mechanism of 1-bromo-2,5-
dimethoxybenzene was activated. Figure 5 clearly shows that 1-bromo-2,5-
dimethoxybenzene can provide a certain amount of overcharge protection, but
the overcharge protection disappeared after 6 cycles with 100% overcharge for
each cycle [14].

(Reprinted from Electrochem. Solid-State Lett., 8(1):159, Copyright (2005), with

permission from the Electrochemical Society.)

Figure 5. Cell potential vs. time for a LiFePO4/graphite cell containing a 1-bromo 2,5-
dimethoxybenzene shuttle additive. The electrolyte salt was 0.7 M LiBOB. The x axis
for (a) covers the time periods of 0–50 h, (b) 50–100 h, (c) 100–150 h, and (d) 150–200
h.
132 Zonghai Chen, Yan Qin and Khalil Amine

As a comparison, Figure 6 shows the voltage profile of another

LiFePO4/graphite lithium-ion cell using 0.08 M 1,4-ditertbutyl-2,5-
dimethoxybenzene as the redox shuttle instead of 1-bromo-2,5-
dimethoxybenzene. Under the same testing condition, the redox shuttle
mechanism of the cell with 1,4-ditertbutyl-2,5-dimethoxybenzene was still
fully functional after more than 120 cycles [14]. The instability of 1-bromo-
2,5-dimethoxybenzene as a redox shuttle can be simply attributed to (1) 1,4-
dimethoxybenzene itself is not stable after oxidation, as shown in Equation 4
and (2) substitution of electron withdrawing group, such as a halogen, on the
benzene ring will increase the positive atomic charge bearing on the aromatic
ring and ease the initiation of the polymerization reaction (Equation 5). The
density function theory calculation shows that the energy needed for reaction
(5), cleavage of C-H bond in the singly oxidized 1,4-dimethoxybenzene, is
about 1,200 kJ/mol. The energy needed for 1,4-difluoro-2,5-
dimethoxybenzene is about 1,000 kJ/mol while the energy needed for 1,4-
ditertbutyl-2,5-dimethoxybenzene is about 1,250 kJ/mol [27]. Therefore, it can
be concluded that the partial substitution of hydrogen in the aromatic ring can
have only a limited impact on the deprotonation reaction (Eq. 5). Therefore,
the exemplary stability of 1,4-ditertbutyl-2,5-dimethoxybenzene cannot simply
be explained by the stabilization effect of the tertbutyl groups that donate an
electron. A reasonable speculation is that the bulky terbutyl groups prevent the
1,4-ditertbutyl-2,5-dimethoxybenzene and its radical cation from attacking
each other and hence suppress the polymerization reaction as shown in
Equation 6 [14].
In order to accelerate the search for stable redox shuttles, Dahn et al.
established a computational method to roughly predict the stability of redox
shuttles [32]. In Dahn’s method, the binding energy (Eb) of an ethyl radical
and candidate redox shuttle molecule is calculated; a low binding energy is
expected to correlate to a higher stability. The computational results of this
method agreed well with the previous experimental results reported by Dahn’s
group; 2,5-tert-butyl-1,4-dimethoxybenzene [14, 33, 34] is the most stable one,
followed by 10-methylphenothiazine [28, 33] and 2,2,6,6,-
tetramethylpiperdine-1-oxyl [33, 35]. By examining Equation 6, one can
quickly find that Dahn’s method basically uses the ethyl radical to mimic the
radical generated after a redox shuttle molecule is oxidized (see Equation 5) to
reduce the computational cost. However, there are still several decomposition
reactions that cannot be predicted with this mechanism. For example, fully
substituted aromatic compounds [27], such as 2,3,5,6-tetrafluoro-1,4-
ditertbutybenzene [36], are unlikely to generate a free radical. There are also
 Chemical Overcharge Protection of Lithium-Ion Cells 133

circumstances in which the decomposition reaction is an SN1 reaction, such as

the cleavage of C-O bond in the alkoxy groups [36].

(Reprinted from Electrochem. Solid-State Lett., 8(1):159, Copyright (2005), with

permission from the Electrochemical Society.)

Figure 6. Cell potential vs. time for a LiFePO4/graphite cell containing a 2,5-
ditertbutyl-1,4-dimethoxybenzene shuttle additive. The electrolyte salt was 0.7 M
LiBOB. The x axis for (a) covers the time period of 0–50 h, (b) 1,000–1,050 h, (c)
2,000–2,050 h, (d) 3,500–3,550 hours.

Figure 7 shows the results of ab initio calculations on the decomposition

pathway of 2,3,5,6-tetrafluoro-1,4-ditertbutybenzene after oxidation. The ab
initio calculation shows that 2,3,5,6-tetrafluoro-1,4-ditertbutybenezene can be
oxidized at a potential of about 4.32 V vs. Li+/Li, which agrees well with the
experimental results as shown in Figure 8a. The ab initio calculation also
shows that 2,3,5,6-tetrafluoro-1,4-ditertbutybenzene radical cation (singly
oxidized) will spontaneously lose a tertbutyl radical and form a semiquinone.
The semiquinone will then be further oxidized at 3.43 V vs. Li+/Li, which is
134 Zonghai Chen, Yan Qin and Khalil Amine

much lower than the first oxidation potential. The ab initio calculation clearly
shows that the final product is 2,3,5,6-tetrafluoroquinone after losing a second
tertbutyl group. These theoretical results were also confirmed with
experimental data, as shown in Figure 8.
Figure 8a shows that one irreversible oxidation peak was observed with
the onset potential at about 4.1 V vs. Li+/Li. Once the irreversible oxidation
reaction occurred, an irreversible reduction peak was observed at about 3.0 V
vs. Li+/Li accordingly. After the electrolyte was tested up to 4.6 V vs. Li+/Li
for several cycles, a small reduction peak was observed at about 2.96 V vs.
Li+/Li even when the upper cutoff potential was set to 4.0 V vs. Li+/Li (see
black line in Figure 8b). In order to confirm the degradation pathway, a small
amount, but not measured, of 2,3,5,6-tetrafluoroquinone (TFQ) was added to
the test electrolyte, and a significant intensity increase of the peak at 2.96 V
was observed (see Figure 8b). This finally confirmed that the product of the
decomposition reaction is TFQ [36]. Another reported example that undergoes
similar decomposition is 2,5-di-tertbutyl-1,4-dimethoxybenzene. Although
2,5-di-tertbutyl-1,4-dimethoxybenzene has been reported as a stable redox
shuttle [13, 14, 33, 34, 37, 38], it can also undergo an irreversible
decomposition reaction after being doubly oxidized [36, 39]. It is believed that
2,5-di-tertbutyl-1,4-dimethoxybenezene is stable up to singly oxidized state,
but can lose one or two methyl groups to form semiquinone or quinone after
being doubly oxidized.

O O O
4.32V vs. Li+/Li 4.88V vs. Li+/Li F F
F F F F
.
+ 2+
F F F F F F
O O O

-790 kJ/mol -1127 kJ/mol

O 3.43V vs. Li+/Li O

F F F F

F F F F
O O

-879 kJ/mol
O
F F

F F
O

Figure 7. Schematic of decomposition pathway of oxidized 2,3,5,6-tetrafluoro-1,4-di-

tertbutybenzene.
 Chemical Overcharge Protection of Lithium-Ion Cells 135

60
(a)

40

Current, μA
20

-20
3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6
+
Potential, V vs. Li /Li
0.5
(b)
0.0

-0.5
Current, μA

-1.0

-1.5
No TFQ added
-2.0 TFQ added

-2.5
2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
+
Potential, V vs. Li /Li
(Reprinted from Electrochim. Acta, Vol 53/2: 453-458, Copyright (2007), with
permission from Elsevier)

Figure 8. (a) Cyclic voltammograms of 50 mM 2,3,5,6-tetrafluoro-1,4-di-tert-

butoxybenzene and 1.0 M LiPF6 in EC/EMC (3:7, by weight), and (b) Cyclic
voltammograms of 50 mM 2,3,5,6-tetrafluoro-1,4-di-tert-bytoxybenzene without and
with the addition of 2,3,5,6-tetrafluorquinone (TFQ).

EXAMPLES OF STABLE REDOX SHUTTLES

Aromatic Redox Shuttles

The discussion so far has demonstrated that redox shuttles can have
multiple decomposition pathways, making the design of a stable redox shuttle
136 Zonghai Chen, Yan Qin and Khalil Amine

very difficult. Several compounds have been reported in the literature as stable
redox shuttles for overcharge protection of lithium-ion batteries [13-17, 28, 35,
40-42], and they are useful models for establishing guidelines for the search
for the next stable redox shuttle.
Aromatic compounds were proposed as promising redox shuttles for
overcharge protection of 4V class lithium-ion batteries about a decade ago.
However, the first stable aromatic redox shuttle was recently reported by Dahn
et al. [14], in which work 2,5-di-tertbuty-1,4-dimethoxy, whose redox
potential is about 3.96 V vs. Li+/Li, showed unprecedented stability as a redox
shuttle for lithium-ion cells (see Figure 9). Figure 9 shows the charge and
discharge capacity of a LiFePO4/graphite lithium-ion cell comprising 0.08 M
2,5-di-tertbuty-1,4-dimethoxybenzene during overcharge test, and the voltage
profile of this cell is shown in Figure 6. It is shown that the cell was charged
for about 290 mAh/g and delivered about 145 mAh/g during discharge. The
difference between the charge capacity and the discharge capacity was caused
primarily by the overcharge of the cell (~100% overcharge) and was handled
by the added redox shuttle, 2,5-di-tertbutyl-1,4-dimethoxybenzene. The
overcharge protection mechanism survived for more than 260 cycles—in other
words, the cell had tolerated more than 260 times of its practical capacity
before the overcharge protection mechanism failed.

(Reprinted from Electrochem. Solid-State Lett., 8(1):159 (2005), Copyright (2005),

with permission from the Electrochemical Society.)

Figure 9. Positive electrode specific capacity vs. cycle number for a LiFePO4/graphite
cell charged and discharged at a C/2 rate at 30°C. A 0.7 M LiBOB-based electrolyte
containing 0.08 M 2,5-ditertbutyl-1,4-dimethoxybenzene was the shuttle. Each
 Chemical Overcharge Protection of Lithium-Ion Cells 137

recharge was for a constant capacity selected to be 200% of the nominal cell capacity.
Each discharge was to a 2.5 V cutoff potential.

Another aromatic redox shuttle reported by Dahn et. al. is 10-

methylphenothiazine (MPT), which has a redox potential of about 3.47 V vs.
Li+/Li. Figure 10 shows (a) the voltage profile and (b) specific
charge/discharge capacity of a LiFePO4/Li4Ti5O12 lithium-ion cell containing
0.1 M MPT in 0.5 M LiPF6 in a mixture solvent of propylene (PC), dimethyl
carbonate (DMC), ethylene carbonate (EC), and diethyl carbonate (DEC) with
a volume ratio of 1:2:1:2 as the electrolyte. Under the specific overcharge
protocol, about 160% overcharge for each cycle, the overcharge protection
provided by the added MPT survived for more than 200 cycles. Compared to
2,5-di-tertbuty-1,4-dimethoxybenzene, MPT would be expected to be very
unstable because of (1) the stabilization effect of N-based substitution is
expected to be much weaker than VI group, such as O- or S-based substitution
groups, and (2) the unprotected C-H bond on the aromatic ring is believed to
be susceptible to attack by radicals (see equations 5 and 6). The surprising
stability of MPT (see Figure 10) can be explained by its low redox potential,
which is about 0.5 V lower than that of 2,5-ditert-butyl-1,4-
dimethoxybenzene. A speculation on the stability of MPT is that MPT
absorbed less energy to be oxidized into a radical cation, and hence the
possibility of C-H cleavage to form a radical (Equation 5) is lower than that of
2,5-di-tertbuty-1,4-dimethoxybenzene.
The redox shuttles mentioned above have a redox potential lower than 4.0
V vs. Li+/Li, and are only practical for overcharge protection of lithium-ion
cells using LiFePO4 as the positive electrode. However, the materials
commonly used in current lithium-ion batteries generally have a higher
working potential (>4.0 V vs. Li+/Li). These materials are primarily LiCoO2
and a small portion of LiMn2O4 and Li[Mn1-x-yNixCoy]O2. Therefore, there is a
need to develop redox shuttles with a redox potential of 4.2 V vs. Li+/Li or
higher.
Dahn et. al. have shown that the redox potential of fluorinated 2,2,6,6-
tetramethylpiperinyl-oxides (TEMPO) increases with the degree of
fluorination [35]. It is well known that the substitution of an electron-
withdrawing group such as F around the redox active site, -N-O radical in the
case of TEMPO, can reduce the electron density on the active site and increase
the energy needed to withdraw one electron out of the active site (oxidation
process). Therefore, substitution of electron withdrawing groups can be an
effective way to increase the redox potential of aromatic redox shuttles for
138 Zonghai Chen, Yan Qin and Khalil Amine

applications in highe-voltage systems. It is also known that the substitution of

electron-withdrawing groups will increase the positive charge density at the
active site after it is oxidized. In the case of fluorinated dimethoxybenzene, the
substitution of strong electron-withdrawing groups like F will facilitate the
deprotonation reaction (Equation 5) and hence enhance the decomposition or
polymerization of aromatic redox shuttles [27]. Therefore, full substitution is a
natural strategy to take advantage of both higher redox potential with electron-
withdrawing substitution and the elimination of the post-oxidation
deprotonation reaction [27]. The discovery of 2-(pentafluorophenyl)-
tetrafluoro-1,3,2-benzodioxaborole (PFPTFBB) as a stable redox shuttle is an
example to apply the full substitution strategy [17].

(Reprinted from J. Electrochem. Soc., 153: A288, Copyright (2006), with permission
from the Electrochemical Society.)

Figure 10. (a) Potential vs. time for a LiFePO4/Li4Ti5O12 coin cell containing 0.1 M
MPT in 0.5 M LiPF6 electrolyte solution charged and discharged at a nominal C/2 rate.
Selected cycles are shown. (b) Positive electrode specific capacity vs. cycle number for
the same cell.
 Chemical Overcharge Protection of Lithium-Ion Cells 139

Figure 11 shows cyclic voltammograms of 0.05 M PFPTFBB and 1.2 M

LiPF6 in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (3:7, by
weight). Figure 11 shows that PFPTFBB has a reversible redox reaction at
about 4.43 V vs. Li+/Li. The onset potential of PFPTFBB is about 4.3 V vs.
Li+/Li, which is high enough to provide overcharge protection for most state-
of-the-art positive electrode materials. Figure 12 shows the charge/discharge
capacity of a graphite/LiNi0.8Co0.15Al0.05O2 lithium-ion cell containing 5 wt%
PFPTFBB in the electrolyte, which was 1.2 M LiPF6 in EC/PC/DMC (1:1:3,
by weight). The cell was charged and discharged at a constant current of C/10
(0.2 mA). During the charging process, the cell was charged to 4.95 V or until
4.0 mAh charge was delivered (100% overcharge). The cell was initially tested
at 25oC for 20 cycles and was then heated in an oven to 55oC for another 50
cycles to check the stability of the redox shuttle under a more aggressive
testing condition. After that, the cell was tested with a higher constant current
of C/5 (as shown above the curve in Figure 12). After 50 cycles at 55oC, the
overcharge protection of the redox shuttle was maintained and the cell
capacity remained very stable, even though the cell was 100% overcharged
every cycle. Afterward, the cell was further tested at 25oC and 55oC with a
constant current of C/5 and 100% overcharge. The overcharge protection
provided by PFPTFBB finally failed after 170 cycles of 100% overcharge.
Figure 12 also shows that the cell completely lost its capacity after 125 cycles.
However, the redox shuttle mechanism remained active for another 50 cycles
at 55oC after the cell failed.
The uniqueness of PFPTFBB is that it also has a boron-based electron-
deficient center, which can serve as an anion receptor with the potential to
improve the performance of lithium-ion cells [43]. Figure 13 shows the
discharge capacity of MCMB/Li1.1[Ni1/3Co1/3Mn1/3]0.9O2 lithium-ion cells with
and without the addition of PFPTFBB as the electrolyte additive. The “AR”
labeled on the graph stands for anion receptor and specifically for PFPTFBB.
It was confirmed that the addition of PFPTFBB to the electrolyte can
significantly improve the capacity retention of lithium-ion cells like other
anion receptors [43]. The improvement on the cycling performance was
believed to be due to (1) the dissolution of LiF, an insulator to both electron
and lithium-ion, from the surface of electrode materials by the added anion
receptor [43] and (2) enhanced formation of a solid electrolyte interphase on
the negative electrode for better protection [43]. Figure 11 shows the CV of
PFPTFBB combining with equivalent amount of LiF. Clearly, the redox
reaction at about 4.4 V vs. Li+/Li was maintained after PFPTFBB reacted with
140 Zonghai Chen, Yan Qin and Khalil Amine

LiF. This confirms that PFPTFBB is a bifunctional electrolyte additive,

serving as both redox shuttle and anion receptor [17].

8
5 mM, 20 mV/sec
6 PFPTFBDB
PFPTFBDB + LiF
4
Current, μA
2

-2

-4

-6
3.6 3.8 4.0 4.2 4.4 4.6 4.8
Potential, V
(Reprinted from Electrochem. Commun., Vol 9: 703-707, Copyright (2007), with
permission from Elsevier)

Figure 11. Cyclic voltammograms of 0.05 M PFPTFBB and 1.2 M LiPF6 in EC/EMC
(3:7, by weight) showing the electrochemical reactivity of PFPTFBB-F- using a
Pt/Li/Li three-electrode cell.

o o o o
25 C 55 C 25 C 55 C
5
C/10 C/10 C/5 C/5
4
Capacity, mAh

1 Charge
Discharge
0

0 20 40 60 80 100 120 140 160 180

Cycle number
(Reprinted from Electrochem. Commun., Vol 9: 703-707, Copyright (2007), with
permission from Elsevier)

Figure 12. Charge and discharge capacity of a graphite/LiNi0.8Co0.15Al0.05O2 lithium-

ion cell during the whole course of overcharge test. The electrolyte used contained 5
wt% PFPTFBB.
 Chemical Overcharge Protection of Lithium-Ion Cells 141

2.0
1.8
1.6
1.4
Capacity, mAh

1.2
1.0
No additive
0.8 3.5% AR
0.6 3.5% AR

0.4
0.2
0.0
0 30 60 90 120 150 180 210 240 270 300
Cycle number
(Reprinted from Electrochem. Commun., Vol 9: 703-707, Copyright (2007), with
permission from Elsevier)

Figure 13. Capacity retention of MCMB/Li1.1[Ni1/3Co1/3Mn1/3]0.9O2 cells showing the

positive impact of PFPTFBB as an anion receptor. The cells were cycled between 3.0
V and 4.0V with a constant current of C/2 at 55oC.

Non-Aromatic Redox Shuttles

In addition to the aromatic redox shuttles discussed above, several non-

aromatic compounds have been reported capable of providing long-term
overcharge protection for lithium-ion cells [15, 35, 41, 44-48]. TEMPO is an
unusually stable neutral radical that has been extensively investigated in
medicinal and biological research. Recently, Dahn et al. reported that TEMPO
is capable of reversible redox reaction at 3.52 V vs. Li+/Li [35, 41], and
suggested TEMPO as redox shuttle for overcharge protection of LiFePO4-
based lithium-ion cells. Figure 14 shows the capacity vs. cycle number of a
Li4Ti5O12/LiFePO4 lithium-ion cell that was cycled for 120 cycles. The
electrolyte tested was 0.3 M TEMPO and 0.5 M LiBOB in PC/DMC/EC/DEC
(1:2:1:2 by volume), and the cell was tested with a constant current of C/5.
During the whole course of overcharge testing, the excess charge shuttled by
142 Zonghai Chen, Yan Qin and Khalil Amine

TEMPO was about 20 Ah, which is about 160 times the practical capacity of
the cell.

(Reprinted from J. Electrochem. Soc., 153: A1800, Copyright (2006), with permission
from the Electrochemical Society.)

Figure 14. Charge and discharge capacity of a Li4Ti5O12/LiFePO4 coin cell with 0.3 M
TEMPO in a 0.5 M LiBOB electrolyte solution charged and discharged with a current
of C/5. Each charge was 20 h long, leading to about 15 h of shuttle-protected
overcharge during each cycle.

Another class of non-aromatic redox shuttles is lithium borate cluster

salts, Li2B12F12-xHx(X=1,2,...12) [15, 44], whose redox potential ranges from
4.2 V to 4.7 V vs. Li+/Li depending on the degree of fluorination. For instance,
Li2B12F12 has a redox potential of 4.74 V vs. Li+/Li and is capable of providing
overcharge protection for all state-of-the-art positive electrode materials. The
biggest advantage of this class of redox shuttles is that they are actually
lithium salts and have much higher solubility in the non-aqueous solvent than
the organic redox shuttles. It was observed that lithium borate cluster salts are
extreme stable; thermal decomposition of the salts was not observed below
400oC, and they also showed great compatibility with moisture. These unique
features are very promising for batteries using HF-sensitive materials like
LiMn2O4 [49].
Most importantly, Li2B12F12-xHx has an intrinsic redox potential above 4.2
V vs. Li+/Li with great reversibility, and hence it is also very promising to
serve as a redox shuttle for overcharge protection of 4V class lithium-ion
 Chemical Overcharge Protection of Lithium-Ion Cells 143

batteries. Figure 15 shows the charge/discharge capacity of a

Li1.1[Mn1/3Ni1/3Co1/3]0.9O2/graphite lithium-ion cell using a Li2B12F9H3 based
non-aqueous electrolyte. The cell had a nominal capacity of 1.6 mAh, and was
charged for 3.2 mAh for each cycle to apply about 100% overcharge to the
cell. The current used for overcharge testing was 0.53 mA (C/3). Figure 15
shows that the overcharge protection mechanism was functional for about 90
cycles.

4.0

3.5

3.0
Charge
2.5 Discharge
Capacity, mAh

2.0

1.5

1.0

0.5

0.0
0 10 20 30 40 50 60 70 80 90 100
Cycle number

Figure 15. Charge/discharge capacity of a Li1.1[Mn1/3Ni1/3Co1/3]0.9O2/graphite lithium-

ion cell using a Li2B12F9H3 based non-aqueous electrolyte. The cell had a nominal
capacity of 1.6 mAh, and was charged for 3.2 mAh for each cycle to apply about 100%
overcharge on the cell. The current used for overcharge test was 0.5 mA (C/3).

CONCLUSION
Overcharging a lithium-ion cell is a severe abuse that can lead to the
thermal runaway and catastrophic failure of a battery pack. Redox shuttles are
intrinsic chemical overcharge protection mechanism for lithium-ion cells.
Several stable redox shuttles have been identified to provide long-term
overcharge protection, without the drawbacks of other technologies, which
include complex electronic control systems for external voltage regulation and
144 Zonghai Chen, Yan Qin and Khalil Amine

permanent cell loss for deactivation agents. Combining theoretical and

experimental investigation on the degradation pathways of redox shuttles can
be the key for designing new stable redox shuttles with better performance.

ACKNOWLEDGMENT
Research was supported by U.S. Department of Energy, FreedomCAR and
Vehicle Technologies Office. Argonne National Laboratory is operated for the
U.S. Department of Energy by UChicago Argonne, LLC, under contract DE-
AC02-06CH11357.

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Chapter 5

THERMAL STABILITY
AND ELECTROCHEMICAL PERFORMANCE
OF LICOO2 AND LICO0.2NI0.8O2
IN LITHIUM-ION BATTERIES

George Ting-Kuo Fey1 and T. Prem Kumar2

1
Department of Chemical and Materials Engineering,
National Central University Chung-Li, Taiwan, R.O.C.
2
Electrochemical Power Systems Division, Central Electrochemical
Research Institute Karaikudi 630006, Tamil Nadu, India.

ABSTRACT
Parallel to the rising market for lithium-ion power packs, more
incidents of severely debilitating and sometimes fatal tragedies, as a
result of battery hazards are being reported. Some of the safety risks of
lithium-ion batteries are inherent in the fact that they combine highly
energetic materials that are in contact with a flammable electrolyte based
on organic solvents. Moreover, the potential ranges experienced by these
cells are beyond the thermodynamic stability windows of the electrolytes,
which can decompose upon contact with the charged active materials.
The interface between the cathode and electrolyte is of special concern
since partial dissolution of the active material can create further
complications. This chapter discusses processes at the positive electrode
that can lead to thermal runaway, especially at those based on the most
148 George Ting-Kuo Fey and T. Prem Kumar

popular cathode materials, LiCoO2 and LiNi0.8Co0.2O2. Measures such as

coating cathode particles with inert oxides have been shown to improve
cell safety by increasing the onset temperature of electrode-electrolyte
reactions and lowering the exothermicity of such reactions. Additionally,
coatings also bestow improved cyclability to the cathodes. Reactivity of
cathode active materials is also related to electrolyte composition.
Electrolyte additives and non-flammable electrolytes are a case in point.
Techniques for studying thermal stability such as differential scanning
calorimetry and accelerating rate calorimetry are also discussed.

1. INTRODUCTION
Several instances of exploding lithium-ion battery packs have been
reported in recent years, which have raised pertinent questions on the safety of
such devices [1]. Faced with the consequences of consumer dissatisfaction,
product recalls and market share loss, manufacturers are placing greater
emphasis on the safety aspects of lithium-ion batteries. Constructed with
highly energetic active materials in contact with a flammable electrolyte based
on organic solvents, the batteries can become unsafe if subjected to conditions
for which they were not designed, such as overcharging, disposing in fire,
external short circuiting and crushing. Moreover, the potential ranges
experienced in common lithium-ion cells are beyond the thermodynamic
stability windows of the electrolytes, which decompose upon contact with the
charged active materials. The cathode/electrolyte interface is further
complicated by partial dissolution of the positive active materials [2–4],
especially at the end of charging and at elevated temperatures [5–11]. Safety
improvements have been made by using safety vents, positive temperature
coefficient elements, shutdown separators/additives, oxidation-tolerant or less
flammable electrolytes and redox shuttles.

2. MEASUREMENT OF THERMAL STABILITY

Many materials are prone to exothermic reactions at elevated
temperatures. Therefore, understanding the conditions that trigger such
reactions is essential for operating devices that use the materials safely. It is
difficult to define the highest safe temperature for a material since it is
complicated by a number of factors such as amount, geometry, surface area,
 Thermal Stability and Electrochemical Performance of LiCoO2… 149

particle size and availability of oxidant. Experimental methods for assessing

the thermal instability/runaway potential are based primarily on
microcalorimetric techniques such as differential thermal analysis (DTA),
thermogravimetry (TG), differential scanning calorimetry (DSC) and
accelerating rate calorimetry (ARC). However, the most common techniques
employed for determining the instability or thermal runaway potential of
battery chemicals are DSC and ARC.

2.1. Differential Scanning Calorimetry

Differential thermal analysis and thermogravimetry are widely used for

first-level thermal hazard evaluation because of their operational simplicity
and approach. The techniques provide quantitative data on sensitivity
(exothermic onset temperature) as well as severity (heat of decomposition)
[12]. Since they are not suitable for large volumes of samples and devices,
have poor reproducibility and use non-adiabatic experimental conditions, these
methods cannot be broadly applied in assessing thermal safety. However, DSC
as a thermal hazard tool is particularly useful for determining the
decomposition mechanisms of reactive chemicals because it measures heat
flow as a function of temperature or time. This is done by measuring the
difference in the power required to maintain the temperatures of reference and
test samples. Typically, a differential scanning calorimeter consists of a
furnace, sample holders for the test and reference materials, and
thermocouples. The furnace is set on a steady ramp. The thermal responses
yield information on onset of heat flow (endothermicity or exothermicity),
heat of decomposition, melting/boiling point, decomposition kinetics, etc..
DSC is a quick and relatively cheap method for thermal screening of small
samples, so it is a popular technique for early stage product development.

2.2. Accelerating Rate Calorimetry

Adiabatic calorimetry is an important technique for the study of self-

propagating and thermally-sensitive reactions. As a thermal hazard evaluation
technique, ARC is particularly suitable for large samples, including cells. ARC
consists of a container that maintains the test sample under adiabatic
conditions with respect to its environment. The inner temperature is
150 George Ting-Kuo Fey and T. Prem Kumar

continuously monitored and the surrounding temperature is suitably adjusted

in order to minimize heat flow between the container and its surroundings.
ARC operates on a heat–wait–search principle to identify the initiation and
progress of exothermic self-heating processes. First, the experiment is initiated
under the ‘heat’ mode, when the temperature of the sample and container are
raised to a set value, followed by a ‘wait’ mode for a fixed duration. During
the subsequent ‘search’ mode, the rate of increase in the temperature of the
sample container is monitored. The ‘heat–wait–search’ procedure is repeated
until the system experiences a self-heating rate above a set threshold. When
self-accelerating exothermicity is detected, the controls activate to maintain
adiabatic conditions, afterwhich any increase in the temperature of the sample
can be attributed totally to the heat generated by the test sample. ARC
provides information on the rate of self-heating as a function of temperature,
variation of temperature with time, variation of pressure with
time/temperature, enthalpy of reactions and kinetic parameters. ARC offers
more sensitivity than DSC.

3. HAZARD TRIGGERS

3.1. Temperature Coefficient of Cell Voltage

The temperature derivative of the free energy change, ΔG, for a reaction
to the associated change in entropy, ΔS, can be written as

[d(ΔG)/dT]p,n(i) = –ΔS, (1)

where T is the absolute temperature. ΔG for an electrochemical reaction is

related to the cell voltage sustaining the electrochemical reaction by the
equation

ΔG = –nFE, (2)

where n is the number of electrons transferred and F is the Faraday. Therefore,

ΔS = nF(dE/dT)P,n(i) (3)
 Thermal Stability and Electrochemical Performance of LiCoO2… 151

Since

ΔG = ΔH – TΔS, (4)

where ΔH is the enthalpy of the reaction,

ΔG = ΔH – nFT(dE/dT). (5)

If the temperature coefficient, dE/dT , is positive, the electrochemical cell

will heat on charge and cool on discharge. Lithium-ion batteries have a
negative dE/dT, which means they can overheat during high-current drains
[13]. The total heat released, including the reversible thermodynamic heat
released along with the irreversible Joule heat from operation of the cell in an
irreversible manner, during charge or discharge at a finite current/rate is
described by the equation

q = TΔS + I(EOCV – ET) (6)

where ET is the terminal voltage and EOCV is the open-circuit voltage. In

general, the entropy heat, TΔS, is negligibly small compared to the irreversible
heat, q, which is released when the cell is in operation. Irreversible behavior
manifests itself as a departure from the equilibrium or thermodynamic voltage.
The total heat released during cell discharge is the sum of the thermodynamic
entropy contribution and the irreversible contributions. A proper dissipation of
the heat generated is critical to the safety of the cell. Poor heat dissipation can
lead to thermal runaway and other catastrophic situations.

3.2. Cell Design

A major factor in the reduced safety of lithium-ion batteries is their

design. The temperature of a cell is determined by the balance between the
amount of heat generation and dissipation. Obviously, the heat balance
depends on the thermal capacity of the cell, as well as the thermal
conductivity, emissivity, external surface area and geometry of the cell. At
temperatures above 130–150◦C, exothermic chemical reactions between the
electrodes and electrolyte set in, which further raise the temperature of the cell.
Any cell design that cannot dissipate this heat will promote exothermic
reactions inside the cell under adiabatic-like conditions, which can rapidly
152 George Ting-Kuo Fey and T. Prem Kumar

increase the cell’s temperature. The increased temperature will further

accelerate the chemical reactions and cause even more heat to be produced,
eventually resulting in thermal runaway [14–16], the onset temperature of
which delineates the safety limits of the device. Any resulting pressure build-
up can cause mechanical failures within cells, such as short circuits, premature
death of the cell due to irreversible interruptions in the current path, or the
distortion, swelling and rupture of cell casing. Processes that trigger thermal
runaway include [16,17]: (i) thermal decomposition of the electrolyte, anode
and cathode; (ii) reactions of the electrolyte with the charged anode and
cathode; and (iii) melting of the separator and the consequent internal short.

3.3. Electrolyte

If there is one determining factor that decides the safety of lithium-ion

batteries, it is the electrolyte. Electrolytes must be stable in the electrochemical
window within which the cell operates. They must also be thermally stable
over a reasonable temperature range, especially when in contact with the
active materials. Non-flammability in air at elevated temperatures is another
requirement in order to withstand abuse conditions. An electrolyte that meets
the above criteria and also possesses desirable properties such as low viscosity
and high conductivity still remains a dream. Lithium is intrinsically unstable
with any commonly known electrolyte. Today’s electrolytes based on alkyl
carbonate solvents are known to react vigorously at elevated temperatures with
lithiated graphite and delithiated cathodes (e.g., LixCoO2 (x < 0.5)) [18–21].
Calorimetric studies have thus become mandatory to determine the safety of
electrode–electrolyte combinations. According to Aurbach et al. [22], the
commonly used electrolytes such as the ones based on LiPF6 in alkyl
carbonate solvents are only a compromise: they are flammable and have
electrochemical windows of about 4.5V. Although several alternatives such as
ionic liquids and alkyl carbonate-based electrolytes containing salts such as
lithium bis(oxalato)borate, LiBC4O8 (LiBOB) [23] and lithium
fluoroalkylphosphates (e.g., Li[PF3(C2F5)3]) [24–26] are being considered as
substitutes for LiPF6, the immediate solution seems to be additives that can
protect electrode-active materials even at high temperatures by forming highly
protective films on the electrodes. Such additives must render the electrode-
electrolyte interface stable, but also have low flammability with cell venting.
 Thermal Stability and Electrochemical Performance of LiCoO2… 153

3.4. Active Materials

Commercial lithium-ion batteries are thermally stable up to about 60◦C

[27], above which their performance declines. Initial reactions are between the
anode and the electrolyte [28]. Reactions between the cathode and electrolyte
dominate the heat-evolution processes at elevated temperatures [20]. Allowing
the latter processes to proceed would lead to disastrous consequences. Violent
reactions are known to occur in the charged state of lithium-ion batteries. In
fact, at small values of x in LixCoO2, LixNiO2 and LixMn2O4, the cathodes can
adversely influence thermal stability [8,29]. Therefore, thermal studies on
cathode materials are performed in their delithiated states. Because cell
temperatures during abuse reactions can even melt the aluminum current
collector used for the positive electrodes, Biensan et al. [30] concluded that
cell temperatures during cell explosion could shoot above 659◦C, the melting
point of aluminum. In this Chapter, we discuss safety issues with special
reference to the thermal stability of LiCoO2 and LiCo0.2Ni0.8O2 in contact with
battery electrolytes.

4. LICOO2
The most exploited cathode material for commercial lithium-ion batteries
is LiCoO2, a layered compound isostructural with the rhombohedral α-NaFeO2
[31]. In its charged state, it is thermally unstable and can decompose, releasing
oxygen at temperatures above 200°C [32–36] according to the reaction [8,37]:

6 Li0.5CoO2 → 3 LiCoO2 + Co3O4 + O2. (7)

The released oxygen can then react with organic solvents to generate heat.
ARC studies by Jiang and Dahn [38] showed that organic solvents can reduce
Li0.5CoO2 to Co3O4 and CoO, eventually even to Co metal. The studies also
showed that the reactivity of LixCoO2 with the electrolyte was affected by
factors such as particle size, surface area, electrolyte composition, etc. [38,39].
According to MacNeil et al. [20], the first thermal processes between LixCoO2
and the electrolyte can be described by an auto-catalytic reaction. In fact, the
reaction of Li0.5CoO2 with EC–DEC begins at 130◦C, which is much lower
than the decomposition temperature of Li0.5CoO2 itself [32]. Jiang and Dahn
[38] showed that the reactivity of Li0.5CoO2 was higher in LiBOB–EC–DEC
154 George Ting-Kuo Fey and T. Prem Kumar

than in LiPF6–EC–DEC. Although LiBOB can effectively stabilize the SEI of

LiC6, the lower stability of the LiBOB-based electrolyte with respect to the
cathode would mean that graphite/LiCoO2 cells cannot be rendered safer by
replacing LiPF6 with LiBOB in the electrolyte. Baba et al. [35], who evaluated
the thermal stability of chemically delithiated LiCoO2 (Li0.49CoO2) by
differential scanning calorimetry (DSC), the decomposition of EC (C3H4O3)
by the cathode material begins at 190◦C according to the reaction [32]:

10 Li0.5CoO2 + C3H4O3 → 5 LiCoO2 + 5 CoO + 3 CO2 + 2 H2O. (8)

The DSC pattern also showed a peak at 230◦C, which Baba et al. [35]
ascribed to the oxidation of the electrolyte caused by oxygen released from
Li0.49CoO2.

4.1. Coated LiCoO2 Cathodes

It is recognized that many safety-related incidents are due to vigorous

exothermic reactions between delithiated cathodes and electrolytes [32,35,40].
Naturally, a logical approach to improve thermal stability would be to provide
a barrier that prevents direct reaction between the constituents. Such barriers
can be effected by modifying cathode surfaces with inorganic coating or by
adding film-forming additives to the electrolyte [41–45]. For example, γ-
butyrolactone as an additive in the electrolyte has been reported to decompose
and form products that encapsulate the cathode [46]. In fact, lithium-ion cells
with this additive did not explode during nail penetration tests at 4.35V and
overcharge tests up to 12V. However, concerns about the compatibility of γ-
butyrolactone with the anode and cathode remain.
Lee et al. [47] used a coating of gel polymer electrolyte based on cPVA
(cyano-substituted polyvinyl alcohol). The –CN group gives the polymer a
high dielectric constant ( = 15 at 1 kHz at 20°C), which facilitates
dissociation of lithium salts, leading to high ionic conductivity (around
7 mS.cm−1 at 25°C). Figure 1 shows the DSC profiles of the bare and cPVA-
coated LiCoO2 charged to 4.2 V. The bare LiCoO2 exhibits large exothermic
peaks (ΔH = 413 J.g−1) between 100 and 300°C [32,35,40]. However, the
cPVA-coated LiCoO2, showed a noticeable decrease in exothermic heat
(ΔH = 31 J.g−1), suggesting that the polymer electrolyte encapsulates the
cathode particles, effectively suppressing the exothermic reaction [47]. The
 Thermal Stability and Electrochemical Performance of LiCoO2… 155

authors [47] proposed that the –CN moiety coordinates with the cobalt cation
in LiCoO2, imparting structural stability to the delithiated cathode, as well as
significantly suppressing exothermic reactions.Recently, several papers
reported enhancement in the cyclability of cathodes by coating cathode
particles with oxides, glasses, etc. [48–58]. A benefit of coated electrodes is an
increase in their thermal stability during contact with the electrolyte. Cho et al.
[59] showed that LiCoO2 coated with nanoparticulate AlPO4 blocked the
thermal runaway of lithium-ion cells, in addition to significantly reducing
electrolyte oxidation and cobalt dissolution into the electrolyte. In another
study, Cho et al. [60] demonstrated the 12 V overcharge behavior of the
AlPO4-coated LiCoO2 in terms of its exothermic behavior. Cho [61] also
showed that an AlPO4 coating thickness of 20 nm was optimal. Although
increased thickness of the coating drastically reduced the exothermic reaction
between

Figure 1. DSC profiles of the bare and cPVA-coated delithiated LiCoO2 active
materials [47].

LixCoO2 and the electrolyte in addition to increasing the onset temperature

of oxygen evolution, the reduced lithium-ion diffusivity was detrimental to
cycling performance. Fey et al. [62] showed that LiCoO2 coated with cobalt
oxides displayed increased resistance to decomposition reactions with the
electrolyte. Not only was the temperature of the reaction raised by 11◦C, but
the coating also reduced the exothermicity of the reaction (Figure 2).
Although the charge decomposition of LiCoO2 (Li0.5CoO2) takes place
above 200°C in the absence of an electrolyte (according to equation 7) [32], its
156 George Ting-Kuo Fey and T. Prem Kumar

decomposition temperature is lowered to 130°C in the presence of EC:DEC

[63]. In line with the fact that the reactivity of LiCoO2 would increase with
increased levels of delithiation, Fey et al. [63] found that the onset
temperatures (To) for decomposition were 151°C and 110°C for LiCoO2
charged to 4.2 and 4.5 V, respectively (Table I). The corresponding values for
LiCoO2 coated with MgAlO4 were 175°C and 145°C, suggesting that thermal
stability improved due to the coating. Moreover, the greatest areas of the DSC
peaks of the charged LiCoO2 electrodes were larger than those for the charged
coated electrodes (Figure 3), which indicates that the amount of heat generated
(a measure of the amount of oxygen released) was reduced upon coating. The
lower exothermicity and higher onset temperature are proof of the higher
thermal stability of the coated electrodes.
Fey et al. [63] also demonstrated the higher thermal stability of LiCoO2
coated with lanthanum aluminum garnet (La3Al5O12) as well as with Li4Ti5O12
and Li4Mn5O12. For example, their DSC studies showed that coatings with
Li4Ti5O12 and Li4Mn5O12 raised the onset temperature of a LiCoO2 sample
charged to 4.2 V by 7°C and 5°C to 471°C and 469°C, respectively. The
coated samples also reduced the exothermic heat from 131 J.g–1 to 120 J.g–1
and 122 J.g–1, respectively, for Li4Ti5O12 and Li4Mn5O12 coatings.

Figure 2. DSC profiles of (a) bare and (b) 0.3-wt.% cobalt oxide-coated LiCoO2 [62].
 Thermal Stability and Electrochemical Performance of LiCoO2… 157

Table I. Data derived from DSC profiles (figure 3) for bare and MgAlO4-
coated LiCoO2 charged to various voltages.

Voltage Cathode Material To (°C)a Td (°C)b Htot (J g-1)c

4.5 V Bare 110 174 205
Coated 145 178 182
4.4 V Bare 120 182 185
Coated 155 188 155
4.3 V Bare 148 186 164
Coated 156 190 142
4.2 V Bare 151 191 131
Coated 175 201 121
a
Onset temperature; b decomposition temperature; c total evolved heat.

Figure 3. DSC profiles of bare LiCoO2 and MgAlO4-coated LiCoO2 charged to various
voltages.

5. LICO0.2NI0.8O2
The general consensus is that solid solutions of the general formula LiNi1–
yCoyO2 are structurally more stable than their pristine end-member
homologues and also exhibit superior performance [64–67]. Typically, the
solid solution of the formula LiNi0.8Co0.2O2, with its higher reversible capacity
158 George Ting-Kuo Fey and T. Prem Kumar

than LiCoO2, as well as significant cost and performance benefits, is

considered a potential next-generation cathode material [68,69]. Several
groups have reported the formation of surface films on cathodes such as
LiCoO2, LiMn2O4, and LiNi1-xCoxO2 [70–78], but the nature of the reactions
that generate the films is unclear. According to Abraham et al. [79], an
oxygen-deficient surface layer was formed on LiNi1-xCoxO2 as a result of
oxygen transfer reactions with the electrolyte. The thermal characteristics of
LiNi1-xCoxO2 is reminiscent of those of LiNiO2, which in its delithiated state
has a poor thermal stability due to the presence of the unstable Ni4+ ion [80].
At an x value of 0.3 in LixNiO2, the compound releases oxygen at a lower
temperature than LixCoO2 (x = 0.4). The lower stability of LixNiO2 is
attributed to the easier reduction of Ni3+ compared to Co3+ [81]. Therefore, a
cell with LiNiO2 should be less tolerant than one with LiCoO2 under abusive
conditions [8]. Ohzuku et al. [82] showed that LixNiO2 (x = 0.15) undergoes
an exothermic reaction at about 200◦C. Arai et al. [81] reported that LixNiO2
transforms into a rocksalt structure at 200◦C due to cation mixing. In the
absence of air, LiNiO2 decomposes, releasing oxygen [83]:

4 LiNiO2 → 2 Li2O + 4 NiO + O2. (9)

Below x values of 0.25, LixNiO2 undergoes highly exothermic reactions

with common electrolytes with an onset temperature around 200◦C. Reflecting
the lower thermal stability of LiNiO2, Fey et al. [63] found that major
exothermic reactions of LiNi0.8Co0.2O2 charged to 4.5V set in around 168°C.
However, this value is lower than the 222°C reported by Ha et al. [84].

5.1. Substituted LiNiyCo1-yO2 Compositions

Several substituted compositions based on LiNiyCo1-yO2 have been

investigated with the dual goal of improving cycle life and thermal stability. A
composition such as LiNi0.8Co0.15Al0.05O2 has been reported to have poor cycle
life, attributable to greater impedance at the cathode [85,86]. The rise in
impedance has been traced to the presence of a NiO-type interfacial film
formed by the reduction of the electrolyte by highly oxidizing and unstable
Ni4+ generated during the charge process [87]. A way out to bypass this rise is
to opt for a similar but more stable cathode material such as
LiNi1/3Co1/3Mn1/3O2 [88,89].
 Thermal Stability and Electrochemical Performance of LiCoO2… 159

5.2. Coated LiNiyCo1-yO2 Compositions

Oxygen release at elevated temperatures is believed to trigger electrolyte

decomposition mainly through surface reactions [35]. Therefore, it is logical to
expect that coatings would suppress them. A composition of interest with a
higher specific capacity than LiCoO2 is LiNi0.8Co0.1Mn0.1O2. However, its
practical application is hindered by its relatively poor thermal stability. In
order to improve its thermal characteristics, Cho et al. [90] coated the cathode
material with AlPO4. The coating did not affect the specific capacity (188
mAh/g at a cut-off voltage of 4.3 V for the bare compound), but noticeably
suppressed violent exothermic reactions between the cathode and the
electrolyte. Safety tests conducted on cells with the AlPO4-coated
LiNi0.8Co0.1Mn0.1O2 cathode exhibited excellent overcharge performance.
Moreover, they did not experience thermal runaway, smoking or explosion, in
contrast to those containing the uncoated cathode material [90]. In a
comparative study of cells with AlPO4-coated LixCoO2 and AlPO4-coated
LixNi0.8Co0.1Mn0.1O2, Cho et al. [62] found that as the rate was increased from
1C to 3 C, the surface temperature of the cell with the coated
LixNi0.8Co0.1Mn0.1O2 did not exceed 125◦C, while that of the cell with the
coated LixCoO2 exceeded 170◦C.
Recently, Fet et al. [63] carried out a detailed study of the thermal
behavior of LiNi0.8Co0.2O2 coated with MgAlO4. Figure 4 gives the DSC
profiles of bare and MgAlO4-coated LiNi0.8Co0.2O2. Major exothermic
reactions of the bare cathode material charged to 4.5V occur around 168C. It
can be seen from Table II that the charged coated material exhibited not only
higher Td and To than the bare sample, but lower Htot too, suggesting the higher
stability of the coated material. They also investigated the thermal behavior of
charged LiNi0.8Co0.2O2 coated with double oxides such as La3Al5O12,
Li4Ti5O12 and Li4Mn5O12 [63]. Their DSC data showed a higher
decomposition temperature for the coated electrodes, suggesting a reduction in
oxygen generation upon coating [91].

6. CONCLUSIONS
Commercial lithium-ion batteries based on flammable non-aqueous
electrolytes and layered oxides such as LiCoO2 and LiNi0.8Co0.2O2 are
inherently unsafe. Thermal reactions in such cells can be triggered by the
160 George Ting-Kuo Fey and T. Prem Kumar

oxidation of solvents by the oxygen released by the unstable charged cathodes

during thermal events. Therefore, it appears that there is probably no
possibility to suppress such hazards with cathodes, although limited success
has been achieved by using coated cathodes and electrolyte additives that react
with the cathode surface to generate a barrier between the active material and
the electrolyte. With such cathode-active materials, substituents that can push
the thermal decomposition point of the material to above 300°C without
compromising capacity are needed, but in all likelihood, cathodes that are not
prone to release oxygen, such as LiFePO4, are probably the only practical
solution for thermally safe cathodes.

Table II. Data derived from DSC profiles (figure 4) for bare and MgAlO4-
coated LiCoO2 charged to various voltages.

Voltage Cathode Material To (°C)a Td (°C)b Htot (J g-1)c

4.5 V Bare 109 168 230
Coated 145 186 195
4.4 V Bare 118 175 210
Coated 172 214 173
4.3 V Bare 120 195 190
Coated 181 227 155
4.2 V Bare 148 200 180
Coated 221 268 150
a
Onset temperature; b decomposition temperature; c total evolved heat.

Figure 4. DSC profiles of bare LiNi0.8Co0.2O2 and MgAlO4-coated LiNi0.8Co0.2O2

charged to various voltages.
 Thermal Stability and Electrochemical Performance of LiCoO2… 161

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Striebel, K; Cairns, EJ; McLarnon, F. J. Electrochem. Soc., 2001, 148,
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[85] Balasubramanian, M; Sun, X; Yang, XQ; McBreen, J. J. Power
Sources., 2001, 92, 1.
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J; Amine, K. Electrochem. Commun., 2002, 4, 620.
[87] Belharouak, I; Sun, YK; Liu, J; Amine, K. J. Power Sources., 2003, 123,
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In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 6

COMPOSITIONAL AND STRUCTURAL

EVOLUTION OF CATHODE PARTICLES
OF THE CYCLED LITHIUM BATTERIES
INVESTIGATED BY ANALYTICAL HIGH
RESOLUTION TRANSMISSION ELECTRON
MICROSCOPY(AHRTEM)

Yuewu Zeng 1∗, Shaofeng Chen2∗, Jinhua He2

and Z.C. Kang 2,3∗
1
Center of analysis and measurement, Zhejiang University,
Hangzhou 310028, China
2
Ningbo Jinhe New Materials Inc, Zhejiang Yuyao 315400 China
3
RE Power-Tech 8211.E.Garfield St. J-201 Scottsdale AZ 85257, USA

∗
Corresponding authors: E-mail: [email protected]
∗
E-mail: [email protected]
∗
E-mail: [email protected]
166 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

1. INTRODUCTION

1.1 The Cathode of Lithium Battery is the Li+ Source and Sinks

As is well known [1-3], the lithium battery is a rechargeable battery and

its lithium comes from the cathode electrode materials such as lithium
intercalated transition metal oxides, for example, LiCoO2, LiNiO2, LiMnO2,
Li(Co1-x-yNixMny)O2, and LiMn2O4. During the charging process, the Li+ ions
pull out from the lithium intercalated oxides by electric field and are expelled
into the carbon layers of graphite anode through an electrolyte. Therefore, the
graphite anode acts as Li+ ions sink. However, during the discharging process,
the Li+ ions stored in the graphite anode act as Li+ source and will flow out
from the graphite anode intercalating into the oxygen closed packed layers of
the dioxide cathode through an electrolyte. So, the cathode is a sink of the
flowing Li+ ions. The anode and cathode both act as Li+ ion source and sink.
The capacity of the lithium battery is dominated by the Li+ ion source storage
capacity and the sink volume. The rate of Li+ ions flow is also related to the
source and sink capability. The cathode and anode, especially the cathode, are
very important for the lithium battery.
The Li+ ions source and sink of a lithium battery are crystalline
compounds: oxides and graphite. Li+ ions inserting or extracting from the
compounds have to make these compounds to capture (during inserting) or to
release (if extracting) electron, which means a redox process has to occur in
these crystals. It was known that Fe, Co, Ni, and Mn can form M2O3 and
M3O4, in which the oxygen assembles a close-packing array and the M occupy
the octahedron and/or tetrahedron voids based on the ratio of metal and
oxygen. Figure 1a shows the location of metal atoms of FeO, Fe2O3 and Fe3O4
on the oxygen closed packing layer. The Fe3+ occupy 2/3 octahedron voids of
a oxygen closed packed layer in Fe2O3 to create a Corundum structure. The
Fe2+ and Fe3+ cations occupy alternately at 1/2 tetrahedron voids and all of the
octahedron voids forming Spinel structure. If Fe2+ cation located at all of the
octahedron voids of the oxygen closed packed layer, it will create a FeO with
NaCl structure (face center cubic (f.c.c. lattice)). Usually Fe atom have 2+ and
3+ valence state and Fe3+ prefer to locate at octahedron, but Fe2+ favor being in
the tetrahedron. However, if Na+ involved in FeO structure and the Na and Fe
ordered as they alternately located in different octahedron layers, then NaFeO2
oxide is formed as shown in Figure 1b. NaFeO2 can be synthesized by
hydrothermal method. Using Li to substitute Na in the NaFeO2 can form
 Compositional and Structural Evolution of Cathode Particles… 167

LiFeO2, but it is not stable. However, LiCoO2 and LiNiO2 can be synthesized
by different methods, but they always have NaFeO2 –related structure.

Figure 1. (a) Oxygen closed packed array and Fe atom located at octahedron and
tetrahedron voids for FeO, Fe2O3 and Fe3O4 (b) NaFeO2 structure

During charging or discharging process, the lithium content of LiMO2

(M=Co, Ni, Mn) cathode has to vary from 1 to x (0<x<1), that implies the
oxide is nonstoichiometric and the metal has different ratio of M3+ and M4+.
The voltage of the cell related to the transference number, tLi+ , of Li+ ions and
lithium content, x, of the cathode, LixMO2, may determine the chemical
potential of the oxide. Then

V=1/4F tLi+ dμ = μ2-μ1/4F = μo2-μo1/4F –RT/4F In ac(x)/aa(1-x)

=Vo – RT/4F In ac(x)/aa(1-x)

= [Ef (Li+) - Ef(M3+/M4+)] – RT/4F In ac(x)/aa(1-x) (1-1)

Where: Ef(Li+) is Fermi energy of the Li metal and Ef(M3+/M4+) is the

Fermi energy of M3+/M4+ redox couple; x is lithium content of cathode and (1-
x) is lithium content of anode; F is Faraday’s constant. It is clear that the
voltage of the Lithium battery is related to the electron band structure, which is
dominated by the crystal structure and the voltage decreasing is related to the
chemical activity of Li+ intercalated layer metal oxides (cathode) and graphite
168 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

(anode). Nonstoichiometry and phase transitions of the nonstoichiometric Li+

transition metal dioxides should dominate the electrochemical property of Li+
battery.
In crystalline solid, the electric neutralization should be held at any place
of the solid. For the cathode and anode of Li+ battery, the motion of the most
mobile ions generally determines the rate of the charging and discharging
process. However, the ionic transport rate may be largely influenced by
interaction with the electrons and holes of the electrodes because the electric
neutralization has to be obeyed. Wagner[4] indicated that the ionic diffusivity,
Di, and the electron transference number, te, chemical activity of the ion
species, and concentration of the ions in the solid dominate the ionic flows.
Therefore, wide nonstoichiometry and electron transference number close to 1
will have more advantageous. Due to Li+ ion migration should be guided by
the navigation of electrons or polarized electron cloud. So the cathode having
electron and ionic mixed conductivity would be able to enhance the charging
and discharging process. It was known [4] that high concentration of mobile
ion and low concentration of electron in a cathode may have higher mobility
of Li+ ions. The range and phase of the Li+ nonstoichiometry of the crystalline
cathode could determine its electric and ionic conductivity resulting excellent
or poor electrochemical performance of a Li+ battery.
Based on our knowledge of the Li+ battery we believe that revealing the
structure variation of the cathode crystalline particles of a discharged or
charged Li+ battery is great important for development of high performance
Li+ battery. Therefore, we used snapshot method, which take the cathode
particle underwent 300 discharge and charge cycles, to observe the surface and
structure of the particles at atomic scale by AHRTEM (Analytic High
Resolution transmission Electron Microscopy). In this paper we review the
compositional and structural evolution of the cycled cathode particles of the
Li+ battery.

1.2 The Compositional and Structural Feature of Surface of a

Cathode Particle

LiMO2(M=Co, Ni, Mn) have NaFeO2-type structure which means the Li

and M (Co, Ni, Mn) alternately distribute in the oxygen closed packed layers,
which are the {111} planes of a face center cubic lattice as shown in figure 1b.
The crystallographic unit cell of LiMO2 (for example LiCoO2) is hexagonal
(R-3) as shown in figure 2. The basic plane of the hexagonal unit cell is a
 Compositional and Structural Evolution of Cathode Particles… 169

{111} plane of NaFeO2 and the Li occupy the octahedron void created by the
successive oxygen closed packed layers (in figure 2 it marked as OA,OB) and
the Co located in other octahedron site formed by other successive oxygen
closed packed layers (in figure 2 it marked as OB and OC). Therefore the
surface (0001)hex is hard to pass through Li ions, but Li+ ions are easy to
escape from the {1-100}hex or {1-210}hex surfaces of the LiCoO2. Therefore,
The cathode particle exposing these surfaces to electrolyte should make the
Li+ ions to intercalate or de-intercalate more easy and also can benefit the
charge or discharge process.

1.3 Fundamental Structural and Compositional Relationships

between the NaFeO2 and LiMO2 (M=Co,Ni,Mn)

As mentioned before, the Li+ inserted into the successive oxygen closed
packed layers will reduce the transition metal cation:

M4+ + e- = M3+

This process may cause following sub-reaction 2M3+ →M4+ + M2+

Figure 2. The crystallographic unit cell (Hexagonal) of LiCoO2 and NaFeO2 frame
(f.c.c lattice).
170 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

It called disproportion. Different cation may prefer to occupy different

coordination environment. For example Ni2+ favor at tetrahedron site.
Therefore the cathode materials, LiCoO2, Li(Co1-xNix)O2,
Li(Co1/3Ni1/3Mn1/3)O2 and Li(Ni1-xMnx)O2 may have ordered cations and/or
ordered Li ions arrays. But if the Co, Ni, and Mn still located in same
successive oxygen closed packed layers, or in other words stay in same
octahedron slab, then the ordered structure and NaFeO2 sub-lattice would hold
same relationship as LiCoO2. For example the ordered Li(Ni1/3Co1/3Mn1/3)O2
unit cell shown in figure 3.
Li ion usually occupies at the octahedron site, but it also may stay in a
tetrahedron site and the Ni2+ also is favor to occupy at tetrahedron site.
Therefore if the disproportionate reaction is occurred and Ni2+ can be formed,
then the formed Ni2+ may move to the tetrahedron site created by successive
octahedra shown in figure 4. The Ni2+ or Li+ located at tetrahedron will
increase the barriers of migrated Li+ ions and induce structural change from
hexagonal to spinel structure as Fe3O4 shown in figure 1a.

Figure 3. Relationship between the ordered Li(Ni1/3Co1/3Mn1/3)O2 unit cell and NaFeO2
sublattice.
 Compositional and Structural Evolution of Cathode Particles… 171

Figure 4. Successive oxygen closed packed layers form octahedron and tetrahedron
located between two octahedra sharing an edge.

1.4 Analytical High Resolution Transmission Electron

Microscopy (AHRTEM) is a Powerful Tool for Revealing
Composition and Structure Variation of the Cathode Particles of
a Cycled Lithium Battery at Atomic Scale

High resolution electron microscopy opens up the possibility of

simultaneously obtain diffraction pattern on the back focus plane and images
showing the projection of the atoms array of the structure of a solid on the
image plane of the object lens. The electron beam size can be adjusted to as
small as 5 nm to obtain the micro-diffraction and X-ray energy dispersive
spectrum (EDX), which gives local structure information and chemical
composition. The high resolution electron microscopy image use the coherent
electron beams (or electron waves) to interact with thin solid sample and to
carry the information of the distances between the atom planes, which is
nearly paralleled to the electron beam direction. The diffraction spots carrying
the structure information can be interfered to form the interference pattern,
which may approximately reproduce the two dimension arrays of the atoms
arrangement of the structure of a solid. Using object aperture in the objective
lens may select different diffraction spots (or mask different diffraction spots)
to interfere each other to obtain the special information of certain crystal
planes of a solid. This technique is very useful for observation of Li+ ion
172 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

intercalation or de-intercalation. We use this technique to reveal the structure

change of the cathode dioxide.

2. BASIC EXPERIMENT TECHNIQUES

2.1 Preparation of the Cycled Cathode Particles for AHRTEM

The observed samples of LiMO2 (M=Co, Ni, Mn) were prepared as

follows: MO2 (for example [Ni1/3Co1/3Mn1/3]O2) precursors were first
synthesized using co-precipitation method. CoCl2, NiCl2 and MnCl2 salts were
used as starting materials for synthesis of the MO2 (for example
[Ni1/3Co1/3Mn1/3]O2 ) powders. The prepared powders were mixed with excess
amount of Li2CO3. After the mixtures were sufficiently ground, the mixtures
were heated in air at 950 ºC for 12 h and followed by slowly cooling to room
temperature. X-ray diffraction data shows that the prepared powders have the
structure of the corresponding LiMO2 (M=Co,Ni,Mn).
Positive electrodes were made by coating a paste of LiMO2 (for example
Li[Ni1/3Co1/3Mn1/3]O2) active material, acetylene black (as a conducting
additive), and polyvinylidene fluoride (PVdF) binder (93:3.5:3.5 (wt.%)) on an
aluminum foil collector. Amount of the active material loaded was 5–6
mg/cm2. The negative electrode was prepared by mixing graphite with 10 wt
% PVdF binders, and the prepared paste was coated on a copper foil. The
electrodes were then dried under vacuum (5x10-2 torr) for 24 h at 120 ºC. The
electrolyte used was 1M LiPF6 in a (1:1:1 (wt.%)) mixture of ethylene
carbonate (EC), polycarbonate (PC), and dimethyl carbonate (DMC). The cells
were assembled inside an Ar-filled dry-box and were evaluated using 053048-
cells (thickness: 5 mm, width: 30 mm, height: 48 mm). The discharge/charge
measurements were carried out between 2.75 and 4.2 V potential ranges at a 1
C rate using an automatic battery tester at room temperature. The specific
capacity vs. cycle number is shown in Figure 5, it can be seen that after 300
cycles, the discharge capacity is about 86% of initial capacity.
After 300 discharge/charge cycling, the cell was discharged to 2 V at 0.2
C and then disassembled. In order to avoid damaging the cycled particle
surfaces, Pieces of the cathode obtained from the disassembled cell were
ultrasonically de-agglomerated in acetone and dispersed on a holey carbon
film supported by a Cu grid for TEM observation. A JEOL-2010 Electron
 Compositional and Structural Evolution of Cathode Particles… 173

microscope operating at 200 kV accelerating voltage and equipped with EDX

was used for imaging, electron diffraction and composition micro-analysis.

Figure 5. Discharge capacity vs. number of cycles of the cell between 2.75 and 4.2 V at
1 C rate.

Figure 6. The different regions were micro-analyzed by EDX with 5 nm diameter

electron beams.
174 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

Figure 7. Relative ratios of Ni, Mn to Co in the atomic percentage decrease from BU,
NS, and SE region of the cycled particles of the Li[Ni1/3Co1/3Mn1/3]O2.

Figure 8. The micro-diffraction patterns can be obtained from the small regions.
 Compositional and Structural Evolution of Cathode Particles… 175

Figure 9. (a) two beams interfere (b) six stronger spots interfere (c) eight spots form
the image demonstrating the structure imperfections.

Figure 10. The structure feature of a 300 cycled LixCoO2 particle.

176 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

2.2 Micro-Diffraction and Micro-Analysis of the Cycled Cathode

Particles

Figure 6 shows the analyzed regions of the cycled particle. BU is the

interior region. NS region is located between the edge and interior of the
cycled particle. SE is placed on edge area of the cycled particle. Using an
electron beam with 5 nm diameter radiating the BU, NS, SE area collects the
data of EDX spectrum and the data collected from region BU were used as
reference for comparison with the data collected from NS and SE area. Figure
7 gives the result of the EDX for the cycled particle of the
Li[Ni1/3Co1/3Mn1/3]O2 as an example.
Figure 8 demonstrates the micro-diffraction patterns of these BU, NS, and
SE small regions and the structure information of these regions may obtain.

2.3 One- and Two- Dimension Lattices Images and Analysis

As mentioned early, using different diffraction spots to form interfered

image may approximately show the special atoms planes in a crystal except
the objective lens of electron microscope could introduce some noise that
should be keep in mind [7-10]. Figure 9 illustrates this method. The diffraction
pattern shown at the top of this figure and the white circles indicate the
diffraction spots to be used imaging. The bottom of this figure presents the
corresponding images. In figure 9a the image reveals the one dimension lattice
planes are not perfect and heavenly distorted. Figure 9b exposes the basic
lattice nets of this crystal and there is some local mismatch. Figure 9c
combines these two information demonstrating the unit cell and structure
Imperfections.

3. COMPOSITIONAL AND STRUCTURAL EVOLUTION OF

THE CATHODE CYCLED PARTICLES OF THE LITHIUM
BATTERIES
3.1 LiCoO2

Nonstoichiometric LixCoO2 (0.5<x<1) has hexagonal structure, but Li+

decrease below x=0.5 it will change to spinel structure, so the available Li+
 Compositional and Structural Evolution of Cathode Particles… 177

source is x=0.5. If Li content decreased more than x=05, the oxygen stacking
sequence will also changed from ABC to AB or AC and that can lead the
metal-insulate transition [10,11]. If Li is completely extracted from LixCoO2
dioxide, It may change to CoO oxide with f.c.c structure. Figure 10 present
structure change of a 300 cycled LixCoO2 particle. At surface region Li is de-
intercalated and some area start to form f.c.c structure. It was known [12] that
AlPO4 coated on the LixCoO2 particle can promote to form spinel structure.
Figure 11 demonstrate this factor. The surface layer of the AlPO4 coated
LixCoO2 particle form spinel structure that may improve the Li+ battery
performance.

Figure 11. AlPO4 coated LixCoO2 particle after 300 cycling process.

Figure 12. AlPO4 coated LiNi1/3Co1/3Mn1/3O2 cathode particle after 300 cycling
process shows spinel structure on the surface region.
178 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

3.2 LiNi1/3Co1/3Mn1/3O2

The Ni and Mn in the LiNi1/3Co1/3Mn1/3O2 cathode [5,6] are easy to be lost

and the surface structure change to f.c.c structure [13,14] as figure 8 shown.
Using AlPO4 coated on the LiNi1/3Co1/3Mn1/3O2 cathode may also form spinel
structure. Figure 12 demonstrate this result.

3.3 LiNi0.8Co0.2O2

The LiNi0.8Co0.2O2 cathode reduces the Co content and may increase the
capacity of Li battery. But Ni3+ may be disproportionation into Ni4+ and Ni2+.
Ni2+ ions are favor in a tetrahedron site producing the spinel structure. Using
AlPO4 coated on the LiNi0.8Co0.2O2 may promotes to form the spinel structure
and depress the Ni3+ disproportionation reaction. Figure 13 show the surface
structure of the AlPO4 coated on the LiNi0.8Co0.2O2. It seems that the spinel
structure on the surface region may pillar up the octahedral layers resulting the
improvement of the Li battery performance.

Figure 13. The AlPO4 coated on the LiNi0.8Co0.2O2 particle after 300 cycling process.
 Compositional and Structural Evolution of Cathode Particles… 179

4. DISCUSSION AND CONCLUSION

Oxygen closed packed array is the basis of the valent variation of high-
valent transition metals as Li is inserting or extracting. The d electrons of the
transition metal, especially Co, Ni, Mn, could exchange their electrons with
banded oxygen atoms to be reduced or oxidized by the inserted or extracted Li
ion. Li migration forced by the electric field have to simultaneously
accompany electron or hole navigation. Two-dimensional octahedral layer
created by successive stacking (as ABC or AB or BC) of oxygen closed
parked arrays is basic structure element for most cathode materials. The high
valent cations are distributed in these octahedral slabs and alternately
separated by the Li ion sheets. The cations in the octahedral slabs may be
ordered and changed the valence state that may cause the rate of Li ion
migration to vary. If the valence of a cation is changed to make this cation to
be preferred in tetrahedron site created by edge shared octahedron, the
structure may change to spinel, having the 2:1 ratio of octahedron and
tetrahedron, or Olivine structure, having 1/2 octahedron site occupied by
cations and 1/8 tetrahedron site occupied by phosphorus anions. Because the
large size of the phosphorus anion can make the distance between the high
valent cation octahedron layers to be large, then Olivine structure may
promote the Li+ ion migration. The LiFePO4 is an example. Therefore, the
cathode materials are family of the oxygen closed packed arrays. Monitoring
the structure evolution of the cathode materials is the key to making a high
quality Lithium battery. These targets can be comprehensively done by
AHRTEM.

ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of
China, Grant 50372058 and the Analysis & Measurerment of Zhejiang
Province Grant 2008F70050. Authors also greatly appreciate the financial
support of Jinhe new material Inc.

REFERENCES
[1] John, B. (2002). Goodenough “Oxide cathodes”, In: Advances in
180 Yuewu Zeng, Shaofeng Chen, Jinhua He and Z. C. Kang

Lithium ion batteries 135 edited by W. Van. Schalkwijk and B. Scrosati

Kluwer Academic/Plenum Publisher.
[2] Rickert, H. (1985). Solid State Electrochemistry, An Introduction.
Spring-Verlag, Berlin, Heidelberg, New York.
[3] Weppner, W. (1985). In “Transport-structure relations in Fast ion and
Mixed Conductors” edited by F. W. Poulsen, N. Hessel Andersen, K.
Clausen, S. Skaarup, O. Toft Sorensen. Riso natl Lab. Roskilde, DK,
199.
[4] Wagner 7th meeting, Intl, C. (1955). Committee on Electrochemical
Thermodynamics and Kinetics Lidau Butterworths, London, 361.
[5] Ariyoshi, K. Iwakoshi, Y. Nakayama, N. Ohzuku, T. Electrochem. J.
(2004). Soc., 151, A296.
[6] Yabuuchi, N. Koyama, Y. Nakayama, N. Ohzuku, T. (2005).
J. Electrochem. Soc., 152, A 1434.
[7] Cowley, JM. Diffraction Physics. North-Holland, Amsterdam.
[8] Spence, JCH. (2003). High resolution Electron Microscopy. Oxford
Univ. Press. Oxford and New York.
[9] Lipson, HS. (1973). Optical Transforms. Academic Press New York.
[10] Van der Ven, A. Aydinol , MK. Ceder, G. Créese, G. hafner, J. (1998).
Physical Review B., Vol. 58, No.6, 2975.
[11] Gerbrand Ceder and Antón Van de Ven, (1999). Electrochmica Acta.,
45, 131.
[12] Youngil Lee, Min Gyu Kim, Jisuk Kim, Yoojin Kim, and Jaephil Cho,
(2005). Journal of the electrochemical society, 152 (9), A1824.
[13] Yuewu Zeng. (2008). Journal of Power Sources, 183, 316-324.
[14] Yuewu Zeng, Jinghua He. (2009). Journal of Power Sources, 189, 519-
521.
In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 7

SOFT SOLUTION PROCESSING

OF NANOSCALED LITHIUM VANADIUM
OXIDES AS CATHODE MATERIALS
FOR RECHARGEABLE
LITHIUM ION BATTERIES

Hao Wang,* HaiYan Xu and Hui Yan

The College of Materials Science and Engineering,
Beijing University of Technology, Beijing, China.

ABSTRACT
Lithium vanadium oxides have been extensively studied because of their
possible application as a cathode material for rechargeable lithium batteries. Due
to their low cost, they are one of the promising substitutes for the expensive
LiCoO2 cathode presently commercially used. Lithium vanadium oxides including
γ-LiV2O5 and LiV3O8 have been prepared by soft solution methods in this study.
In the first part of this work, γ-LiV2O5 nanorods have been prepared directly by a
simple solvothermal method using ethanol as a solvent, which also serves as a
reducing agent. The γ-LiV2O5 nanorods with diameters of 30-40 nm obtained at
160 oC shows a larger capacity of 259 mAh/g in the range of 1.5 - 4.2 V, and its
capacity remained 199 mAh/g after 20 cycles. In the second part, LiV3O8 nanorods

*
Corresponding author: E-mail: [email protected]
182 Hao Wang, HaiYan Xu and Hui Yan

have been obtained by a novel hydrothermal-based two-step method. The LiV3O8

sample treated at 300 oC shows a poor crystallinity while a specific capacity of
302 mAh/g in the range of 1.8 - 4.0 V, and its capacity remained 278 mAh/g after
30 cycles. It indicates that the lithium vanadium oxide nanorods prepared by the
above methods have potentiality to be used as cathode material in rechargeable
lithium ion batteries.

INTRODUCTION
Worldwide research and development is in progress for rechargeable
lithium ion batteries because of its wide application in portable electronic
goods, electric vehicle systems and dispersed-type energy storage system.
Much of this effort is focused on developing the cathode material for lithium
ion batteries because the performance and cost of the batteries are often
decided by the properties of the cathode material. In the last 20 years,
vanadium oxides have been widely investigated as cathode materials in lithium
ion batteries due to their low cost, low toxicity, high specific energy, and long
cycle life. Lithium ion can react with V2O5 to form various compounds such as
LiV3O8 [1-5], LiV2O5 (LiV2O5 has many modifications including α-, β-, ω-, γ-
LiV2O5) [6-10], LiV2O4 [11], Li0.6V2-δO4-δ [12] etc. Among them, γ-LiV2O5
and LiV3O8 were most intensively studied [1-10, 13-15].
The preparation method has significant influences on the electrochemical
behavior of γ-LiV2O5 and LiV3O8, therefore a great deal of work has been
done on their preparation to improve their electrochemical performance. In
this study, soft solution methods including a solvothermal route and a
modified hydrothermal-based method have been performed to prepare γ-
LiV2O5 and LiV3O8 nanorods, respectively.

LI1+XV3O8
Introduction

LiV3O8, as a species of the lithiated vanadate family, has very attractive

characteristics such as high specific energy, good rate capacity, and long cycle
life. The structure of LiV3O8 can be shown as in Figure 1. [16] It has a
monoclinic structure and the space group in P21/m. The structure consists of
VO6 octahedra and VO5 distorted trigonal bipyramids and is built up by
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 183

sharing the edges and corners of the trigonal bipyramids and the octahedra to
form a zigzag ribbon. Lithium can be localized in both of two kinds of vacant
sites named octahedral and tetrahedral sites (Figure 1), in which the original
combined lithium atoms occupy octahedral coordinated sites and the
intercalated ones occupy tetrahedral sites, respectively.
It is well known that the preparation methods and post-treatments have
significant influences on the electrochemical properties of LiV3O8. The
conventional method was high temperature melting in which LiV3O8 was
produced by reaction between Li2CO3 and V2O5 at 680 oC [17, 18]. This
method has met difficulty to control the composition and homogeneity of the
final products. Meanwhile, the product LiV3O8 had a low capacity of 180
mAh/g in the range of 1.8-4.0 V. Afterwards, many improved solution
methods were proposed [2, 4, 19-21]. The solution method does not need a
high reaction temperature, and the products could reach a high homogeneity
and high capacity.
As one of the solution methods, hydrothermal method has been
extensively used for the synthesis of inorganic compounds. Chirayil et al. had
obtained a new layered lithium vanadium oxide LixV2-δO4-δ·H2O via
hydrothermal method using tetra-methyl ammonium as template [11]. Oka et
al. had prepared AV3O8 (A=K, Rb, and Cs) by the hydrothermal treatment of
V2O5 and ANO3 solutions at 250 oC. The results showed that RbV3O8 had the
known structure of the KV3O8 and CsV3O8 compounds [22, 23]. However,
attempts to make LiV3O8 and NaV3O8 hydrothermally were unsuccessful.

Figure 1. Structure model of LiV3O8. Key: (●) octahedral and (□) tetrahedral.
184 Hao Wang, HaiYan Xu and Hui Yan

Some reports have also noticed the importance of crystallinity on the

electrochemical properties of LiV3O8. It was shown that the poorly crystallized
LiV3O8 or LiV3O8 modified by ultrasonic treatment or hydrothermal
introduction of small amounts of inorganic compounds such as H2O, CO2 and
NH3 achieved an improved electrochemical performance [3, 5]. It is known
that the electrochemical behavior of cathode materials strongly depends on the
particle size: the bigger the particle size, the higher the cell polarization and
the lower the cell capacity [8]. In the present paper, LiV3O8 nanorods have
been prepared by a novel method, which is based on the hydrothermal
reaction, the experimental procedure and results are described below.

Experimental Section

Synthesis and characterization of LiV3O8

The starting materials were analytically pure LiOH, V2O5 and NH3⋅H2O (1
mol/L). First, sotoichiometric LiOH and V2O5 (Li : V = 1 : 3, molar ratio)
were blended in the deionized water. LiOH was dissolved completely and part
of V2O5 was dissolved. When NH3⋅H2O was added to the above mixture, V2O5
was dissolved completely into solution. The pH of the solution was 9. The
resultant dark green solution was then transferred to a 50 ml Teflon lined
autoclave. The autoclave was sealed and heated at 160 oC under auto-
generated pressure for 12 h. After hydrothermal treatment, a colorless clear
solution whose pH changed to 7 was obtained. This solution was dried in air at
100 oC to evaporate the water till an orange gel was prepared. The gel was
then heat-treated at different temperatures in the range of 300-600 oC for 12 h.
The gel was characterized by thermo-gravimetric analysis (TGA) using a
Model STA 449C (Germany, NETZSCH-Gerätebau GmbH Thermal
Analysis). The structure of the heat-treated products was examined by X-ray
diffractometry (XRD, Japan Rigaku D/Max-3C) using CuKα radiation (λ =
1.5405Å). The morphology was investigated by transmission electron
microscopy (TEM, Model Hitachi H-700H, 200 KV). Fourier transform
infrared (FTIR) absorption spectra were obtained by using a Nicolet Magna-IR
560 spectroscopy.

Electrochemical measurements
Electrochemical characterization of the products was performed in cells
with metallic lithium as the negative electrode and a liquid organic electrolyte
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 185

[LiPF6 in a volume ratio of 50:50 mixture of ethylene carbonate (EC) and

diethyl carbonate (DEC), absorbed in porous polypropylene separators,
Celgard 2400]. The cathode was a mixture of the active material, acetylene
black and poly (tetrafluoroethylene) (PTFE) in a weight ratio of 80:10:10. The
cells were assembled in an argon-filled dry box. Charge-discharge tests were
carried out at a constant current density of 0.3 mA/cm2 in a range of 1.8-4.0 V.
All the tests were performed at room temperature.

Results and Discussion

The TGA result of the precursor gel which was derived by hydrothermal
reaction and subsequent evaporation of water is illustrated in Figure 2. It can
be seen that in the range of 140 ~ 320 oC, the weight loss is about 15 %.
Above 320 oC, the weight remains stable up to 600 oC. The weight loss
process can be divided into two stages. The first weight loss begins at 140 oC
and ends at 230 oC with a weight loss of 13%, which mainly resulted from the
evaporation of NH3 and water. The second weight loss occurred in the range of
250 ~ 320 oC with a weight loss of 2 %, which was caused by the de-
intercalation of some strongly-bound water.

TGA result

104

100

96
Weight (%)

92

88

84

80
100 200 300 400 500 600
o
Temperature ( C)

Figure 2. TGA curve of the precursor gel.

186 Hao Wang, HaiYan Xu and Hui Yan

The XRD and the Structure of LiV3O8

Figure 3 shows the XRD patterns of the products heated at 300, 350, 400
and 600 oC. These XRD patterns reflect the structural variation during the
treatment process. With an increase in heat temperature the intensity of peaks
becomes stronger and the full width of half maximum intensity (FWHM)
decreases, which indicates that the crystallinity becomes higher.
In addition, it is noted that there is an obvious difference among the four
XRD patterns. The relative intensity of (100) peaks at around 13.86o becomes
stronger with increasing heat temperature. In the 600 oC diffraction pattern, the
intensity of (100) peak is stronger than any other peaks. While in the 300 oC
diffraction pattern, the relative intensity of (100) peak has much decreased. It
suggests that the particle shape of LiV3O8 depends on the heat temperature,
and higher heat temperature favors the preferential ordering of crystallites. It is
known that the intercalation process of Li+ ion between the layers of the
cathode is a diffusion process. Therefore the preferential ordering which
would lead to a long path for Li+ ion is not advantageous to intercalation [2].
100

-111
-202
103

(d)
-302

020
203
003

212
012
011
002

122
Intesnity (a.u.)

204
201

(c)

(b)

(a)

10 20 30 40 50 60

2 θ (deg.)

Figure 3. The XRD patterns of the samples heat treated at (a) 300, (b) 350, (c) 400,
(d) 600 oC.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 187

(a)

(b)

(c)

Figure 4. TEM micrographs of the samples heat treated at (a) 300, (b) 350, (c) 400 oC.
188 Hao Wang, HaiYan Xu and Hui Yan

The morphology of the as-synthesized LiV3O8

The TEM micrographs of the synthesized LiV3O8, at different heat
temperatures, are demonstrated in Figure 4. It can be seen that the heat
treatment has caused a change in the LiV3O8 crystallinity and morphology.
The sample treated at 300 oC (Figure 4a) consists of an agglomeration of small
rods. The shapes of the rods are not well recognized, indicating they are
relatively poorly crystallized. The diameters of the rods are about 40 nm and
the lengths are mostly less than 600 nm. Figure 4b is the micrograph of the
sample treated at 350 oC. Comparing to the 300 oC sample, the 350 oC sample
is well rod-shaped. The diameters of the rods are about 70 nm while the
lengths are diverse in the 0.5-2 μm range. The 400 oC sample which is shown
in Figure 4c consists of wider (>150 nm) and longer rods. The sizes of the
particles treated at 600 oC are much larger than that of the 400 oC sample, the
micrograph of which is not shown here. These results are in agreement with
the XRD data. With the increase in temperature, the particles of the products
become larger and more crystallized.

(d)

(c)
Intensity (a.u.)

(b)

(a)

1100 1000 900 800 700

-1
Wavenumber (cm )

Figure 5. The FTIR spectra of the samples heat treated at (a) 300, (b) 350, (c) 400,
(d) 600 oC.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 189

FTIR of the as-synthesized LiV3O8

FTIR spectra of LiV3O8 obtained at different heat temperatures are shown
in Figure 5. For the four curves, it can be seen that the FTIR absorption in the
spectral region of 700 ~ 1100 cm-1 is dominated by bands at 995, 954 and 744
cm-1, respectively. This data is compared with LiV3O8 synthesized from solid
state reactions, where major FTIR bands corresponding to V = O and V-O-V
vibrations are located at 996, 954 and 746 cm-1, respectively [24]. The sample
treated at 300 oC gives the same FTIR responses as that of crystalline LiV3O8,
suggesting that it is almost iso-structural with the latter.

Electrochemical properties of the as-synthesized LiV3O8

The charge-discharge curves at the second cycle of cells from products
heat treated at 300, 350, 400, 600 oC, respectively, are illustrated in Figure 6. It
is found that the specific capacities of the samples decrease with increasing the
heat temperature. The discharge capacity for the 300 oC sample is 302 mAh/g
in the range of 1.8 - 4.0 V, which is much higher than that of 600 oC sample
(190 mAh/g). Notably, the value of 302 mAh/g is considerably higher than the
capacities of 220 ∼ 274 mAh/g of LiV3O8 synthesized by other solution
methods [2, 4, 19-21], and exceeds the capacity of about 280 mAh/g of
hydrothermally and ultrasonically treated LiV3O8 [3, 5]. From the XRD data
we have known that the sample treated at higher temperature has higher
crystallinity. The above results also suggest that the well-crystallized sample
does have poor specific capacity, which is in agreement with the previous
studies [2-5, 19-21].

5
2
2nd cycle, current density: 0.3 mA/cm
(d) (c) (b) (a)
4
Potential (V vs Li/Li+)

2
(d) (c) (b) (a)

0 50 100 150 200 250 300 350

Specific Capacity (mAh/g)

Figure 6. Charge-discharge curves of the samples heat treated at (a) 300, (b) 350, (c)
400, (d) 600 oC. Current density: 0.3 mA/cm2.
190 Hao Wang, HaiYan Xu and Hui Yan

In Figure 7, the discharge capacities are shown as a function of cycle

number. It can be seen that the samples synthesized via this novel method
show better capacity retention. The capacity of the 300 oC samples is 278
mAh/g after 30 cycles. Meanwhile, the 300 oC sample shows better cycling
behavior compared with the samples treated at higher temperature.

CONCLUSION
In this study, a novel method, which is based on the hydrothermal reaction
has been performed to synthesize LiV3O8 nanorods. This hydrothermal
reaction did not directly yield a solid product. A gel, which was used as the
precursor for the post heat treatment was obtained after evaporation of the
hydrothermal treated solution. The gel was homogeneous and ultrafine, which
should be the reason why the LiV3O8 nanorods could be obtained in this study.
Heat treatment at different temperatures influenced the particle size and
crystallinity of the products, which consequently affected their electrochemical
performance. The sample treated at 600 oC shows a good crystallinity and a
low discharge capacity. In contrast, the sample treated at 300 oC shows a
poorer crystallinity while a better capacity of 302 mAh/g in the range of 1.8 -
4.0 V, and its capacity remained 278 mAh/g after 30 cycles.

350

300
Specific capacity (mAh/g)

(a)
250 (b)
(c)
200

(d)
150

100
0 4 8 12 16 20 24 28 32
Cycle number

Figure 7. The cycle performance of the cells with LiV3O8 heat treated at (a) 300, (b)
350, (c) 400, (d) 600 oC as cathode active material. Current density: 0.3 mA/cm2.
Voltage window: 1.8-4.0 V.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 191

γ-LIV2O5

Introduction

Figure 8. Schematic crystal structure of γ-LiV2O5 projected onto the orthorhombic a-b
plane and a-c plane. The filled circles represent Li+ ions. The squares represent V
atoms. The white and shaded square pyramids show two kinds of VO5 pyramids (two
crystallographic vanadium sites).
192 Hao Wang, HaiYan Xu and Hui Yan

γ-LiV2O5, as one of the promising cathode materials for rechargeable

lithium batteries, has attracted tremendous research interest in recent years [6,
9, 10]. Orthorhombic γ-LiV2O5 has a layer structure with lithium ions between
the layers. In this structure, there are two crystallographic vanadium sites that
form two kinds of zigzag chains, the shaded and the white zigzag chains, as
shown in Figure 8 [25]. The valence states of the vanadium ions were inferred
from the results of structural analysis to be V4+ for the shaded zigzag chains
and V5+ for the white zigzag chains [25]. Within the layers, V4+O5 (shaded)
zigzag chains are linked to V5+O5 (white) zigzag chains by corner sharing, as
shown in Figure 8.
In particular, a lot of work has been devoted to the synthesis of γ-LiV2O5,
because it is very difficult to synthesize this compound, in which there are two
valence states (V5+ and V4+) of vanadium co-existing. So far, solid-state
reaction routes2 and a procedure developed by Murphy et al. [7] were the two
commonly used preparation method for the synthesis of γ-LiV2O5. By solid-
state reaction routes, the mixture of LiVO3, V2O5, and VO2 or V2O3 was
heated at above 600 oC under vacuum or nitrogen protected atmosphere in
order to control the valence balance of V4+ and V5+. This calcinating method is
usually faced with difficulty to control the homogeneity and particle size of the
final products. It has been shown that the electrochemical behavior of cathode
materials strongly depends on the particle size: the bigger the particle size, the
higher the cell polarization and the lower the cell capacity [8]. The synthetic
method developed by Murphy et al. includes two steps: firstly, δ-LiV2O5 was
synthesized through the reduction of V2O5 with appropriate amount of lithium
iodide in acetonitrile (CH3CN) at ambient temperature; secondly, the as-
prepared δ-LixV2O5 was heated at 350 oC under argon to obtain γ-LiV2O5.
Such route has demonstrated the feasibility of preparing γ-LiV2O5 as a cathode
material for rechargeable lithium ion batteries. However, the high cost and
sensitivity to moisture of LiI and CH3CN make it not viable as a low cost and
low toxicity preparation method for cathode materials.
We have proposed a simple and mild solvothermal method for the
synthesis of γ-LiV2O5. In this process, γ-LiV2O5 nanorods were synthesized
directly from the solvothermal reaction of V2O5, LiOH and ethanol at 160-200
o
C in an autoclave. Ethanol was employed as a solvent as well as a reducing
agent. Compared with the two commonly used preparation methods for γ-
LiV2O5, the newly developed solvothermal method is cheaper and milder, for
example, vaccum or argon/nitrogen protected atmosphere or post annealing is
not necessary for this simple one-step process. Therefore, the solvothermal
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 193

process seems to offer a potentially low-temperature, low-cost and

environmentally friendly way of producing single-phase, uniform-particle size
and fine-grained γ-LiV2O5 for rechargeable lithium batteries. In this paper, the
effect of experimental parameters including temperature and time on the
properties of γ-LiV2O5 was also investigated. The as-obtained products were
further characterized by X-ray diffraction (XRD), Fourier transform infrared
(FTIR) spectroscopy, X-ray photoelectron spectrscopy (XPS), and
transmission electron microscopy (TEM). The electrochemical performance of
γ-LiV2O5 nanorods with different size was studied.

Experimental Section

Synthesis and characterization of γ-LiV2O5

In a 50 ml Teflon vessel, 0.02 mol of analytically pure LiOH and V2O5
were mixed in 40 ml of ethanol. Be well stirred, the Teflon vessel containing
the mixture was put into a stainless steel autoclave. After the autoclave was
kept at 160, 180, 200 oC under autogeneous pressure for 12-48 h, it was
allowed to cool to room temperature naturally. The as-formed solid precipitate
was filtered, washed with ethanol, and dried at 100 oC for 2 h.
For all products, XRD (Japan Rigaku D/Max-3C, Cu Kα radiation) was
utilized to identify the produced phase. Fourier transform infrared (FTIR)
absorption spectra were obtained by using a Nicolet Magna-IR 560
spectroscopy. XPS measurements were performed on a PHI-5300/ESCA
system with Mg Kα radiation as the exciting source, where the binding
energies were calibrated by referencing the C 1s peak to reduce the sample
charge effect. The morphology and particle sizes of the as-obtained γ-LiV2O5
were determined by TEM (Model Hitachi H-700 H, 200 KV).

Electrochemical measurements
Electrochemical tests were performed in cells with metallic lithium as the
negative electrode. The electrolyte was LiPF6 in the mixture of ethylene
carbonate (EC) and diethyl carbonate (DEC) (50:50), Celgard 2400 as
separators. The positive electrode composites were made by mixing the active
material, acetylene black and poly (tetrafluoroethylene) (PTFE) (80:10:10).
All cells used in this study were assembled in an argon-filled dry box. Charge-
discharge tests were carried out at a constant current density of 0.3 mA/cm2 in
a range of 1.5 - 4.2 V. All tests were performed at room temperature.
194 Hao Wang, HaiYan Xu and Hui Yan

Results and Discussion

The XRD results and the kinetic processing of the formation of γ-LiV2O5
Figure 9 shows the XRD patterns of the black products solvothermally
synthesized at 160, 180, 200 oC for 24 h. As can be seen, all the obtained
products have almost the same XRD patterns; which can be assigned to an
orthorhombic structure γ-LiV2O5 according to JCPDS cards No. 018-756. It is
suggested the formation of γ-LiV2O5 without any trace of impurities such as
V2O5, Li3VO4 and LiVO2 by this solvothermal route.
Figure 10 shows the XRD patterns of the products solvothermally
synthesized at 160 oC for 12-48 h. It is obvious that the variation of reaction
time causes a change in the XRD patterns of the resulting products. For 12 h,
the obtained product mainly consists of V2O5, in which the average valence of
vanadium is +5; For 18-24 h, the obtained product is pure γ-LiV2O5, in which
the average valence of vanadium is + 4.5. When the reaction time is further
prolonged to 48 h, the obtained product is chiefly LixV2-δO4-δ·H2O [11] with a
minor amount of γ-LiV2O5, in which the average valence of vanadium is lower
than +4. The above results indicate that when the reaction temperature is fixed
at 160 oC, the reaction time plays an important role in determining the phases
of products. We have also investigated the effect of the reaction time on the
phase(s) of the resulting products at the temperatures of 180 and 200 oC, and
obtained the similar results. It is suggested that, in this study, the formation of
γ-LiV2O5 can be attributed to a process that is mainly controlled by kinetics.
002

103

(a)
301
112
102

302
111
200

105
312
Intensity (a. u.)

013

304
205
011
201

202

020
313

123
204

306
022

414

(b)

(c)

10 20 30 40 50 60
2 θ (deg.)

Figure 9. The XRD patterns of the samples synthesized at (a) 160, (b) 180, (c) 200 oC
for 24 h.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 195

γ -L iV 2 O 5 ‹ L i x V 2 -δ O 4 -δ H 2 O ‡ V 2O 5
‹ ‹
‹
48 h
‹ ‹ ‹ ‹‹ ‹

24 h
Intensity (a.u.)

18 h

‡ ‡ ‡
12 h
‡ ‡ ‡‡ ‡ ‡

10 20 30 40 50 60
2 θ ( d e g .)

Figure 10. The XRD patterns of the samples synthesized at 160 oC for (a) 12, (b) 18,
(c) 24, (d) 48 h.

In our experiment, the synthesis of γ-LiV2O5 is carried out using a great

excess of ethanol as a solvent through a solvothermal process. To the ethanol,
a portion of it is oxidized (by V2O5) to aldehyde, which is experimentally
confirmed through chemical analysis of the final solution mixture. From the
above results, it can be seen that the ethanol acts not only as a solvent but also
as a reducing agent in the synthesis of γ-LiV2O5 powders. The possible
formation mechanism of γ-LiV2O5 through the solvothermal reaction of LiOH
and V2O5 in ethanol medium is a reductive recombination pathway. Thus, the
formation mechanism of γ-LiV2O5 through the reaction of LiOH, V2O5 and
excess ethanol under the solvothermal condition can be expressed as the
following:

2 LiOH + 2 V2O5 + CH3CH2OH → 2 γ-LiV2O5 + CH3CHO + 2 H2O

If the reaction time is further prolonged, the obtained γ-LiV2O5 may be

reduced to LixV2-δO4-δ·H2O, and the reaction equation can be expressed as the
following:

γ-LiV2O5 + CH3CH2OH → LixV2-δO4-δ·H2O + CH3CHO

196 Hao Wang, HaiYan Xu and Hui Yan

FTIR of the as-synthesized γ-LiV2O5

Figure 11 shows the FTIR spectra of the as-synthesized γ-LiV2O5 at 160
o
C for 24 h and the starting material V2O5. It can be seen, the FTIR absorption
bands of γ-LiV2O5 are different from those of V2O5 in the spectral region of
400 ~ 1200 cm-1. The FTIR spectrum of the as-synthesized γ-LiV2O5 (Figure
11 (a)) displays four major absorption bands at 1006, 952, 592, and 565 cm-1,
which are in agreement with the literature values. The absorption bands at
1006 and 952 cm-1 are attributed to V=O stretching vibrations, and the
absorption bands at 592 and 565 cm-1 are attributed to V-O-V bending
vibrations [26]. The FTIR spectrum of the starting material V2O5 (Figure 11
(b)) exhibits four major absorption bonds at 1025, 824, 600 and 473 cm-1
which have been associated with the V=O and V-O-V vibrations [26].

596 563
1006 954
Absorption Intensity (a.u.)

738
(a)

820
1024 586
(b) 474

1200 1000 800 600 400

-1
Wavenumber (cm )
Figure 11. The FTIR spectra of (a) γ-LiV2O5 synthesized at 160 oC for 24 h, and (b) the
starting material V2O5.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 197

516.7

(b)
Intensity (a.u.)

V (2p 3/2 )
517.5

(a)

511 513 515 517 519 521 523

Binding Energy (eV)
Figure 12. The XPS spectra of (a) γ-LiV2O5 synthesized at 160 oC for 24 h, and (b) the
starting material V2O5.

XPS of the as-synthesized γ-LiV2O5

Figure 12 shows the XPS spectra of the starting material V2O5 and the as-
synthesized γ-LiV2O5. It is obvious that the binding energy of V 2p for the as-
synthesized γ-LiV2O5 is lower than that for the starting material V2O5. The
binding energy of V 2p3/2 for the starting material V2O5 is 517.5eV, which
agrees with the literature value of V2O5 [27]. The binding energy of V 2p3/2 for
the as-synthesized γ-LiV2O5 is 516.7 eV, which is between those of V 2p3/2 for
V2O5 and VO2 (516.3 eV [27]). The average valence of vanadium in V2O5, γ-
LiV2O5 and VO2 is +5, +4.5 and +4, respectively.
198 Hao Wang, HaiYan Xu and Hui Yan

(a)

(b)

(c)

Figure 13. TEM micrographs of the γ-LiV2O5 synthesized at (a) 160, (b) 180, (c) 200
o
C for 24 h.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 199

5.0
2
1st cycle, current density: 0.3 mA/cm
4.5
+
Potential V vs Li/Li 4.0

3.5

3.0

2.5

2.0

1.5
(c) (b) (a)
1.0

0.5

0.0
0 50 100 150 200 250
Specific Capacity (mAh/g)

Figure 14. Charge-discharge curves of the cells with γ-LiV2O5 synthesized at (a) 160,
(b) 180, (c) 200 oC for 24 h as cathode active material. Current density: 0.3 mA/cm2.

300

250
Specific Capacity (mAh/g)

200 (a)

150 (b)
(c)
100

50

0
0 5 10 15 20
Cycle Number

Figure 15. The cycle performance of the cells with γ-LiV2O5 synthesized at (a) 160,
(b) 180, (c) 200 oC for 24 h as cathode active material. Current density: 0.3 mA/cm2.
Voltage window: 1.5-4.2 V.
200 Hao Wang, HaiYan Xu and Hui Yan

The morphologies of the as-synthesized γ-LiV2O5

Figure 13 shows the TEM micrographs of the as-synthesized γ-LiV2O5 at
160,180, 200 oC for 24 h. As can be seen, the solvothermal reaction
temperature has an effect on the particles size of the as-synthesized γ-LiV2O5.
With the increase in solvothermal reaction temperature, the as-synthesized γ-
LiV2O5 particles become larger and even their size distribution becomes
wider. The as-synthesized γ-LiV2O5 at 160 oC (Figure 13a) comprises
nanorods with diameters of 30-40 nm and lengths of 0.4-2 μm; The as-
synthesized γ-LiV2O5 at 180 oC (Figure 13b) consists of wider and longer rods
with diameters of 50-120 nm and lengths of 0.7-3.5 μm; The as-synthesized γ-
LiV2O5 at 200 oC for 24 h (Figure 13c) is composed of rods with diameters of
70-160 nm and lengths of 0.7-4 μm.

Electrochemical properties of the as-synthesized γ-LiV2O5

Figure 14 shows the charge-discharge curves of the cell with the
solvothermally-synthesized γ-LiV2O5 at 160, 180 and 200 oC for 24 h during
the first cycle. It can be seen that the discharge capacity for the product
synthesized at 160oC is 259 mAh/g in the range of 1.5 - 4.2 V, which is much
higher than that of the product synthesized at 200 oC (218 mAh/g) and 180 oC
(228 mAh/g). From the TEM results, we know that the solvothermal-
synthesized γ-LiV2O5 at 200 oC has a larger size than that of the product
obtained at 160 oC. Thus, it is reasonable to infer that the product with smaller
particle size has a higher specific capacity, which is also consistent with the
previous report [5].
Figure 15 shows the cycle performance of the cell with the as-synthesized
γ-LiV2O5 at 160, 180 and 200 oC for 24 h. It can be seen that the
solvothermally synthesized γ-LiV2O5 shows better capacity retention. In the
first 6 cycles, the specific capacities of three cells reduce quickly, and then
maintain stable in the subsequent cycles. The specific capacity for the cell with
γ-LiV2O5 synthesized at 160 oC is 199 mAh/g after 20 cycles. The specific
capacity for the cell with γ-LiV2O5 synthesized at 180 oC and 200 oC is 152
mAh/g and 129 mAh/g after 20 cycles, respectively. The above results indicate
that the γ-LiV2O5 nanorods synthesized by this solvothermal method have
potentiality to be used as a cathode material in rechargeable lithium cells.
 Soft Solution Processing of Nanoscaled Lithium Vanadium Oxides… 201

CONCLUSION
In summary, LiV3O8 nanorods have been obtained by a novel two-step
method which was based on the hydrothermal reaction. The as-prepared
LiV3O8 nanorods showed a good charge-discharge and cycle performance.
Heat treatment at different temperatures influenced the particle size and
crystallinity of the products, which consequently affected their electrochemical
performance. The sample treated at 300 oC shows a poorer crystallinity while a
better capacity of 302 mAh/g in the range of 1.8 - 4.0 V, and its capacity
remained 278 mAh/g after 30 cycles. Meanwhile, A simple and low-cost
solvothermal method has been developed to synthesize γ-LiV2O5 nanorods by
using ethanol as a solvent as well as a reducing agent. Preliminary
electrochemical tests indicated that the γ-LiV2O5 obtained at 160 oC has an
initial specific capacity of 259 mAh/g in the range of 1.5–4.2 V. It indicates
that the lithium vanadium oxide nanorods prepared by the above methods have
potentiality to be used as cathode material in rechargeable lithium batteries.

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202 Hao Wang, HaiYan Xu and Hui Yan

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Electrochimica Acta., 2004, 49, 349.
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In: Lithium Batteries: Research, Technology… ISBN: 978-1-60741-722-4
Editors: Greger R. Dahlin, et al. © 2010 Nova Science Publishers, Inc.

Chapter 8

ADVANCED LITHIUM-ION BATTERIES

FOR PLUG-IN HYBRID-ELECTRIC
VEHICLES

Paul Nelsona and Khalil Amineb

a
Argonne National Laboratory, 9700 S. Cass Ave, Argonne,
IL 60439, USA, 630-252-4503.
b
Aymeric Rousseau, Argonne National Laboratory
Hiroyuki Yomoto, EnerDel Corp., Argonne, IL 60439, USA.

ABSTRACT
In this study, electric-drive vehicles with series powertrains were
configured to utilize a lithium- ion battery of very high power and
achieve sport-sedan performance and excellent fuel economy. The battery
electrode materials are LiMn2O4 and Li4Ti5O12, which provide a cell area-
specific impedance of about 40% of that of the commonly available
lithium-ion batteries. Data provided by EnerDel Corp. for this system
demonstrate this low impedance and also a long cycle life at 55oC. The
batteries for these vehicles were designed to deliver 100 kW of power at
90% open- circuit voltage to provide high battery efficiency (97-98%)
during vehicle operation. This results in battery heating of only 1.6oC
per hour of travel on the urban dynamometer driving schedule (UDDS)
cycle, which essentially eliminates the need for battery cooling. Three
vehicles were designed, each with series powertrains and simulation test
weights between 1575 and 1633 kg: a hybrid electric vehicle (HEV) with a
204 Paul Nelson and Khalil Amine

45-kg battery, a plug-in HEV with a 10-mile electric range (PHEV10) with
a 60-kg battery, and a PHEV20 with a 100-kg battery. Vehicle
simulation tests on the Argonne National Laboratory’s simulation
software, the Powertrain System Analysis Toolkit (PSAT), which was
developed with MATLAB/Simulink, showed that these vehicles could
accelerate to 60 mph in 6.2 to 6.3 seconds and achieve fuel economies
of 50 to 54 mpg on the UDDS and highway fuel economy test (HWFET)
cycles. This type of vehicle shows promise of having a moderate cost if it is
mass produced, because there is no transmission, the engine and generator
may be less expensive since they are designed to operate at only one
speed, and the battery electrode materials are inexpensive.

Keywords: vehicle simulation, lithium-ion batteries, series-engine hybrid

1. INTRODUCTION
Lithium-ion batteries show promise for powering hybrid electric vehicles
(HEV) and plug-in hybrid vehicles (PHEVs), but the batteries under
development differ widely in their capabilities. Also, a variety of vehicle types
are under consideration and the requirements for their batteries vary
considerably: some demand high energy per unit volume and weight, and
others place greater emphasis on high power. For these vehicle applications,
the batteries are required to have safe and consistent performance throughout a
life of about 15 years and be available in mass production at a moderate price.

2. STATUS OF ADVANCED BATTERY DEVELOPMENT

Table 1 presents the characteristics of several lithium-ion batteries in
various stages of development. These batteries promise markedly different
levels of performance for the various criteria for which batteries are evaluated
for the HEV and PHEV applications.
The LiNi0.8Co0.15Al0.05O2 (NCA)-graphite system has good power and
energy characteristics because of its high voltage, good electrode specific
capacities and good area-specific impedance (AS I) [1, 2]. Projections show it
would have a moderate cost in production and good life if the state of charge
(SOC) is maintained between 90% and 30%. Work remains to be done to
increase the useful fraction of the (SOC) range and achieve excellent battery
life (15 years). Also, at present the NCA electrode has a tendency to release
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 205

significant amounts of oxygen during thermal runaway, resulting in oxidation

of the electrolyte [3,4]. The graphite electrode adds chemically bound energy
to such a catastrophic incident.
The LiFePO4 (LFP) electrode is more stable and does not generate
oxygen during heating and, thus, appears to be safer at this time than the NCA
electrode. Otherwise, the performances of the first two systems in Table 1 are
expected to be similar, but the LFP-graphite system shows promise of a
slightly lower raw material cost. However, developing a low-cost process for
preparing nano-LiFePO4 material, which is required for good power, requires
additional effort.
The third system in Table 1, MS-TiO, has electrodes with low capacity,
and the couple has lower voltage than those of the first two systems. The
lithium-spinel positive electrode does not form a good couple with a graphite
negative electrode because manganese dissolves in the electrolyte and poisons
the graphite electrode [5-8]. Against a lithium-titanate electrode, however, it
forms a very stable couple, albeit with a low voltage. The titanate electrode
has a voltage that is 1.5 V higher than that of lithium, whereas a good graphite
electrode is only about 0.1 V higher. The combination of low voltage and low
specific capacities for both electrodes in the MS-TiO system results in lower
specific energy for the battery than for most lithium-ion systems. This is
somewhat mitigated by the very stable performance and long cycle life for
100% discharges, as discussed below, which permit operating MS-TiO
batteries over the SOC range of 100% to 10% for the PHEV application.
Another favorable characteristic of the MS-TiO system is very low ASI, which
results in very high power. The safety characteristics appear to be excellent; it
is very tolerant of excessive voltage upon charging, with a much reduced
likelihood of lithium deposition, and the stored chemical energy in the system
is very low when compared with that of systems with graphite electrodes. As
will be shown by the data that follow, the cycle life for the MS-TiO system is
excellent. Cost projections are only tentative, but the MS-TiO system appears
to have inherent advantages over the other systems in that its electrode
materials have low cost and are plentiful.
The fourth system in Table 1, MNS-TiO, is similar to the MS-TiO system,
but with a manganese- nickel spinel positive electrode that operates at a very
high voltage versus lithium (4.8 V at full charge) and with improved capacity
relative to manganese spinel. At the present time the ASI is higher than for the
MN-TiO system, but it is believed that this can be improved sufficiently to
achieve the required power (100 kW for the PHEVs in this study) for a 40-
mile range PHEV.
206 Paul Nelson and Khalil Amine

Table 1. Selected Lithium-Ion Battery Systems for Plug-in

Hybrid Electric Vehicles.

System NCA- LFP- MS- MNS- MN-

Graphite Graphite TiO TiO Graphite
Electrodes LiNi0.8Co0.1 LiFePO4 LiMn2O4 LiMn1.5Ni0 Li1.2Mn0.6N
Positive 5Al0.05O2 Graphite Li4Ti5O12 .5O4 i0.2O2
Negative Graphite Li4Ti5O12 Graphite
Capacity, 155 162 100 130 275
mAh/g 290 290 170 170 290
Positive
Negative
Voltage, 50% 3.6 3.35 2.52 3.14 3.9
SOC
ASI for 10-s 25 25 9.2 100 25
Pulse, ohm-cm2
Safety Fair Good Excellent Excellent Excellent
Life Potential Good Good Excellent Unknown Unknown
Cost Moderate Moderate Low Moderate Moderate
Status Pilot Scale Pilot Scale Develop. Research Research

The highest capacity positive electrode in Table 1 is in the MN-graphite

system developed at Argonne [9,10]. This would result in the lowest battery
weight for a 40-mile PHEV for the batteries reviewed in Table 1. This system
requires more development work, but it illustrates the improvements in battery
performance that may come in the future.

3. SPINEL-TITANATE BATTERY PERFORMANCE

MODELING

3.1 Approach

Despite its low capacity and low voltage, we have studied the MS-TiO
system to determine if a battery-vehicle combination could be found that
exploits the very high power of the MS-TiO system. A type of vehicle that
may be particularly enhanced by very high battery power is one with a series-
connected powertrain with sport-sedan performance. For such a vehicle to
achieve high fuel economy, the engine should operate close to its peak
efficiency, which requires that the battery have high power to accept charging
at a high rate. Therefore, we decided to design a battery that could discharge at
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 207

the 100-kW rate for a 10-s burst at 90% open-circuit voltage (OCV) so that the
overall battery efficiency would exceed 97% for most vehicle-driving cycles.
The high battery power would also make possible higher vehicle performance
than is usually expected of HEVs and more like that of a sport-sedan.
Through a collaboration between Argonne and EnerDel, experimental data
became available that establish the low area-specific impedance of the MS-
TiO system and the promising long cycle life for deep discharges, which
justify the assumption that the battery can be operated between 100% and 10%
SOC. Two types of modeling were required to characterize the battery for
vehicle simulation studies: (1) design modeling to determine the battery
weight, volume and electrical performance and (2) impedance modeling. The
experimental data and modeling are discussed below.

3.2 Experimental Data

Tests with a 1 .8-Ah MS-TiO cell demonstrated outstanding power; 97%

of the capacity measured at the 1C discharge rate was delivered at the 50C rate
(Fig. 1) [11]. These results were correlated to obtain the impedance equations
required for the vehicle simulation tests.

2.8

2.6
2C
2.4 5C
Voltage(V)

10C
2.2 20C
30C
2.0 40C
50C
1.8

1.6

1.4
0 10 20 30 40 50 60 70 80 90 100 110
% of 1C Capacity

Figure 1. Lithium-Manganese Spinel/Lithium-Titanate 1 .8-Ah Cell Charged at 1C

Rate and Discharged at Varying Rates at 30oC [11]
208 Paul Nelson and Khalil Amine

The capacity stability was demonstrated in tests in which the entire cell
capacity was discharged and charged at the 5C rate at an elevated temperature
of 55oC to accelerate degradation. After 2,300 cycles there was little
indication of capacity loss (Fig. 2) [11]. Pulse power characterization tests
were carried out at 30oC after 1,000 and 2,000 cycles and demonstrated little
loss of power with cycling, and incidentally, restored the full initial capacity.
The promising results obtained in these aggressive tests at high temperature
indicate that MS-TiO batteries may be able to achieve the 5,000 cycles
required for the PHEV application.

3.3 Battery Design Modeling

We have developed a method, based on Excel spreadsheets, for designing

cells and batteries that has been applied for several battery systems. In recent
years, the method has been used primarily for designing lithium-ion batteries
for HEVs and PHEVs [12,13]. One form of input for this method is test results
from measurements of capacity and ASI on small cells with areas of only a
few square centimeters. It is also possible to accept data from larger cells by
accounting for the resistance of the current collection system in the tested
cells. The method calculates the volumes and weights of all of the cell and
battery components and the electrical performance of the battery. By this
method, three batteries were designed for a series-connected vehicle from the
data in Table 1 for the MS-TiO system and from other proprietary input. The
results are shown in Tables 2 and 3.

2.0
1.8
1.6
1.4
Capacity (Ah)

1.2
1.0
0.8
55oC
0.6
5C charge
0.4 5C discharge
0.2 100% DOD
0.0
0 500 1000 1500 2000 2500
Cycle Number

Figure 2. Deep Discharging of Lithium-Manganese Spinel/Lithium-Titanate Cell to

Demonstrate Long Cycle Life [11]
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 209

Table 2. Cell Parameters for Lithium-Manganese Spinel/Lithium-

Titanate Batteries for HEVs and PHEVs.

Cell Parameters HEV 10-Mile* 20-Mile*

PHEV PHEV
Cell Capacity (1/C rate), Ah 10.0 16.6 33.3
Positive First Charge Loading Density, 0.54 0.88 1.79
mAh/cm2
Negative-to-Positive 1st Charge Capacity 1.0 1.0 1.0
Ratio
Maximum Voltage on Charging, V 2.7 2.7 2.7
Average Voltage on Discharge, V 2.51 2.51 2.51
Positive Electrode
Active Material Li1 .06Mn1 Li1 .06Mn1 Li1 .06Mn1
.94O4 .94O4 .94O4
Thickness of Coating (each side), µm 25 40 82
Negative Electrode Material
Active material Li4Ti5O12 Li4Ti5O12 Li4Ti5O12
Thickness of Coating (each side), µm 21 34 70
Total Cell Area, cm2 20,500 20,500 20,500
Cell Dimensions, mm
Height 189 219 219
Width 104 116 187
Thickness 12.2 12.4 12.5
Cell Weight, g 471 648 1102
Power, W 1251 1251 1251
Cell Specific Power, kW/kg 2.66 1.93 1.14
Cell Specific Energy (1/C rate), Wh/kg 53 64 76
*Based upon energy usage of 300 Wh/mile.

Table 3. Battery Parameters for Lithium-Manganese Spinel/Lithium-

Titanate Batteries for HEVs and PHEVs.

Battery Parameters HEV 10-Mile* 20-Mile*

PHEV PHEV
Number of Cells in Battery 80 80 80
Number of Modules (10 cells each) 8 8 8
Energy Storage (1-h rate), kWh 2.0 3.3 6.7
Useable Energy
HEV, 60% to 35% SOC 0.50
PHEV, 100% to 10% SOC 3.0 6.0
Discharge Power (10 s), kW 100 100 100
Discharge Voltage af Full Power (50% SOC), V 181 181 181
% of Open Circuit Voltage 90 90 90
Power Density, kW/L 3.59 2.81 1.81
Current on Discharge, A
210 Paul Nelson and Khalil Amine

Table 3 – (Continued)

Battery Parameters HEV 10-Mile* 20-Mile*

PHEV PHEV
At Rated Power (50% SOC, 90% OCV) 552.5 552.5 552.5
Maximum Allowed (30 s) 560.0 560.0 560.0
Maximum Regeneration Power, kW
Short-Term (2-s regen braking) 100 100 100
Long-Term (up to 60 s) 70 70 70
Maximum Charge Voltage, V 216 216 216
Insulated Battery Wall Thickness, mm 7 7 8
Battery Dimensions, mm
Length 852 973 973
Width 266 270 274
Height 123 135 207
Volume, L 28 36 55
Weight, kg 45 60 100
Total Weight of Cells, % of Battery Weight 84 86 88
Cooling Fluid (exterior of modules only) Air Air Air
*Based upon energy usage of approximately 300 Wh/mile.

3.4 Impedance Modeling

On the basis of the data shown in Figures 1 and 2, the impedance of

the experimental cell was modeled to fit Equation (1) in Figure 3 [14].

Equation (1) 1000*(OCV-VL)/IL = R = Ro+Rp1*Ip1/IL+Rp2*Ip2/IL

Where, OCV = open circuit voltage, V

VL = cell voltage, V
R = total cell impedance, milliohms
Ro = cell internal ohmic resistance, milliohms
Rp1 = first internal polarization resistance, milliohms
Rp2 = second internal polarization resistance, milliohms IL = cell load
current, A
Ip1 = current through first polarization resistance, A
Ip2 = current through second polarization resistance, A
The values for Ip1 and Ip2 are derived by integration of the differential
equation:
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 211

Equation (2) dlp/dt = (IL-Ip)/ô

The results were adjusted to simulate a 1 -Ah cell to facilitate use in

calculating battery impedance for any desired capacity and number of cells
and are shown in Table 4, in which the values of Tau1 and Tau2 are time
constants expressed in seconds for the two polarization resistances in the
model.
The impedance parameters for the 1-Ah Cell of Table 4 were applied for
the 100-kW batteries of Table 3 with the result illustrated in Table 5.

IL Ro

VL OCV

Rp1 Rp2

Ip1 Ip2

Figure 3. Impedance Model for Lithium-Manganese Spinel/Lithium-Titanate

Batteries [14]

Table 4. Parameters for Calculating Impedance of a 1-Ah Lithium-

Manganese Spinel/Lithium-Titanate Cell.

DOD, % OCV Ro Rp1 Rp2 Tau1 Tau2

0 2.661 0.00320 0.00220 0.00100 10 270
10 2.621 0.00320 0.00220 0.00120 10 270
20 2.593 0.00320 0.00209 0.00130 10 270
30 2.569 0.00320 0.00220 0.00130 10 270
40 2.543 0.00320 0.00230 0.00140 10 270
50 2.514 0.00320 0.00266 0.00140 10 270
60 2.483 0.00320 0.00313 0.00132 10 270
70 2.446 0.00320 0.00355 0.00108 10 270
80 2.408 0.00320 0.00420 0.00100 10 270
90 2.368 0.00320 0.00500 0.00100 10 270
95 2.336 0.00380 0.00600 0.00100 10 270
100 1.6 0.00440 0.00700 0.00100 10 270
212 Paul Nelson and Khalil Amine

Table 5. Impedance, Voltage, and Current for 10-second Power Burst

for 1 00-kW Lithium-Manganese Spinel/Lithium-Titanate Batteries

10-s Burst Discharge at 100 kW 10-s Burst Power

SOC, % R-10s V %OCV A at 560 A, kW
100 0.0342 195.4 91.8 511.8 108.5
90 0.0343 191.8 91.5 521.3 106.7
80 0.0338 189.6 91.4 527.3 105.6
70 0.0343 187.2 91.1 534.2 104.3
60 0.0348 184.6 90.7 541.7 103.0
50 0.0364 181.0 90.0 552.5 101.2
40 0.0386 176.8 89.0 565.6 99.1
30 0.0405 172.2 88.0 580.8 96.9
20 0.0435 166.5 86.5 600.4 94.2
10 0.0472 160.0 84.4 625.2 91.3
5 0.0562 149.2 79.9 670.1 87.0
0 0.0652

4. VEHICLE SIMULATION FOR HIGH-POWER BATTERIES

4.1 Approach

The Powertrain System Analysis Tool (PSAT) [15, 16], developed with
MATLAB/Simulink, is a vehicle-modeling package used to simulate
performance and fuel economy. It allows one to realistically estimate the
wheel torque needed to achieve a desired speed by sending commands to
different components, such as throttle position for the engine, displacement for
the clutch, gear number for the transmission, or mechanical braking for the
wheels. In this way, we can model a driver who follows a predefined speed
cycle. Moreover, as components in PSAT react to commands realistically, we
can employ advanced component models, take into account transient effects
(e.g., engine starting, clutch engagement/ disengagement, or shifting), and
develop realistic control strategies. Finally, by using test data measured at
Argonne’s Advanced Powertrain Research Facility (APRF), PSAT has been
shown to predict the fuel economy of several hybrid vehicles within 5% on the
combined cycle. PSAT is the primary vehicle simulation package used to
support the U.S. Department of Energy’s (DOE’s) FreedomCAR research and
development activities.
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 213

4.2 Vehicle Characteristics

Several vehicles were sized for different specifications based on the

same vehicle attributes:

• HEV
• PHEV with 10 miles All Electric Range (AER)
• PHEV with 20 miles All Electric Range (AER)

The main component masses are shown in Table 6 and Table 7 lists the
main characteristics of the simulated midsize car.
As shown in Figure 4, the configuration selected is a series engine
hybrid, very similar to the one used in the GM Volt [17].
Five driving cycles are considered in the study to evaluate the impact
of advanced lithium-ion batteries on fuel economy: UDDS (urban
dynamometer driving schedule), HWFET (highway fuel economy test), LA92
(1992 test data from Los Angeles), NEDC (new European driving cycle) and
Ford ATDS. The main characteristics of each cycle are summarized in
Table 8.

Table 6. Mass of Vehicle Components (kg)

Component HEV PHEV10 PHEV20

Engine Mass 120 120 120
Generator Mass 86 86 87
Motor Mass 144 144 146
Battery Mass 45 60 100
Vehicle Mass 1575 1590 1633

Table 7. Vehicle Main Specifications

Component Specifications
Engine 2004 US Prius
Electric machine Ballard IPT - Induction
Single Gear Ratio 2
Final Drive Ratio 3.8
Frontal Area 2.1 m2
Drag Coefficient 0.25
Rolling Resist. 0.007 (plus speed related term)
214 Paul Nelson and Khalil Amine

Wheel radius 0.317 m

Figure 4. Series Engine Configuration.

Table 8. Drive Cycle Characteristics.

Unit UDDS HWFET LA92 ATDS NEDC

Duration S 1372 764 1435 1799 1180
Distance Km/mi 11.92/7.45 16.38/10.24 15.7/9.81 25.2/15.75 10.9/6.84
Average Speed mph 19.5 48.26 24.6 31.5 20.86
Average Accel m/s2 0.5 0.19 0.67 0.55 0.59
Average Decel m/s2 -0.57 -0.22 -0.75 -0.55 -0.78
Number stops 17 1 16 18 13
Percent Stops 18.92 0.65 16.3 20.73 24.9
Note that all the simulations performed in PSAT represent hot conditions.

4.3 Component Sizing Algorithm

The components of the different vehicles were sized to meet the same
vehicle performances:

• 0-60 mph in less than 7sec

• Gradeability of 6% at 65 mph

To quickly size the component models of the powertrain, an automated

sizing process was developed. A flow chart illustrating the sizing process logic
is shown in Fig. 5. While the engine power is the only variable for
conventional vehicles, HEVs have two variables: engine power and electric
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 215

power. In that case, the engine is sized to meet the gradeability requirements
while the battery is sized to meet the performance requirements. In the study,
we also insure that the vehicle can capture the entire energy from regenerative
braking during decelerations on the UDDS.
Similar to the HEV configuration, the engine and generator powers are
sized to meet the gradeability requirements. In addition to HEVs, the battery
power has to be sized to follow the UDDS driving cycle while in all-electrical
mode. Finally, the battery energy is sized to achieve the required AER of the
vehicle. The AER is defined as the distance the vehicle can travel on the
UDDS without starting the engine. Note that a separate control algorithm is
used to simulate the AER. This algorithm forces the engine to remain off
throughout the cycle, regardless of the torque request from the driver.

Vehicle Assumptions

Motor Power

Battery Power

Engine Power

Battery Energy

No
Convergence

Yes

Figure 5. PHEV Component Sizing Process.

The main component characteristics resulting from the sizing algorithm

are described in Table 3.

Table 9. Component Sizing Results.

HEY PHEY10 PHEY20

Engine Power kW 100 100 102
Generator Power kW 95 95 96
Motor Power kW 130 130 132
Battery Power kW 100 100 100
Vehicle Mass kg 1575 1590 1633
Accel. Time 0-60 mph s 6.2 6.2 6.3
216 Paul Nelson and Khalil Amine

4.4 Control Strategy Philosophy

The control strategy of the PHEVs can be separated into two distinct
modes, as shown in Figure 6:

• Charge-Depleting (CD) Mode: Vehicle operation on the electric drive,

engine subsystem or both with a net decrease in battery SOC.
• Charge-Sustaining (CS): Vehicle operation on the electric drive,
engine
• subsystem or both with a ‘constant’ battery state-of-charge (i.e.,
within a
• narrow range), which is similar to that in current production HEVs.

During a simulation, the engine is turned on when the battery SOC is low
or the power requested at the wheel cannot be provided by the battery alone.
Turning the engine on expends fuel but conserves battery energy, so that more
miles can be traveled before the battery reaches its discharged state. When the
engine is ON, it is operated close to its best efficiency curve. As a result, the
battery is being charged by the engine during low power requests, leading to
lower electrical consumption.

100
veh_lin_spd_out [mile/h]
eng_pwr_out [kW]
80 ess_soc_abs [%]

60

40

20

-20
0 500 1000 1500 2000 2500 3000
time

Figure 6. Control Strategy SOC Behavior on.

 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 217

The initial SOC of the battery, which is also the battery’s maximum
charge, is 100%, and the final SOC of the battery, which is also the battery’s
minimum charge, is 10%. For the CD mode, the engine logic was written in
StateFlow and used several conditions, such as battery SOC, motor power
limits, and vehicle speed, to determine when the engine should turn on and the
output torque of the engine. The logic of the CS mode was similar to that of
current HEVs.

4.5 Fuel Economy Results

As previously mentioned, several driving cycles have been considered to

evaluate the benefits of the advanced lithium-ion batteries on PHEVs. Table 4
summarizes the electrical consumption on each PHEV vehicle on the first
cycle of each drive cycle. These results highlight the differences between the
different drive cycles. As expected, the standardized drive cycles (UDDS,
HWFET and NEDC) require a lower electrical consumption than the cycles
that are more “real-world”. The ATDS is the most aggressive drive cycle.

400 300

350 Series HEV

Series HEV
Series PHEV 10AER 250
300 Series PHEV 10AER
Series PHEV 20AER
Fuel Economy (mpg)

Series PHEV 20AER

Fuel Economy (mpg)

200
250

200 150

150
100
100

50
50

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
UDDS Cycle Number HWFET Cycle Number

Figure 7. Fuel Economy on UDDS and HWFET.

Table 10. PHEV Electrical Information.

UDDS HWFET NEDC LA92 ATDS

10 Elec Cons. First Cycle (Wh/mile) 224.6 204.3 234.1 282.6 190.4(1)
miles All Electric Range (miles) 13.8 14.3 12.8 10.3 9.5
AER
20 Elec Cons. First Cycle (Wh/mile) 257.9 209.9 241.6 297.9 300.8
miles All Electric Range (miles) 26.6 28.6 26.5 20.4 19.9
AER
218 Paul Nelson and Khalil Amine

(1) Engine started during the first cycle

Because the primary goal of PHEVs is to maximize the fuel displacement,
the following analysis focuses on fuel consumption. Figure 7 shows the
evolution of the fuel economy when each cycle is repeated 10 times.
The benefit of high-power batteries is noticeable on the more aggressive
driving cycles (Fig. 8). When an engine start would have been necessary for
low power batteries, the initial distance can be performed in EV mode without
any help from the engine. Note, however, that previous studies [18] have
demonstrated the need to know the trip distance to properly minimize fuel
consumption. However, higher battery power allows additional flexibility in
deciding when to start the engine.
Table 5 shows the charge sustaining fuel economies of the different
vehicles. Due to increased vehicle mass, the fuel economy decreases slightly
with an increase in All Electric Range.
Figure 9 shows the evolution of the electrical consumption for the UDDS
and ATDS drive cycles. The impact of the cycle aggressiveness can be seen by
the slope of the electrical consumption. In the case of the ATDS, the slope is
much stiffer than for the UDDS.

50 120

45 Series HEV
100 Series PHEV 10AER
40
Series PHEV 20AER
35
F u el E co n o m y (m p g )
F u e l E c o n o m y (m p g )

80
30 Series HEV
Series PHEV 10AER
25 60
Series PHEV 20AER
20
40
15

10
20
5

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
LA92 Cycle Number ATDS Cycle Number

Figure 8. Fuel Economy Evolution on LA92 and ATDS

Table 11. Charge Sustaining Fuel Economy (mpg)

UDDS HWFET NEDC LA92 ATDS

HEY 51.9 54.4 52.3 39.3 40.0
PHEY 10 51 53.3 51.5 38.6 38.8
PHEY 20 49.6 52 50.5 37.9 38
 Advanced Lithium-Ion Batteries for Plug-in Hybrid-Electric… 219

300 350

Series HEV 300 Series HEV

250
Series PHEV 10AER Series PHEV 10AER
Electrical Consumption (Wh/mile)

Electrical Consumption (Wh/mile)

250 Series PHEV 20AER
200 Series PHEV 20AER

200
150
150
100
100

50
50

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
-50 -50
UDDS Cycle Number ATDS Cycle Number

Figure 9. Electrical Consumption Evolution on UDDS and ATDS

Table 11. Component Average Efficiencies (%) on UDDS

Component HEY PHEY10 PHEY20

Engine 36.9 37.2 37.2
Generator 91.9 91.9 91.9
Motor 80.4 80.4 80.4
Battery 98.4 97.5 97.4
Gear 97.5 97.5 97.5

The efficiencies of the vehicle components are very high as illustrated

in Table 11 for theUDDS cycle. Improvement in the fuel economy for these
vehicles could be achieved by increasing the motor efficiency. An additional
motor of low power (30-50 kW) could be provided to be used under light
loads under which it could operate at higher efficiency than the high-power
motor (130 kW) in the evaluated designs.
The high battery efficiency, results in very little battery heating. One hour
of travel on the UDDS cycle would heat up the PHEY10 battery by only1.6 oC
under adiabatic conditions.

5. CONCLUSIONS
High vehicle performance, of the type expected from sport sedans, and
high fuel economy can be achieved at the same time by a vehicle having a
series powertrain and a high-power manganese spinel/lithium titanate battery.
Further improvement in fuel economy might result from improving the motor
efficiency. This battery can provide high power at such high battery efficiency
220 Paul Nelson and Khalil Amine

that battery cooling is virtually unnecessary. This type of vehicle shows

promise of having a moderate cost if it is mass produced because there is no
transmission, the engine and generator may be less expensive since they are
designed to operate at only one speed and power, and the battery electrode
materials are inexpensive.

ACKNOWLEDGMENTS
This work was supported by DOE’s FreedomCAR and Vehicle
Technology Office under the direction of Tien Duong and David Howell of
that program. The submitted manuscript has been created by the UChicago
Argonne, LLC, Operator of Argonne National Laboratory (“Argonne”).
Arrgonne, a U.S. Department of Energy Office of Science laboratory, is
operated under Contract No. DE-AC02-06CH1 1357. The U.S. Government
retains for itself, and others acting on its behalf, a paid-up nonexclusive,
irrevocable worldwide license in said article to reproduce, prepare derivative
works, distribute copies to the public, and perform publicly and display
publicly, by or on behalf of the Government.

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I; Vissers, D; Henriksen, G. Journal of Power Sources., 2001, 97-8, 684-
687.
[2] Abraham, DP; Liu, J; Chen, CH; Amine, K. Journal of Power Sources.,
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[3] Belharouak I; Lu, WQ; Vissers, D. et al. Electrochemistry
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[4] Doughty, DH; Roth, EP; Crafts, CC; Nagasubramanian, G; Henriksen,
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 INDEX

cell, x, 184, 192, 200, 203, 207, 208, 210,

A
211
absorption, 184, 189, 193, 196 chemical energy, 205
absorption bands, 196 collaboration, 207
absorption spectra, 184, 193 components, 208, 212, 214, 219
accounting, 208 composites, 193
acetonitrile, 192 composition, 183
adiabatic, 219 compounds, 182, 183, 184
aggressiveness, 218 configuration, 213, 215
algorithm, 215 Congress, 221
all‐electric, 215 consumption, 216, 217, 218
annealing, 192 control, 212, 215, 216
application, 205, 208 cooling, x, 203, 220
argon, 185, 192, 193 crystallinity, x, 182, 184, 186, 188, 189, 190,
201
crystallites, 186
B
cycles, xi, 204, 207, 208, 213, 217, 218
batteries, x, 181, 182, 192, 193, 201, 203, cycling, 208
204, 205, 206, 208, 211, 213, 217, 218
battery, x, 203, 204, 205, 206, 207, 208, D
211, 215, 216, 217, 218, 219
bending, 196 degradation, 208
benefits, 217 density, 185, 189, 190, 193, 199
binding energies, 193 Department of Energy, 212, 220
deposition, 205
diffusion, 186
C
diffusion process, 186
cathode materials, 182, 184, 192 discharges, 205, 207
displacement, 212, 218
224 Index

E I

electric power, 215 impurities, 194

electrode, 184, 193 indication, 208
electrodes, 205 integration, 210
electrolyte, 184, 193, 205 ions, 191, 192
electron microscopy, 184
energy, 182, 197, 204, 205, 209, 210, 215,
J
216, 221
energy characteristics, 204
Japan, 221
engagement, 212
ethanol, x, 181, 192, 193, 195, 201
ethylene, 185, 193 K
evaporation, 185, 190
evolution, 218 kinetics, 194

F L

fast Fourier transform infrared (FTIR), 184, likelihood, 205

188, 189, 193, 196 lithium, x, 181, 182, 183, 184, 192, 193,
flexibility, 218 200, 201, 203, 204, 205, 208, 213, 217,
flow, 214 219
Ford, 213 Lithium, 203, 204, 206, 207, 209, 211, 212
fuel, x, 203, 206, 212, 213, 216, 218, 219 lithium ion batteries, x, 182, 192
Los Angeles, 213
low power, 216, 218, 219
G

gel, 184, 185, 190 M

Germany, 184
graphite, 204, 205, 206 manganese, 205, 219
gravimetric analysis, 184 Manganese, 207, 209, 211, 212
melting, 183
mixing, 193
H modeling, 207, 212
models, 212, 214
heat, 184, 186, 187, 188, 189, 190, 219
modules, 210
heating, x, 203, 205, 219
moisture, 192
high temperature, 208
morphology, 184, 188, 193
homogeneity, 183, 192
hybrid, x, 203, 204, 212, 213
 Index 225

N S

nanorods, x, 181, 182, 184, 190, 192, 200, safety, 205

201 sensitivity, 192
nickel, 205 shape, 186
nitrogen, 192 simulation, x, 203, 204, 207, 212, 216
simulations, 214
software, x, 204
O
solid state, 189
solution, x, 181, 182, 183, 184, 189, 190,
oxidation, 205
195
Oxides, x, 181, 182
solvent, x, 181, 192, 195, 201
oxygen, 205
spectroscopy, 184, 193
speed, xi, 204, 212, 213, 217, 220
P spine, 205
spreadsheets, 208
particles, 188, 200 stability, 208
permit, 205 stages, 204
plug‐in, x, 204 steel, 193
poisons, 205 strategies, 212
polarization, 184, 192, 210, 211 stretching, 196
polypropylene, 185 Sun, 221
power, x, 203, 204, 205, 206, 207, 208, 214, synthesis, 183, 192, 195
215, 216, 217, 218, 219
powers, 215
production, 204, 216 T
program, 220
temperature, 183, 186, 188, 189, 190, 192,
193, 200, 208
R test data, 212, 213
thermogravimetric analysis (TGA), 184, 185
radiation, 184, 193 torque, 212, 215, 217
radius, 214 toxicity, 182, 192
range, x, 204, 205, 216 transmission, xi, 204, 212, 220
raw material, 205 transmission electron microscopy (TEM),
reaction temperature, 183, 194, 200 193
reaction time, 194, 195 transportation, 221
reduction, 192 travel, x, 203, 215, 219
research and development, 182, 212 treatment, 183, 184, 186, 188, 190, 201
resistance, 208, 210
room temperature, 185, 193
runaway, 205
226 Index

V W

vacuum, 192 water, 184, 185

values, 210, 211
vanadium, x, 181, 182, 183, 191, 192, 194,
X
197, 201
variables, 214
X‐ray diffraction, 193
vehicles, x, 203, 204, 212, 213, 214, 218,
X‐ray diffraction (XRD), 193
219