Towards competitive European batteries
[Link].2013-1 Grant. 608936
2020
Basics of rechargeable batteries
Alexander Warnecke
Workshop EPE Conference – Geneva (Switzerland)
9th of September 2015 1
Motivation
Batteries2020 – “Towards Realistic European Competitive Automotive
Batteries”
Potential customers complain about
range and price of electric cars
Objectives: Source: [Link]
- Batteries with higher energy
density
- Cheaper batteries
- Second life usage for cost
optimization
Source: [Link]
2
Introduction
120 Scientists
About 100 students
Research fields:
- Power Electronics and
Electrical Drives
- Battery research Prof. De Doncker Prof. Sauer
(Head of Instiute)
Symbiosis of electronics and
batteries
Source: [Link]
3
INDEX
1. Battery Technology
2. Working Principle Lithium Ion Batteries
3. Components and Structure
4. Typical Materials
5. Safe use of lithium-ion batteries
Battery technologies
SuperCap Li-Ion
Very High Power automotive cells Batteries2020
10,000
Li-Ion cells
Specific Power, W/kg
Blei „spiral High Power
wound“
1,000 NiMH
consumer cells
NaNiCl2
“Zebra”
NiCd
100 Li-ion
LiM-Polymer High
Blei Energy
10
1
0 20 40 60 80 100 120 140 160 180 200 220 240
Specific Energy, Wh/kg
Source: Saft
No lifetime information in this graph!
5
Classification and types of Li-Battery systems
Li-Systems
Systems with metallic Systems without
Anode material lithium metallic lithium:
(neg. electrode)
Li-Metall Lithium-Ion
Liquid Polymer Liquid Polymer
Different type of electrolyte: electrolyte: electrolyte: electrolyte:
electrolytes Li-Metall- Li-Metall- Li-Ion- Li-Ion-
Liquid Polymer Liquid Polymer
Only for Not many EV & HEV Higher
coin cells activities temperatures and
EV: Electric Vehicle, Application
USA: AVESTOR reduced power
HEV: Hybrid Electric Vehicle Fr: Bollore application
6
Working principle
e-
LiMO2 Graphit
R e-
Oxygen
Li+ LiC6
Metall-Ion
Graphit
e
Separator Li+ Li+
Electrolyte
POSITIVE & Separator NEGATIVE
Source: Saft
7
Solid-Electrolyte interface (SEI)
Charging
graphite
layer
oxigen anion
electrolyte
metallic cation
lithium cation
Li+ cation SEI
Solid Electrolyte Interface (SEI)
Source: LITHIUM-ION BATTERIES, Perla B Balbuena & Yixuan Wang
8
Solid-Electrolyte interface (SEI)
Charging
On the negative active material
surface a passivating layer is
created, the so called SEI (solid
electrolyte interface)
Its creation can‘t be stopped
SEI Formation is influenced by the
oxigen anion
electrolyte
metallic cation
lithium cation
Creation during first charging
process
The cell characteristic is
influenced by SEI -> ions have to
pass it (higher inner resistance)
SEI growing is the main ageing
process of Li-Ion batteries
Solid Electrolyte Interface (SEI)
Source: LITHIUM-ION BATTERIES, Perla B Balbuena & Yixuan Wang
9
Components and structure
Anode:
graphite on Cu-foil
Cathode:
Li-Me-mixed oxide on Al-foil
Material content
in mass-%
(consumer cells)
Source: IME / RWTH Aachen housing ~ 25
Metal prices
(LME) LiCoO2 ~ 20
Co (59 u) ~ 95 US$/kg graphite ~ 20
Ni (59 u) ~ 20 US$/kg electrolyte ~ 15
Mn (55 u) ~ 3 US$/kg Cu-foil ~9
Fe (56 u) ~ 0,7 US$/kg Al-foil ~5
Li (as Li2CO3) (7u) ~ 43 US$/kg separator ~5
10
Componentes in lithium-ion cells
Anode, cathode and separator are porous materials that are filled with
electrolyte
High-Power cell design
High-Energy cell design
Aluminium
Aluminium
Seperator
Seperator
Cathode
Cathode
Cathode
Cooper
Anode
Anode
11
Componentes in lithium-ion cells
Anode, cathode and separator are porous materials that are filled with
electrolyte active materials passive materials
High-Power cell design
High-Energy cell design
12
Designs of lithium-ion cells
Round cells
A lot of experience in cell design
High life-time
Complex Cooling
Supplier e.g. Saft, GAIA, A123, Sanyo
„Pouch“ cells
Good cooling character
High energy density
Main question: Tightness of the film
Supplier e.g. Leclanché, Kokam
Prismatic cells
Easy stacking in battery packs
Combines characteristics of the other cell designs
Supplier e.g. Sanyo, SBLimotive
13
Active materials in lithium-ion batteries
Li-Ion liquid
cathode material anode material
Good lifetime high LiCoO2 Hard Carbon “3.7 V material”,
safety risk LiC6 small number of full cyles
Highest safety risk, good
LiNiO2
performance “3.7 V material”, expensive,
Graphite
Cheaper, safety better than LiC6 high number of full cycles
LiMn2O4
for Co & Ni
Popular material, wide range of
LiCo1/3Ni1/3Mn1/3O2 Titanate “2.2 V material”, safe,
variability for optimizing prop.
Li4Ti5O12 low energy density
Wide variability in materials LiCoxNiyMnzO2
Silicium “3.7 V material”, high
3.3 V material”, cheap & safe LiFePO4 Li22Si6 energy density,
currently F&E
14
Electric properties
4400 Only cathode materials
vs. Li / Li+
4200
LiMn2O4
4000
mV Li/Li+
3800 Li(Ni,Co,Mn)O2
in vs.
LiCoO2
Potential in mV
3600
Li(Ni,Co)O2
Potential
LiFePO 4 4
3400
3200
Quelle:
Source:ZSW UlmUlm
ZSW
3000
0 20 40 60 80 100 120 140 160 180 200
Specific Capacity
spezifische [mAh/g] [mAh/g]
Kapazität
15
Operation limits
7 Discharging of
Collector-
corrosion Normal operation „Metalloxid-
Voltage (V)[V]
6
sponge“
Zellspannung
4
Allowed operation
range
3
Cell
0
-50 0 50 100 150 200
eingeladene
Charged Ladungsmenge
amount in % of ratedincapacity
% der Nennkapazität
16
Operation limits
Negative Positive
4.2 V (fully charged)
Lithium plating
C6 / LiMeO2 (Me = Co, Ni, Mn, Al)
3.6 V (fully charged)
Safe
C6 / LiFePO4
0V 1V 2V 3V 4V Potential
vs. Li/Li+ [V]
2.7 V (fully charged)
Safe
LTO / LiMeO2
2.1 V (fully charged)
Safe
Safe
LTO / LiFePO4
18
Conclusion
Lithium-ion systems have excellent electrical performance
New materials still offer a high research potential
Safety and costs are the main „real“ issue
Requests on lifetime for HEV and EV are fulfilled
NiMH (HEV) and NaNiCl2 high temperature batteries as technology
alternatives show worse performance
19
