Journal of Power Sources 162 (2006) 1379–1394

A review on electrolyte additives for lithium-ion batteries

Sheng Shui Zhang ∗
U.S. Army Research Laboratory, AMSRD-ARL-SE-DC, Adelphi, MD 20783-1197, USA
Received 5 July 2006; received in revised form 21 July 2006; accepted 21 July 2006
Available online 10 October 2006

Abstract
This paper reviews electrolyte additives used in Li-ion batteries. According to their functions, the additives can be divided into these categories:
(1) solid electrolyte interface (SEI) forming improver, (2) cathode protection agent, (3) LiPF6 salt stabilizer, (4) safety protection agent, (5) Li
deposition improver, and (6) other agents such as solvation enhancer, Al corrosion inhibitor, and wetting agent. The function and mechanism of
each category additives are generally described and discussed.
Published by Elsevier B.V.

Keywords: Electrolyte; Additive; Solid electrolyte interface; Overcharge; Li-ion battery

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1379
2. SEI forming improver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1380
2.1. Understanding of SEI formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1380
2.2. Reduction-type additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1380
2.3. Reaction-type additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1382
2.4. SEI morphology modifier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
3. Cathode protection agent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1385
4. LiPF6 salt stabilizer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1386
5. Safety protection agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
5.1. Overcharge protector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1387
5.2. Fire-retardant additive . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1388
6. Li deposition improver . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1389
7. Other . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
7.1. Ionic salvation enhancer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1390
7.2. Al corrosion inhibitor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1391
7.3. Wetting agent and viscosity diluter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1391
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1391
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1391

1. Introduction performance. Usually, the amount of an additive in the elec-

trolyte is no more than 5% either by weight or by volume
Use of electrolyte additives is one of the most economic while its presence significantly improves the cycleability and
and effective methods for the improvement of Li-ion battery cycle life of Li-ion batteries. For better battery performance,
the additives are able to: (1) facilitate formation of solid elec-
trolyte interface/interphase (SEI) on the surface of graphite, (2)
∗ Tel.: +1 301 394 0981; fax: +1 301 394 0273. reduce irreversible capacity and gas generation for the SEI for-
E-mail address: szhang@[Link]. mation and long-term cycling, (3) enhance thermal stability of

0378-7753/$ – see front matter. Published by Elsevier B.V.

doi:10.1016/[Link].2006.07.074
1380 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394

LiPF6 against the organic electrolyte solvents, (4) protect cath- takes places in two major voltage stages [12,13]. The first stage
ode material from dissolution and overcharge, and (5) improve takes place before the intercalation of Li+ ions into graphite
physical properties of the electrolyte such as ionic conductivity, and the SEI formed in this stage is structurally porous, highly
viscosity, wettability to the polyolefine separator, and so forth. resistive, and dimensionally unstable. The second stage occurs
For better battery safety, the additives are able to: (1) lower simultaneously with the intercalation of Li+ ions and the result-
flammability of organic electrolytes, (2) provide overcharge ing SEI is more compact and highly conductive. For a specific
protection or increase overcharge tolerance, and (3) terminate electrolyte system of a 1.0 M LiPF6 3:7 (wt.) EC–ethyl methyl
battery operation in abuse conditions. This paper reviews these carbonate (EMC), these two stages produce nearly same irre-
additives and discusses their functions in improving Li-ion bat- versible capacities. The irreversible capacities suffered in the
tery performance. second stage are associated not only with the reduction of sol-
vent molecules, but also with the electrochemical reduction of
surface functional groups, such as carbon–hydrogen bond, car-
2. SEI forming improver boxyl, carbonyl, and lactone, on the edge sites of graphite [5].
In the view of chemical composition, the SEI formed in the first
2.1. Understanding of SEI formation stage is more enriched with inorganic components, while that
formed in the second stage with organic components. Better sta-
Extensive investigations using various spectroscopic tech- bility of the latter is attributed to the formation of a network
niques have identified that the main components of SEI are the between organic compounds through the coordination of Li+
decomposed products of electrolyte solvents and salts. These ions and organic carbonate anions as below [14]:
components include Li2 CO3 , lithium alkyl carbonate, lithium
alkyloxide, and other salt moieties such as LiF for LiPF6 -based
electrolytes [1,2]. Based on this fact, two mechanisms have
been proposed for the electrochemically induced reduction of
carbonate-based solvents, for example ethylene carbonate (EC):

where RA is an abbreviation for “radical anion”. Both of these

two mechanisms are present in the process of SEI formation As suggested by its chemical composition, the “dried” SEI
and compete with each other. When mechanism (I) is predomi- itself is neither ionic conductive nor electronic conductive. The
nate, the reduction of solvents generates more gaseous products, ionic conduction in the SEI must origin from the migration of
and the resulting SEI is Li2 CO3 -abundant and less stable. On solvated Li+ through the micro-pores of SEI. Therefore, the ionic
contrary, mechanism (II) leads to less gaseous products and conductivity of SEI can be taken as the measure to evaluate the
the resulting products are substantially insoluble in the elec- compactness and stability of SEI. Generally, high resistance cor-
trolyte. As a result, the formed SEI is more compact and stable. responds to a compact and stable SEI [13]. Xu et al. [15] further
Many researches have indicated that these two mechanisms are examined the stability of the SEI formed in an EC-based elec-
affected by the morphology and chemistry of graphite surface, trolyte with different voltage range by changing the electrolyte
and are associated with the catalytic activity of the fresh graphite into a fresh propylene carbonate (PC) electrolyte, and found that
surface. The catalytic effect has been confirmed by the strong the SEI formed above 0.5 V versus Li+ /Li, i.e., corresponding
location-dependence of SEI composition [3,4]. That is, the SEI to the first stage, was unable to suppress the reduction of PC
formed in prismatic (edge) areas of a highly oriented pyrolytic molecules. The information described above would be very use-
graphite is enriched with inorganic compounds, while that in ful to understand and develop a desirable additive.
basal planes is enriched with organic compounds [3,4]. The
catalytic phenomenon was further supported by the fact that
surface modification, such as mild chemical oxidization [5–8] 2.2. Reduction-type additive
and physical surface coating [9–11], on graphite materials sig-
nificantly facilitated SEI formation and reduced gas generation As described above, the SEI formed before the intercalation
in the first intercalation of Li+ ions into graphite. These modifi- of Li+ ions is unstable and abundant with inorganic compounds.
cations are considered to deactivate the catalytic activity of the Furthermore, this period produces more gaseous products, espe-
fresh graphite surface. cially for PC-containing electrolytes. In the similar manner as
On the other hand, a dynamic study using an electrochemical surface modification, the SEI formation can be facilitated by
impedance spectroscopy (EIS) reveals that the SEI formation chemically coating an organic film onto the surface of graphite
 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394 1381

Scheme 1. Chemical structure of polymerizable additives.

through an electrochemical reduction of additives. This type The mechanism of the polymerizable additives in facilitating
of additives usually has higher reductive potentials than the SEI formation is based on an electrochemically induced poly-
electrolyte solvents. Prior to electrochemical reduction of the merization, which can be described by a general equation:
electrolyte solvents, the additives are preferably reduced to form
an insoluble solid product, which subsequently is covered onto
the surface of graphite as a preliminary film to deactivate cat-
alytic activity. Therefore, use of these additives not only reduces
gas generation but also increases the stability of the SEI due to
the participation of additive molecular moieties into the SEI.
According to the characteristic of additive reactions, these addi- where the radical anion can be terminated by the solvent
tives can be divided as polymerizable monomer and reductive molecules to form an insoluble and stable product as the pre-
agent. The former as shown in Scheme 1, which is featured liminary SEI nuclei. Electrochemically, this type of additives is
by one or more carbon–carbon double bonds in their molecules, very effective since the electron transference is only involved
includes vinylene carbonate (VC, 1) [16–21], vinyl ethylene car- in the first step. In addition to the reductive polymerization,
bonate (2) [20,22], allyl ethyl carbonate (3) [23], vinyl acetate the opposite oxidative polymerization also can occur on the
(4) [24,25], divinyl adipate (5) [25], acrylic acid nitrile [26], positive electrode, which inevitably increases impedance and
2-vinyl pyridine (6) [27], maleic anhydride (7) [28], methyl cin- irreversibility of the cathode. Therefore, the reasonable amount
namate (8) [29,30], phosphonate (9) [31], and vinyl-containing of such additives in the electrolyte is not to exceed 2 wt.%. Effec-
silane-based compounds (10) [32] and (11) [33]. In addition, tiveness of such additives is affected by many factors, including:
furan derivatives that contain two double bonds in each molecule (1) efficiency of the electrochemical polymerization, (2) solubil-
have recently been reported as the very effective SEI forming ity of the resulting polymer, and (3) adhesion of the polymer to
agent by Korepp et al. [34], who described that the presence of graphite surface. Since the reductive polymerization takes place
as low as ∼1% 2-cyanofuran could effectively suppress exfoli- at higher potentials than the solvent reduction, the improvement
ation of graphite structure in a 1 M LiClO4 PC electrolyte. This of such additives are mainly on the initial stage of SEI formation,
merit is attributed to the highly effective reduction polymeriza- which results in: (1) reduction of gas generation, (2) reduction
tion of the furan ring, which takes place at higher potentials than of irreversibility capacity, and (3) stabilization of the SEI against
PC reduction. There was no further information available about the extended cycling.
the effect of 2-cyanofuran on the cathode although the furan Reductive agents assist SEI formation through adsorption of
derivatives are known among the excellent electrochemically their reduced products onto the catalytic active sites of graphite
polymerizable (oxidative) monomers for conducting polymers surface. Effectiveness of such additives in facilitating SEI for-
[35,36]. mation is affected by the affinity of molecular moieties of the
1382 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394

reduced products to the graphite active sites. Most of this type where charging at fast rate or at low temperature is required
of additives belong to sulfur-based compounds, including SO2 since these conditions inevitably result in lithium plating
[37,38], CS2 [39], polysulfide (Sx 2− ) [40,41], cyclic alkyl sul- [53].
fites (12) such as ethylene sulfite [42–44] and propylene sulfite
[44,45], and aryl sulfites [44]. The effectiveness of these addi- 2.3. Reaction-type additive
tives seems to increase with the content of sulfur in the molecule,
which is in consistence with the poisoning effect of sulfur- This type of additives may not be reduced electrochem-
containing compounds on many other catalysts. It should be ically in the whole potential range of Li+ -ion intercalation,
noted that all of these sulfur compounds are soluble in the organic however, they are able to either scavenge radical anions, an
electrolytes and anodic unstable at high potentials, their pres- intermediate compound of the solvent reduction (see Section
ence may result in a high self-discharge rate as a result of the 2.1), or combine with the final products such as lithium alkyl
internal redox shuttle. Therefore, the amount of sulfur-based dicarbonate and lithium alkyloxide to form more stable SEI
additives must be strictly limited. A favorite impact is that the components. Early report about this type of additives was that
SEI formed in the presence of polysulfide exhibited higher diffu- the presence of CO2 reduced the initial irreversible capacity
sion of Li+ ions, which was indicated by the reduced resistances and stabilized SEI [38,41,54–56]. A Fourier transform infrared
at low frequencies [41]. Another example that is similar with the (FTIR) spectroscopy analysis by Zhuang et al. [57] revealed
adsorption of the reduced products was demonstrated by Wu et that Li2 C2 O4 -like compounds were present in the SEI formed
al. [46], who described that the addition of 5 wt.% AgPF6 into with EC and PC-based electrolytes. Therefore, two reactions
1.0 M LiPF6 3:2 (vol.) PC–DEC electrolyte could effectively below can be proposed to explain the fact of CO2 facilitating SEI
formation:

which indicate that CO2 stabilizes the SEI through its direct
suppress PC reduction and graphite exfoliation due to the prefer- incorporation to the SEI formation.
able deposition of Ag particles at 2.15 V versus Li+ /Li. Their The similar results were obtained by using dialkyl pyrocar-
conclusion was supported by XRD analysis and SEM observa- bonate as an in situ CO2 -provider [58,59] through the decom-
tion. posing reaction:
The other reductive additives include N2 O [41], nitrate
(13) [47], nitrite (14) [48], halogenated ethylene carbonate
(15) [43,49–51], halogenated lactone such as ␣-bromo-␥-
butyrolactone (16), and methyl chloroformate (17) [52] as shown
in Scheme 2. The later three compounds contain a carbonyl
(>C O) group, which can be electrochemically reduced in the
similar manner as EC. Their function in facilitating SEI for- The advantage of this approach is that it solves the problem
mation is attributed to the possible bonds between the halo- of low solubility and high vapor pressure with CO2 gas. More
gen species of the SEI consisting of the reduced products interestingly, the SEI thus formed shows much low resistance at
of electrolyte solvents and halogen-containing additive [52]. low temperatures [58]. Other similar approaches are the satura-
Fluoroethylene carbonate (FEC, 15) [43,51] is an interesting tion of the electrolyte solution with Li2 CO3 [60,61], which has
compound, which itself does not contain vinyl group, how- proven to reduce gas generation, increase initial reversibility,
ever, it can lose a HF molecule to form a VC molecule as and extend cycle life of the Li-ion battery. These improvements
below: are attributed to the formation of a more compact and thin SEI
[60].
A series of carboxyl phenol (18) [62], aromatic esters (19)
[62], and anhydride (20) [63] has been proposed to improve
SEI formation (see Scheme 3). These compounds feature a
well-conjugated structure, which is believed to be capable of
The resulting VC in turn severs as a polymerizable addi- stabilizing intermediate RAs through delocalization of the rad-
tive and HF effectively improves the cycleability of metal- ical. For example, catechol carbonate (20) can capture a less
lic lithium (to be discussed in Section 6). Therefore, FEC stable RA to form more stable one (21), which further results in
could be of special importance for these specific operations the formation of more stable SEI [63].
 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394 1383

Scheme 2. Chemical structure of reduction-type additives.

Other additives having the similar functions include maleic

anhydride [28], succinimide (22) [64] and N-benzyloxy car- cases, such additives may not reduce the irreversible capacity
bonyloxy succinimide (23) [64], where “N” atom is linked of the first cycle, but significantly increase cycle life of the
by two carbonyl groups with strong RA-delocalizing ability cell [63]. On the other hand, aromatic isocyanate compounds
(Scheme 3). All these additives (18–20, 22, 23) are very effective (24, where X is hydrogen or halogen) were claimed as a new
in suppressing PC reduction and stabilizing the SEI. A com- multifunctional additive for the improved Li-ion battery per-
mon characteristic of these additives is that the potential of the formance [65]. First, the isocyanate stabilizes SEI through the
SEI formation during the initial Li+ intercalation is very close reactions with the chemisorbed oxygen groups such as phenol
to that of the solvent reduction [62] since the additives them- and carboxyl on the surface of graphite particles based on the
selves do not involve reduction, instead capture the less stable speculation that the resulting products have much stronger affin-
solvent RA to form the more stable RA (see Fig. 1). In some ity to the subsequently formed SEI components. Second, the
isocyanate scavenges water and acidic HF from the electrolyte
based on its extremely high reactivity to these impurities. Third,
the lone-pair electrons in nitrogen of isocyanate molecule severs
as a weak Lewis base to deactivate the reactivity of electron-
deficient PF5 with the electrolyte solvents. It was shown that
the addition of 5 wt.% of phenyl isocyanate or 4-fluorophenyl
isocyanate enabled graphite to be cycled reversibly in a 1.0 M
LiPF6 1:1 (wt.) PC–EC electrolyte without any adverse impact
on the cell performance [65].
Boron-based compounds have been extensively studied as
the electrolyte additive to increase the cycle life of Li-ion batter-
ies, in which their function is believed to stabilize the resulting
SEI. These compounds include inorganic B2 O3 [66], organic
borates with undisclosed structure [18], boroxine family com-
pounds (25) such as trimethoxyboroxine and trimethylboroxin
[67], and lithium salt-based boron compounds (26) [19] and (27)
[68]. They were found not only to reduce capacity fading rate
but also to increase rate capability and low temperature perfor-
Fig. 1. Voltage curves of the first cycle of Li/graphite cells in a 1.0 M LiPF6
mance of the Li-ion batteries [18]. Spectroscopic analyses on the
(3:2 vol.) PC–DEC electrolyte without (a) and with (b) the addition of 2 wt.%
phenyl acetate. (Reproduced from Fig. 1 of ref. [62] by permission of the Elec- electrode surface by FTIR and XPS revealed that the effect of
trochemical Society, Inc.) these additives on the electrodes’ performance was attributed
1384 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394

Scheme 3. Schematic structure of reaction-type additives.

to their incorporation to the surface chemistry of electrode tronic transference, instead of a series of complicated exchange
[19]. reactions between B–O and R–O bonds [73–75]. Further study
Lithium bis(oxalato) borate (LiBOB, 28) was initially studied revealed that LiBOB still retained its strong ability to facilitate
as an alternative salt to improve the high temperature perfor- SEI formation even its content in the electrolyte was reduced to
mance of Li-ion batteries [69]. It is shown that this salt not an additive level [74–77]. For example, the addition of 1 mol.%
only is capable of suppressing PC irreversible reduction, but LiBOB is high enough to enable graphite cycling reversibly in a
also significantly stabilizes the SEI against the extended cycling 1 M LiPF6 1:1 (wt.) PC–EC electrolyte [76,77] and a 1 M LiBF4
[70]. Analyses of IFTR [71] and XPS [72] verify that B–O- electrolyte with the same solvent [74], respectively. Another salt
based molecular moieties are clearly present in the SEI formed is lithium oxaltodifluoroborate (LiODFB, 29) [75,76], which has
in LiBOB-based electrolytes. Based on this fact, it was pro- the similar function to stabilize the SEI as LiBOB does, but it
posed that LiBOB reacts with the major SEI components such is superior to LiBOB in many other properties such as the solu-
as lithium alkyl dicarbonate and lithium alkoxide to form a bility in carbonate solvents and the ability to provide better rate
more stable oligomer (30), where R presents the molecular capability and low temperature performance of Li-ion batteries
moieties of the reduced products of the electrolyte solvents [75].
[72,73]. On the other hand, absorption-type additive also was stud-
ied to improve SEI formation [9,52,78]. This type of additives
generally has strong affinity to the graphite surface, and they are
physically adsorbed on the active sites of graphite to suppress
PC reduction. Since the adsorption is a simple physical pro-
cess, such an additive can be applied either by adding it into the
electrolyte [52,78], or by pretreating graphite with the additive
[9,52,78]. This type of additives was exampled by halogenated
According to the chemistry of LiBOB and the final product, organic compounds [52], polydimethylsiloxane [9], and silane
the formation of compound (30) may not involve any elec- [78].
 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394 1385

2.4. SEI morphology modifier

As described in Section 2.1, the stability of SEI is affected

by the content of inorganic components. In the SEI formed
with LiPF6 –carbonate electrolyte, the main inorganic compo-
nents are known to be Li2 CO3 and LiF, in which the presence
of isolated LiF crystals has been identified as the important
factor to result in SEI unstable [79]. For this reason, many
boron-based anion receptors have been developed to dissolve
LiF [80–83]. Among these anion receptors, the most represen-
tative compound is tris(pentafluorophenyl) borane (TPFPB), in
which boron atom is extremely electron-deficient due to the
strong electron-withdrawing and excellent conjugated proper-
ties of the perfluorinated phenyl groups. Theoretically, TPFPB
can coordinate LiF to form a 1:1 complex and easily dissolves
Fig. 2. Voltage profiles of the first cycle of the graphite electrodes without (a) and
more than 1 M of LiF in many organic solvents [84,85]. It has
with (b) pretreatment using a 5.0 wt.% Na2 CO3 aqueous solution in a 1 M LiClO4
been reported that the addition of 0.1–0.2 M TPFPB is suffi- 1:1 EC–DEC electrolyte. (Reproduced from Fig. 2 of ref. [88] by permission of
cient to improve the cycleability and capacity retention of Li-ion the Electrochemical Society, Inc.)
cell for both LiPF6 [80,81,83] and LiBF4 [82] electrolytes. The
improvement is attributed to the dissolution of LiF out of the SEI.
A negative impact of TPFPB is that it captures LiF from LiPF6 a K salt decreased solvation of Li+ ions by EC molecules, which
to release highly reactive PF5 , which accelerates deterioration mitigates solvent decomposition and results in the formation of
of the electrolyte solvents, i.e., more porous and thinner SEI. The latter has been confirmed by
much lower surface resistance and charge-transfer resistance.
LiPF6 + BX3 ⇔ LiBX3 F + PF5 On the other hand, it was reported that 12-crown-4 and 15-
where X represents tris(pentafluorophenyl) group [83,86]. crown-5 could effectively suppress PC reduction during the ini-
Therefore, the amount of TPFPB added to the electrolytes tial SEI formation [91,92], which is attributed to their extremely
should be strictly controlled so that the adverse effect can be strong solvating ability to Li+ ion [93]. In the presence of these
minimized. crown ethers, solvation of Li+ ions by PC molecules is greatly
Alkali metal salts also have been attempted to improve SEI weakened so that PC has less chance to co-intercalate with the
formation. Komaba et al. [87] first reported that the addition solvated Li+ ion into graphite, which as a result reduces PC
of 0.22 M NaClO4 into a 1 M LiClO4 1:1 (vol.) EC–diethyl reduction. However, their high toxicity makes it impossible to
carbonate (DEC) electrolyte obviously reduced the initial irre- use crown ethers as the electrolyte additive in Li-ion batteries.
versible capacity and resulted in the better capacity retention.
The SEI formed in the presence of sodium ions is more uni- 3. Cathode protection agent
form and has much smaller resistance compared with that
obtained in the absence of sodium ions. Alternatively, a pre- In the view of electrolyte, performance deterioration of the
treatment of graphite materials using sodium salts that are cathodes origins from two factors: (1) water and acidic impuri-
insoluble in organic electrolytes such as Na2 CO3 and LiCl ties, and (2) irreversible oxidization of the electrolyte solvents.
has been attempted to improve SEI formation [88]. In addi- Since the contents of water and acidic impurities (HF) in the
tion to increasing reversible capacity and enhancing capacity electrolyte have been strictly controlled before use, these impu-
retention, such a pretreatment led to a small elevation in the rities are mainly generated during charging, especially during
potentials of intercalation and de-intercalation of Li+ ions with occasionally overcharging. A possible mechanism proposed by
graphite, as indicated in Fig. 2. This feature is very impor- Wang et al. [94] shows that the solvents are chemically oxi-
tant for the development of high power Li-ion battery. One can dized by the oxygen released from the cathode to generate H2 O
adopt this feature to eliminate lithium plating on the graphite and CO2 , and that the resulting H2 O further hydrolyzes LiPF6 to
anode when the Li-ion batteries are charged at high rate or low form acidic products such as HF and POF3 . Since HF is the main
temperatures. source for the dissolution of the cathode materials, especially
Opposite impacts of potassium ions on the SEI formation spinel LiMn2 O4 , most of the current efforts have been focused on
have been observed from different electrolytes [89,90]. Zheng these additives capable of scavenging water and acids. Aiming at
et al. [90] attributed this phenomenon to the high selectivity of reducing the dissolution of spinel LiMn2 O4 , Saidi et al. [95] pro-
K+ ions to the electrolyte composition. A very obvious improve- posed amine-based organic base such as butylamine to scavenge
ment by K+ ions was obtained from 1 M LiClO4 EC–DEC acidic impurities, while Takechi et al. [96] used carbodiimide-
system [90], which showed that the addition of small amount based compounds such as N,N -dicyclohexylcarbodiimide to
of K2 CO3 significantly increased graphite’s reversible capacity react with water to prevent acid generation. Both approaches
and improved cell’s rate capability. Based on Raman spectro- showed in different degree improvement on the capacity reten-
scopic analysis, Zheng et al. [90] concluded that the presence of tion of LiMn2 O4 cathode. In their further efforts, Takechi and
1386 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394

Shiga [97] proposed a bifunctional additive based on a series of uble and stable surface layer with a network structure (32) like
“N–Si”-based compounds, such as N,N-diethylamino trimethyl- below:
silane (31), which are capable of scavenging both H2 O and HF
via breaking “N–Si” bond as below:

Based on the descriptions above, the functions of the cath-

ode protection agents can be divided into two categories: (1) to
Deactivation of PF5 would be the other reason for scavenge water and acidic impurities, and (2) to combine the dis-
amines to reduce the dissolution of the cathode materials, solved metal ions into a protective surface layer. Since water is
which has been less recognized. Chemically, the equilib- inevitably generated by the oxidization of solvents during charg-
rium of “LiPF6 ⇔ LiF + PF5 ” is always present in the elec- ing and occasionally overcharging [94], the combination of these
trolyte, and the reaction (here using MnO as an example) two approaches seems the best way to protect the cathode from
of “PF5 + MnO → POF3 + MnF2 ” is possible. Due to their performance deterioration.
electron-donating property, the amine molecules can complex
PF5 to reduce the reactivity and acidity of PF5 and as a result 4. LiPF6 salt stabilizer
suppress the dissolution of the cathode materials.
The other approach was to form a protective film on the Thermal instability of LiPF6 -based electrolytes is attributed
cathode surface to prevent further dissolution. The idea is to two factors of: (1) high equilibrium constant of the decomposi-
that the additive molecules combine with the dissolved metal tion “LiPF6 ⇔ PF5 + LiF” and (2) high reactivity of the resulting
ions to form substantially insoluble products, which are sub- PF5 with the organic solvents. Beside this, the resulting PF5 can
sequently covered onto the cathode surface to prevent fur- deteriorate the stability of the SEI on the graphite surface via
ther dissolution. In the effort to search for such an addi- a series of reactions with most of the SEI components, such as
tive, Amine et al. [98] added LiMn2 O4 powder into a 0.7 M Li2 CO3 , RCO2 Li, and ROCO2 Li, even in the absence of H2 O
LiBOB [Link] EC–PC–DMC electrolyte and stored the mix- and other acidic impurities, for example:
ture at 55 ◦ C for 4 weeks. After this, they found almost no
Li2 CO3 + PF5 → POF3 + 2LiF + CO2
Mn ions in the electrolyte. In their further effort [99], they
used LiBOB as the additive at the concentration of no more
RCO2 Li + PF5 → RCOF + LiF + POF3
than 0.1 M to examine the power and capacity performance of
graphite/LiMn1/3 Ni1/3 Co1/3 O2 cells in LiPF6 -based electrolyte.
ROCO2 Li + PF5 → RF + LiF + CO2 + POF3
The results showed that such cells exhibited excellent capacity
retention at 55 ◦ C and their impedance met the requirement set As a result of these reactions, the content of LiF in the SEI
by the FreedomCar Partnership. Although the mechanism for is increased and the pressure inside the battery is build-up by
the role of LiBOB in suppressing the Mn2+ dissolution has not the generated gaseous products. Therefore, the efforts to sta-
been understood well, a possible one is that the dissolved Mn2+ bilize the electrolytes have been focused on solving the above
and BOB anion are combined with each other to form an insol- two problems. For the first issue, Hiroi et al. disclosed [100] that

Scheme 4. Schematic structure of LiPF6 thermal stabilizer.

 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394 1387

dissolution of as low as 0.05 wt.% LiF into the LiPF6 -based elec- date for the redox shuttle additive in the past decade has been
trolyte can significantly reduce gas generation. This improve- carried out mainly on a trial-and-error basis until recently a quan-
ment is attributed to the suppression of decomposition reaction tum chemical calculation software (Gaussian ver. 03TM 20 ) was
by the excess LiF in a chemical equilibrium principle. Solu- developed to accelerate the screening process [112].
tions to the second problem have been focused on weakening the Early-investigated shuttle additives include metallocenes
reactivity and acidity of PF5 by adding small amount of Lewis [108,113–117], tetracyanoethylene, tetramethylphenylenedi-
basic additive. Based on the electron-deficient property of PF5 , amine [118], dihydrophenazine derivatives bearing either 2-
electron-rich compounds should be effective for this purpose. hydroxypropyl or ethyl substituents on both N atoms [119], and
Ideally, these compounds should be a weak or mild Lewis base so a series of substituted aromatic or heterocyclic compounds and
that their presence does not promote the equilibrium moving for- their alkali metal salts [109]. Since all these compounds have
ward decomposition. As an example, tris(2,2,2-trifluoroethyl) a redox potential ranging between 2.8 and 3.5 V, they are only
phosphite (TTFP, 33, Scheme 4) is capable of stabilizing LiPF6 - suitable for low voltage lithium batteries. Meanwhile, these com-
based electrolytes [86,101], which is attributed to the formation pounds show some adverse impacts on the cell performance.
of a 1:1 weak complex (34) between TTFP and PF5 . In the simi- For example, metallocenes are strongly adsorptive to the sur-
lar principle, many amide-based compounds have been reported face of cathode materials, which blocks ionic conduction path
as the LiPF6 stabilizer. These compounds include 1-methyl-2- and results in the loss of both rate and power capability [115].
pyrrolidinone (35) [102,103], fluorinated carbamate (36) [104], Aromatic and heterocyclic compounds have low solubility and
and hexamethyl-phosphoramide (37) [105], in which the nitro- slow mobility in the electrolyte, which limits their shuttle effec-
gen core with its lone-pair electrons being well delocalized by tiveness (current) [119]. Some metal complexes of Fe, Ru, Ir,
the electron-withdrawing >C O or >P O groups acts as the or Ce with phenanthroline or bipyridine have around 4 V versus
weak base site to deactivate the reactivity of PF5 . Li+ /Li of reversible redox potentials, however, they did not work
well due to their low solubility and mobility [120].
5. Safety protection agent Extensive investigations have been focused on anisole-family
compounds [111,120–123] because of their relatively high redox
5.1. Overcharge protector potential and high solubility in the lithium battery electrolytes.
The shuttle mechanism of these compounds can be generally
According to the function, the overcharge protection addi- described as below:
tives can be classified as redox shuttle additive and shutdown
additive. The former protects the cell from overcharge reversibly,
while the latter terminates cell operation permanently. Idea of the
redox shuttle is not new, its initial study started with I2 /I3 − redox
couple to protect 3 V lithium batteries [106,107]. Basically,
the shuttle molecules are required to be oxidized reversibly at
slightly higher potentials than the normal end-of-charge poten-
tial of the positive electrode. When overcharging, the shuttle
molecules are oxidized at the positive electrode and the oxidized
shuttle species diffuse to the negative electrode and are reduced where R1 and R2 are independent alkyl groups, and X1 and
back to the neutral molecule. In this way, the shuttle molecules X2 are H, halogen, or independent alkyl groups. The poten-
act as an internal discharger and the potential of the positive tials of these redox shuttle molecules are affected by the type
electrode is indefinitely locked at the oxidizing potential of the and position of the substituents linking to the aromatic ring,
shuttle molecules while the current supplied in the overcharge is and in most cases are ranged in 3.8–4.0 V versus Li+ /Li with a
converted to heat. The maximum current that the shuttle additive reversible electrochemical window up to 4.2 V [120,122]. Mean-
can carry depends on several factors, including the concentra- while, the position of alkyloxy groups and substituents and the
tion of the shuttle molecules in the electrolyte, the diffusion type of the substituents affect the reversibility and shuttle effi-
constant of the shuttle molecules, and the number of charges ciency of these compounds. For example, Adachi et al. [120]
carried by the shuttle molecules [108,109]. Ideally, the shuttle investigated a series of anisole compounds and found that only
additive should meet these requirements of: (1) the shuttle reac- those having two methoxy groups at 1,2- (ortho-) and 1,4- (para-)
tion must be highly reversible, (2) its oxidation potential must positions showed reversible redox at the 4.0 V region, while the
be slightly higher than the normal end-of-charge potential of 1,3- (meta-) counterpart was oxidized irreversibly. This is due to
the positive electrode but lower than the decomposing potential that the 1,2- and 1,4-positions are more favorable for the delo-
of electrolytic solvents, (3) it must be electrochemically stable calization of radical cation (RC, the oxidized product), which
within the cell operating potentials, and (4) its oxidized and is responsible for the high reversibility of redox shuttle. The
reduced forms must be highly soluble and mobile (high diffu- effect of delocalization was furthermore confirmed by substitut-
sion) in the electrolyte. There are thousands of organic molecules ing hydrogen at the 4-position for a bromine, which significantly
showing reversible redox in the time scales of cyclic voltamme- increased the shuttle efficiency [120]. This is because the p-orbit
try [110], however, only few fairly have been found to meet the and its two lone-pair electrons in the bromine core participate
requirements above [111]. The search for the potential candi- into the conjugated structure, which in turn stabilizes the RC.
1388 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394

In the similar principle, 2,5-ditertbutyl-1,4-dimethoxyben- wettability of liquid electrolyte to the non-polar polyolefine sep-
zene shows excellent redox shuttle behavior at 3.85–3.92 V ver- arator because of their non-polar property. The negative impact
sus Li+ /Li because the presence of two ditertbutyl groups at the of these compounds is on the long-term operation and storage
1- and 4-positions stabilizes the RC [121–123]. According to performance of the Li-ion batteries due to the slow and irre-
their redox potentials and electrochemical stability, the anisole- versible oxidation of these compounds.
family compounds are most suitable for LiFePO4 -based Li-ion On the other hand, it has been reported [142] that LiBOB
batteries. Other aromatic compounds that have been reported to can act as a shutdown additive to provide excellent overcharge
have the similar functionalities are monomethoxy benzene class tolerance. In a 1C-overcharge test on 8 Ah cylindrical Li-ion
compound [124], hexaethyl benzene [125], bipyridyl or biphenyl batteries, the LiBOB battery only experienced mild vent with
carbonates [126], difluoroanisoles [126], and some S- or N- the maximum temperature not exceeding 100 ◦ C and it did not
containing hertocyclic aromatic compounds such as thianthrene catch any fires and sparks, while the LiPF6 counterpart battery
and 2,7-diacetyl thianthrene [127], as well as phenothiazine- not only caught fire but also resulted in a violent explosion
based compounds [128]. with the maximum temperature reaching 400 ◦ C. The excel-
Recently, Dantsin et al. [129] introduced a new approach lent overcharge tolerance of LiBOB battery is attributed to the
toward the development of the redox shuttle additive. They fact that the oxalate molecular moieties of LiBOB are prefer-
reported that the weakly coordinated perfluoroborane cluster ably oxidized to produce CO2 by the oxygen released from the
salts, i.e., lithium fluorododecaborates (Li2 B12 Fx H12−x ), not cathode [75]. This process generates much less heat than the
only function as the electrolyte salt but also serve as a redox oxidization of solvents as occurred in the LiPF6 battery. As a
shuttle. The doubly charged anion, (B12 Fx H12−x )2− , can be oxi- result of the mild oxidization of LiBOB, the internal pressure
dized reversibly to the singly charged anion at about 4.5 V, which is rapidly built up by the released CO2 , which consequently
is the highest potential that the redox shuttle molecules have been opens safety vent before thermal runway occurs. The similar
know to reach without structural deterioration. Therefore, this result also was presented by Amine et al. [143], who described
unique oxidation chemistry provides inherent protection against that the graphite/LiBOB/spinel Li-ion cells exhibited excellent
the overcharge and may be well suited to the high voltage cathode abuse tolerance.
materials such as LiCoO2 and LiMn2 O4 . Equal interest is in the
redox potential that can be changed by controlling the degree of 5.2. Fire-retardant additive
fluorination in the fluorododecaborate anion. It has been demon-
strated [129] that the small graphite/LiNi0.8 Co0.15 Al0.05 O2 cell Safety concern has been a main obstacle for the applica-
incorporating this salt exhibited 1C-overcharge protection for tion of Li-ion batteries in hybrid electric vehicles and electric
almost 100 h without visible discharge capacity loss. vehicles, which is greatly related to the high flammability of
The “shutdown additive” is based on the idea that at high the liquid electrolytes. Therefore, many researches have been
potentials, the additive molecules polymerize to release gas, focused on the development of fire-retardant (FR) additive to
which in turn activates the current interrupting device (CID), lower the flammability of the liquid electrolytes. The concept
while the resulting polymer is covered onto the surface of cath- of the FR additives has been long known and studied for the
ode to isolate the cathode from further overcharge. Without protection of the solid polymers and woods [144,145]. There
few exception [29], majority of such additives belong to the are two mechanisms proposed to explain the flame retardation:
aromatic compounds, such as xylene [130], cyclohexylbenzene (1) physical char-forming process, which build-up an isolating
[29,131], biphenyl [29,131–140], 2,2-diphenylpropane [139], layer between the condensed and gas phases to stop combustion
phenyl-tert-butyl carbonate [141], phenyl-R-phenyl compounds process [146,147], and (2) chemical radical-scavenging pro-
(R = aliphatic hydrocarbon, fluorine substituted) [139], and 3- cess, which terminates radical chain reactions responsible for
thiopheneacetonitrile [139]. Lee et al. described that mixing the combustion reaction in the gas phase [147,148]. Although
cyclohexyl benzene (CHB) and biphenyl gave much more effec- these two processes are coexistent in most cases, the former
tive protection than CHB alone and the mixture expanded the is more applicable to the condensed phase while the latter to
safety region up to 12 V/2 A for a 0.76 Ah graphite/LiCoO2 Li- the vapor phase. So far most of FR additives used in the liq-
ion battery, which the CHB alone can never reach [131]. This uid electrolytes are based on organic phosphorus compounds
result suggests a new approach toward the more efficient shut- [148–155] and their halogenated derivatives [156–160], and
down protection against the overcharge. More recently, Abe et the radical-scavenging mechanism seems to be more accept-
al. [136] described that some benzene derivatives (biphenyl and able [147,148,161]. Among various testing methods, differen-
o-terphenyl) and heterocyclic compounds (furan, thiophene, N- tial scanning calorimetry (DSC), accelerating rate calorimeter
methylpyrrole, and 3,4-ethylenedioxythiophene) could be elec- (ARC), and self-extinguishing time (SET) have been most exten-
trochemically oxidized to form a very thin film on the cath- sively adopted for the evaluation of the FR effectiveness. Gen-
ode surface during the battery cycling, and that the resulting erally, the presence of FR reduces the self-heating rate and
film is electric conductive (therefore they called it as “electro- delays the temperature at which the propagating self-heating
conducting membrane (ECM)”). In the case of slight amount of initiates.
addition, therefore, the ECM film could improve the cycleabil- Trimethyl phosphate and triethyphosphate are among the ear-
ity of the cathode. In addition, most of these shutdown additives liest investigated FRs [148–151,154,155]. Unfortunately, both
described above could sever as a wetting agent to increase the of them are unstable against the low reductive potentials on the
 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394 1389

graphite anode surface [149,151]. Due to the high content of ing on the number of fluoride substituents [165]. Fluorinated
phosphorus, trimethyl phosphate has better FR effectiveness but propylene carbonates were superior to MFE in both FR and cell
shows inferior reductive stability on the graphite anode surface performance. For MFE, Arai evaluated MFE electrolyte using
[149,151]. This fact indicates a trade-off relationship between Li/graphite and Li/LiCoO2 half-cells by comparing it with the
the FR effectiveness and reductive stability. The reduction in counterpart LiPF6 EC–EMC. Results showed that the MFE elec-
flammability with the addition of these FRs has to be realized at trolyte provided nearly same performance for Li/LiCoO2 cell,
an expense of the other performances such as ionic conductivity however, it resulted in very high polarization for Li/graphite
of the electrolyte and reversibility of the cell. Therefore, Xu et al. cell [168]. Therefore, further work should be carried out for the
[151] concluded that it is impractical to use alkyl phosphates as MFE-based electrolytes.
the FR in Li-ion batteries. In their continued efforts, Xu and co-
workers [156–160] synthesized a series of partially fluorinated 6. Li deposition improver
alkyl phosphates and found that the presence of fluoride not
only improved reductive stability but also increased FR effec- Additives to improve the cycling efficiency of metallic Li
tiveness. When 20 wt.% of tris(2,2,2-trifluoroethyl) phosphate have been long investigated for use in rechargeable Li batteries.
was added, for example, the electrolyte became non-flammable These additives are of special importance to develop high power
while having no any adverse impacts on both graphite anode Li-ion batteries. In fact, power loss of the Li-ion batteries is in a
and cathode of the Li-ion batteries [156,158]. Other successful great degree related to Li plating on the graphite anode, which
examples to improve the reductive stability of phosphates are: promotes undesirable growth of the SEI since Li plating often
(1) to increase the number of carbons in the alkyl groups [152], occurs in the late period of charging Li-ion battery at constant
(2) to partially replace alkyl groups with the aryl (phenyl) group current, especially at high rate or low temperatures [53]. The
[152,153], and (3) to form cyclic structural phosphate [154]. On poor cycleability of metallic Li is mainly attributed to two fac-
the other hand, cyclophosphazene family compounds seem to tors: (1) high reactivity of Li with the electrolyte solvents, and
be a very promising FR [101,162,163]. The advantages of these (2) poor morphology of the plated Li such as the formation of
compounds include: (1) the increased FR effectiveness due to needle-like dendrite and very porous sponge-like Li. The reac-
the high content of phosphorus related to their ring structure, tivity of metal Li is affected not only by the inherently chemical
and (2) the excellent stability at low potentials with respect to property but also by the surface specific area. Therefore, most of
the graphite anode. It was evaluated [151,162,163] that hexam- previous efforts were focused on the second problem to improve
ethoxycyclotriphosphazene had no any negative effects on the the morphology of Li deposition. The idea was based on the for-
graphite anode, while provided highly effective FR and remained mation of an ion-conducting surface layer or a Li–metal alloy to
stable up to 5.0 V against the anodic potentials. facilitate a uniform deposition of Li.
In addition to P(V) phosphate and phosphazene, the phos- In early efforts, it was found that low concentration (ppm
phites with P(III) also have been reported as the very effec- level) inorganic compounds such as SO2 [169], polysulfide
tive FR [86,101,155,164]. The advantages of P(III) phosphate [40,41], CO2 [170,171], and even water [169] were effective
over the P(V) phosphate are that: (1) it is superior in facilitat- to improve the cycling efficiency of Li on an inert metal sub-
ing SEI formation [155] and (2) it is capable of deactivating strate in LiClO4 –PC solution. This improvement was attributed
PF5 [86]. Among these compounds, tris(2,2,2-trifluoroethyl) to the fact that these compounds incorporated to the formation
phosphite was found to be very promising, which not only of a Li+ -conductive film, which resulted in smother surface mor-
reduced the flammability of the liquid electrolyte, but also phology. In the similar manners, the increased coulombic effi-
improved the cycleability of the Li-ion cells [101,164]. For ciencies of Li cycling in LiClO4 /PC or PC–DME solution were
example, adding 5 wt.% TTFP as the additive into a 1.0 M obtained by the addition of some organic compounds such as
LiPF6 [Link] PC–EC–EMC electrolyte significantly improved 2-methyltetrahydrofuran [172–174], 2-methylthiophene [173],
the cycleability of Li-ion cells although this amount was not and nitromethane [169]. This is because these compounds are
sufficient to retard flaming. When the content of TTFP was preferably reduced before Li plating, and the resulting products
increased to 20 wt.% as the co-solvent, the electrolyte became build-up to form a SEI, which subsequently suppresses the for-
non-flammable and the Li-ion cells using it could be cycled at mation of Li dendrites. More interestingly, their presence favors
60 ◦ C for 200 cycles without visible capacity loss. decreasing electric resistance at the electrode–electrolyte inter-
On the other hand, fluorinated propylene carbonates [165] face [173].
and methyl nonafluorobuyl ether (MFE) [166–168] have been Based on the principle of the surface layer to promote smooth
studied as the non-phosphorus FR. The “no flash point” elec- and uniform deposition of Li, both ionic and non-ionic sur-
trolytes by the addition of these solvents were obtained only factants were proposed to improve Li cycling efficiency. It is
when they became the major solvent (>70% by volume). This is assumed that the surfactant molecule can be physically absorbed
because they themselves are neither radical-scavenging nor char- on the surface of Li, and the adsorption depends on the local
forming. Their function of making electrolyte non-flammable morphology of the Li surface. Physically, the dendrite sites are
is only to dilute the other highly volatile and flammable co- preferably absorbed due to their much higher specific surface
solvent. As an example, DSC results showed that they were able area, and in this way the growth of dendrites is suppressed.
to delay the exothermal peak temperature of the mixture of the The surfactants that have been studied and found to be effective
fully charged LiCoO2 powder and solvent up to 40 ◦ C, depend- include tetraalkylammonium chlorides with a long alkyl chain
1390 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394

[175], cetyltrimethylammonium chlorides [175], lithium and The opposite results about the impact of VC on the Li depo-
tetraethylammonium salts of perfluorooctanesulfonate [176], sition have been reported by different authors [43,188]. Mogi
perfluoropolyethers [177]. Based on the SEM observation, Ribes et al. [43] observed that the surface of the Li deposited from
et al. [176] concluded that the presence of surfactants favored the a 5 wt.% VC-containing electrolyte contained more solids and
deposition of less porous Li due to an enhanced and more uni- had higher resistance, while Ota et al. [188] found that the addi-
form nucleation, and the improvement was attributed to the mor- tion of 2 wt.% VC increased the cycling efficiency of Li and the
phological properties of the Li surface. On the other hand, it was deposited Li had lower surface resistance. This difference could
reported [178] that the addition of the other surfactant-like com- be associated with the concentration of VC contained the solu-
pounds such as nitrile sucrose and nitrile cellulose could signifi- tions, and it clearly indicates the importance of the selection for
cantly reduce the interface resistance between Li and electrolyte. an appropriate concentration of the electrolyte additives.
Another approach is based on the formation of Li–metal alloy,
which has been verified to be very effective in increasing the 7. Other
cycling efficiency of Li. So far only two salts, AlI3 and SnI2 , have
been studied by Ishikawa et al. [174,179,180], who concluded 7.1. Ionic salvation enhancer
that the formation of Li–metal alloy layer could limit the growth
of Li dendrites or brittle Li, and stabilize the interfacial resistance It has been long known that 12-crown-4 is of excellent
of Li. For example, addition of hundreds of ppm AlI3 into a selectivity to coordinate Li+ ion, and in this way its presence
1.0 M LiN(C2 F5 SO2 )2 PC–DMC electrolyte could increase the effectively promotes the solubility of Li salts and increases
cycling efficiency of Li by 5–10% [180]. More interestingly, the ionic conductivity [189–191]. As a result of the increased geo-
increased efficiency was retained even if the Li was transferred metric size of the solvated Li+ ion, the mobility of Li+ ion
to the blank electrolyte without AlI3 after the first deposition of is definitely decreased so that the increased conductivity is
Li. They thought that the residual Al was permanently remained mainly contributed by the anion. Furthermore, the strong chelat-
in a form of Li–Al alloy on the surface of Li, which provided ing interaction between crown ligand and Li+ ion enhances
durable Li interface with better Li cycleability. the activity energy of the desolvation that must take place
Beside the approaches above, acidic HF was proposed to on the electrolyte–electrode interface before Li+ ion interca-
improve the morphology of Li deposition [181–183]. The idea of lates into the electrodes. These disadvantages and high tox-
this method is based on the fact that the uneven current distribu- icity make it impossible to use crown ether in the Li-ion
tion caused by non-uniform SEI layer on Li surface is the main batteries.
reason for the deposition of dendrite Li [179,184–186], and all To increase the transference number of Li+ ion, Zhang and co-
the components to build SEI on the Li surface are strong alkali workers [192,193] and Lee et al. [194] independently proposed
[187]. Acidic HF can react with the alkali SEI components, such an “anion-receptor” concept to coordinate selectively anion of
as lithium akalycarbonate, lithium alkyoxide, and Li2 CO3 , to the salt. Based on this concept, Zhang and co-workers [192,193]
form more even and LiF-rich SEI. Results showed that the pres- designed a series of borate compounds where the boron core is
ence of 5 × 10−3 to 20 × 10−3 M HF in the electrolyte could very electron-deficient, while Lee et al. [194,195] synthesized a series
effectively suppress the growth of Li dendrite [181,182], which of linear and cyclic aza-ether compounds (38) where nitrogen
was attributed to the formation of a LiF-rich SEI. Probably in is linked by a strong electron-withdrawing substituent to make
the same mechanism, Mogi et al. [43] described that the addition it electron-deficient. Their results showed that both approaches
of 5 wt.% fluoroethylene carbonate into 1 M LiClO4 PC elec- were successful. In the continued efforts, Lee et al. designed and
trolyte significantly improved the cycling efficiency of Li. An in synthesized numerous boron-based anion-receptors with par-
situ observation using atomic force microscope (AFM) indicated tially or per-fluorinated substituents. According to the chemical
that the surface of Li was covered with a uniform and closely structure, these compounds can be categorized as borate (39)
packed layer of particle-like deposit of about 100–150 nm diam- [84,85,192,193,196–198], borane (40) [80,81,84,85,196,197],
eter, and the film had lower resistance compared with that formed and borole (41) [199,200], as indicated in Scheme 5.
in the additive-free solution. As described in Section 2.2, there Results indicated that all these anion receptors (39–41)
is a chemical equilibrium of “FEC ⇔ VC + HF”. Thus, the FEC are in different degrees capable of coordinating the anion
may slowly release HF that in turn severs as the additive for Li and increasing the solubility of salts such as LiF, LiCl, and
deposition. Due to the above merits, FEC seems to be a very LiBr, and theoretically they can coordinate anion to form
promising additive for the efficient deposition of Li. a 1:1 complex. Among these boron-based anion-acceptors,

Scheme 5. Schematic structure of the anion receptors.

 S.S. Zhang / Journal of Power Sources 162 (2006) 1379–1394 1391

tris(pentafluorophenyl) borane (TPFPB) has been most exten- among the best candidates for the wetting agents. Cyclic alkyls
sively studied. In many organic solvents or their mixtures, and aromatic compounds with low molecular weight also can be
TPFPB can dissociate up to 1.0 M LiF and the resulting solu- considered. The minimum criterion for the selection of wetting
tions are electrochemically stable [84,85]. For example, with agents is that their introduction should not bring other negative
a 1:2 EC–DMC mixture, the resulting electrolyte has an about impacts on the cell performance. As mentioned in Section 5.1,
5.0 V of electrochemical window on a glass carbon electrode some of shutdown additives for the overcharge protection are of
and its cathodic potential is limited by metallic Li plating at 0 V wet-enhancing function. In the other efforts, Wang et al. [103]
versus Li+ /Li [198]. Furthermore, the solution was thermally introduced that the Li/graphite cells with 2–5% cyclohexane
more stable than the counterpart LiPF6 electrolyte [197,198], added into the electrolyte (1 M LiPF6 1:2 EC–DEC) exhibited
and hence it could support Li/LiMn2 O4 cell cycling at 55 ◦ C higher reversible capacity (354 mAh g−1 versus 347 mAh g−1 )
for 50 cycles with only 16% of capacity loss versus 44% in and coulombic efficiency (91% versus 84%) in the first cycle
the counterpart LiPF6 electrolyte [198]. In addition, better elec- than those without the addition of cyclohexane. This improve-
trolyte retention in the separator has been observed as a result of ment is probably due to that cyclohexane improved the wetta-
the interaction between TPFPB and DMC [201]. In contrary to bility of the electrolyte to the separator and electrodes, which
the addition of crown ethers, the addition of TPFPB decreases hence increases the utilization of the electrode materials. In addi-
total ionic conductivity and increases the transference number tion, it was reported that the addition of an appropriate amount
of Li+ ion [198,201]. There was no further report on the effect of of trialkyl phosphate [208] or linear eaters with high molecular
the decreased conductivity on the rate and power performance of weight [209], such as methyl decanoate, dodecyl acetate, and a
the battery. Since TPFPB anion receptor offers a verity of merits, series of eaters of tertiary carboxylic acids, was very effective
its application in the Li-ion batteries seems very promising if its to enhance the electrolyte permeation into polyolefin separator.
cost and toxicity can be acceptable in industry standards. On the other hand, Zhong and Sacken [210] claimed that the
addition of small amount of P2 O5 into the electrolyte could effec-
7.2. Al corrosion inhibitor tively reduce the viscosity of LiPF6 -based electrolytes. Since the
issue of viscosity mostly appears at the low temperatures, this
Al corrosion in Li-ion electrolytes has been recognized approach could be of great interest in the development of the
for many years, extensive studies revealed that the corrosion low temperature Li-ion batteries.
mainly depends on the Li salt, instead of the electrolyte sol-
vents [202–205]. Spectroscopic analyses indicated that molecu- 8. Conclusions
lar moieties of the salt anion were inevitably present on the pas-
sivation layer for these Al surfaces without corrosion [204,205]. There are numbers of electrolyte additives available for the
This fact reveals that the salt anion plays an essential role in Li-ion batteries. Each additive exhibits one or more of unique
promoting passivation of Al surface. Based on this idea, some functions to improve the battery performance. However, in many
Li salts that are know to passivate Al very well have be pro- cases use of an additive more or less introduces other negative
posed as the corrosion inhibitor to protect Al from corrosion. As impacts while improving the targeted performance. For example,
an example, Tsujioka et al. [206,207] selected either LiBOB or appropriate amount of VC is favorable for the SEI formation and
LiODFB to suppress Al corrosion in the PC–DEC or EC–DMC Li cycling, however, excess VC results in the cells low cycling
solution of lithium bis(perfluoroalkyl sulfonyl) imide (Li-imide, efficiency and high self-discharge rate. Among numerous addi-
having a general formula of LiN(SO2 Cn F2n+1 )2 , with n = 2, 3, or tives, LiBOB seems to be the only one that is multifunctional
4). Their results showed that when 5 mol.% LiBOB or LiODFB for the improvement of Li-ion batteries. The functions that have
was added to the solution (total salt concentration was 1 M), been found from LiBOB include: (1) it cooperates to SEI forma-
the Al corrosion could be completely suppressed, as indicated tion and stabilizes SEI, (2) it reduces dissolution of the cathode
by the zero current flow during a 5.0 V dc-polarization and by materials, (3) it provides excellent overcharge tolerance, and (4)
the microscope observation showing no any changes of the Al it facilities Al passivation in the electrolyte solution. In addition,
surface before and after polarization test. This protection is due LiODFB is expected to have the similar functions as LiBOB
to that one or more of O–B bonds in LiBOB or LiODFB anion due to their similar structure. Desirable improvement may be
break and the resulting new anion constantly combines with Al3+ achieved by combining several additives together provided that
to form a very stable passivation layer with network structure they are not interfered with each other.
[75].
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