SOLID

STATE
ELSEVIER Solid State lonics 84 (1996) 1-21
IONICS

Review
Cathode materials for lithium rocking chair batteries
R. Koksbang *, J. Barker, H. Shi, M.Y. Sa~di
Valence Technology, Inc.. 301 Conestoga way, Henderson. NV 89015, USA
Received 21 November1995; accepted 14 December 1995

Abstract

Cathode materials for rechargeable rocking chair or lithium-ion batteries, are reviewed, The emphasis is placed on the
comparison between specific capacities and rechargeability of lithium-containing high voltage cathode materials such as
manganese oxides and LiMO 2 compounds, where M is Co or Ni. It is generally found that the maximum reversible
capacities for the most promising materials fall in the range 100-120 mAh/g, and decaying to around 75 mAh/g after
several hundred cycles. The rechargeability is similar for the most commonly considered materials: LiMn20 a, LiCoO 2 and
LiNiO 2. No improvements in capacity or rechargeabilityl beyond what have been found for these materials, is observed by
substitution of other elements into these compounds.

Keywords: Lithium battery; Lithium cobalt oxide; Lithium manganeseoxide; Rocking chair

1. Introduction derived from concentration cells [2] which consist of

There has been considerable research and devel-
opment activity targeted towards the commercial
manufacture of battery systems based on lithium
insertion cathodes and metallic lithium anodes. This
effort was primarily driven by the desire for inexpen-
sive high energy density rechargeable batteries, which
could be utilized in applications ranging in size from
cellular telephones and other electronic devices to
electric vehicles.
Lithium metal free lithium batteries have been
known for several years, and were originally termed
"rocking chair" batteries (RCB) by Armand [1]. The
basic concept of operation for RCB's was partially
• Corresponding author. Fax: (702) 558-1001; Phone: (702)
558-1032; E-mail: 103061.1742@Compuserve.com.
essentially identical electrodes containing different
reactant concentrations, and also from carbon~carbon
cells based on cation insertion in one electrode and
anion insertion in the other [3-5]. Shortly after the
RCB concept was revealed by Armand [1], the con-
cept was demonstrated [6-10] using transition metal
compound anodes and cathodes. Later, new names
for this technology appeared: Lithium ion [11], Shut-
tlecock [12], Swing Electrode System [13], etc., but
the fundamental concept remained the same. In 1990,
Sony Energytech Inc. [14], announced the commer-
cial availability of their "lithium ion rechargeable
battery" based on a carbon (non-graphitic) anode
and a LiCoO2 cathode. Sony has ~ince made several
iterative improvements to the performance of their
particular RCB system. Further, several other
Japanese companies have since also announced com-
mercialization of their particular lithium ion technol-

0167-2738/96/515.00 © 1996 Elsevier Science B.V. All fights reserved

PIl S0167-2738(96)00016- 1
2 R. Koksbang et a L / S o l i d State Ionics 84 (1996) 1-21
ogy, i.e. A & T Battery, Hitachi Maxell, Mitsubishi
and Sanyo. These batteries apparently all show ac-
ceptable performance characteristics under a variety
of different design applications. In a number of cases
a higher specific capacity graphitic anode has re-
placed the non-graphitic type used in the original
Sony configuration. Furthermore, prismatic designs
as well as cylindrical ones are now commercially
available.
The intention of this paper is to provide the reader
with an overview of the battery related properties of
cathode materials, including preparation procedures
and electrode characteristics, i.e. the applied aspects
of the cathode materials. Several excellent reviews
covering the fundamental structural and electrochem-
ical properties of cathode [15,16] and anode [17,18]
materials have appeared recently as well as an
overview of the rocking chair battery technology
[19]. For other cathode materials, the reader is re-
ferred to earlier reviews [20-22].
2. Electrode materials
The electrode materials considered in this review
are all characterized by providing the lithium needed
for the RCB reaction. The number of different com-
pounds which are known, is rather limited, and are
arbitrarily divided into LiMO z (e.g LiCoO z and
LiNiO 2) compounds, manganese oxides (e.g
LiMn20,,) and other materials. These compounds are
characterized by being strongly oxidizing in nature
and as such reversibly intercalate lithium ions above
3 V versus Li. The cobalt compound (used in con-
junction with a coke anode) was used in the original
commercially available RCB from Sony. Although
this is a relatively expensive material, its favorable
electrochemical properties mean it is continuing to
find application in recently developed RCB's from
other manufacturers, The nickel compound on the
other hand, is comparatively inexpensive but is much
more difficult to prepare in the electrochemically
active form. There are several proponents for appli-
cation of the manganese spinel material. Tarascon
and co-workers for instance [23], describe the
LiMn204 compound as follows: "based on abun-
dance, ease of preparation, material cost, and the
environmental friendliness, LiMn20 a is favored over
its counterparts".
In the following, the properties of the materials
listed in Table 1, will be discussed and where appro-
priate, additional material will be discussed. The
table contains information regarding the materials,
the preparation conditions, and the electrolytes used
for the electrochemical measurements as well as the
current and voltage conditions applied, initial and
reversible capacities and cycle life. Each entry is
numbered and will be referred to throughout the text,
by reference to (#xx), where xx is the line entry in
the table. Contrary to these references, literature
references are given in square brackets.
3. LiMO z materials
Only the first row transition metal compounds are
considered in this review because of the relatively
low insertion potentials versus Li of the LiMO z
compounds of the heavier transition metals, e.g.
LiWO2, LiMoO 2 and LiRuO z [20,21]. The poten-
tials of these compounds are typically lower than 2
V versus Li, and in fact, for the three examples
mentioned here, the potentials are closer to 1 V
versus Li.
Layered metal oxides of the type LiMO 2 (where
M = C o or Ni) have a rhombohedral structure
[112,113] where lithium and transition metal atoms
are ordered alternate (111) planes in a distorted
cubic-close-packed oxygen ion lattice. The layered
framework provides a two dimensional interstitial
site which allows for relatively facile extraction and
insertion of lithium ions. The materials will be dealt
with separately in the following discussion.
4. LiCoO 2
The lithium cobalt oxide, LiCoO z , was among the
lithium insertion compounds first described by
Mizushima et ai. [114] in 1980, and is currently the
most extensively used cathode material for rocking
chair batteries. Removal of lithium corresponding to
x = 1 in LixCoO 2, is equivalent to a theoretical
capacity of about 274 mAh/g. However, due to
 R. Koksbang et a l . / Solid State Ionics 84 (1996) 1-21
structural restrictions [115], lower amounts of lithium
may be removed and inserted reversibly. The general
consensus between independent researchers appears
to suggest that a maximum of around 150 m A h / g
may be reversibly cycled over many charge-dis-
charge cycles without appreciable specific capacity
loss (# 1-18). In most instances groups testing under
rates of insertion/extraction consistent with cell us-
age, report reversible specific capacities in the range
120-140 mAh/g. Very high cycle numbers are ob-
tained with commercially available batteries from
Sony and others, with minimal capacity losses.
Several synthesis routes have been attempted to
improve the performance, including the conventional
sintering of a carbonate mixture ( # 1-2, 11), nitrate
mixtures (#5), LiOH and either a carbonate (#6), an
oxide (#7) or a nitrate (#8) of cobalt. The general
trend suggests that the high temperature synthesis
methods have little or no influence on the electro-
chemical performance of the LiCoO 2 material since
essentially identical results are obtained. The differ-
ences observed can probably be ascribed to elec-
trolyte properties, choice of current collectors, or
electrode preparation. Most reports on materials pre-
pared at low temperature show only a restricted
number of charge/discharge cycles. For example,
[69] demonstrates an unusually high specific capacity
for the low temperature material but unfortunately
only a few cycles are reported and the long term
cycle life is unknown.
The structure of LiCoO 2 [116-118] and the struc-
ture varations during lithium insertion and lithium
extraction, have been studied in detail [112,117]. The
structural differences between LiCoO 2 prepared by
conventional high temperature synthesis and the so-
called LT-LiCoO2 (#19-21) prepared at about
400°C, are discussed in [47,117]. Lithium ion trans-
port has been described in [119]. In addition to the
insertion of lithium into the Li~,CoOz lattice, the
corresponding sodium reactions were also studied in
[120].
The influence on the insertion properties by the
formation of interracial layers [121] on the LiCoO 2
has been described. The formation of this cathode-
electrolyte interface layer, apparently formed by re-
action between the electrolyte (IM LiBF4/PC) and
the cathode components was indicated by ac
impedance measurements. It is formed in an analo-
3
gous fashion to the solid electrolyte interface model
(SEI), originally postulated by Peled and co-workers
[122] to characterize the interfacial properties be-
tween metallic lithium and non-aqueous electrolytes.
The cathode interracial layer model was expected to
moderate the electrochemical properties of the
LiCoO 2 composite electrode. The film formation
was then further substantiated by electron micro-
graph pictures of a LiCoO 2 composite cathode sur-
face in contact with the electrolyte surface [121].
The use of LiCoO 2 as a cathode material in large
test/prototype cells, has been demonstrated by sev-
eral organizations [31,123-126]. Cylindrical 30 All
batteries constructed from plates using metallic Li
anodes [123,124] were cycled 40-50 times without
appreciable loss of discharge capacity. Cylindrical
1.5-2 Ah and 8 Ah cells, having a flat plate con-
struction inside [124], were assembled and tested,
together with two types of spirally wound cells of
0.3-0.5 Ah, and 4-6 Ah capacities, respectively. In
addition, prismatic 3 Ah rocking chair (carbon an-
ode) cells were also tested [123]. Cylindrical " C "
size cells based on both LiCoO 2 and LiNiO 2 cathode
materials and with a lithium anode [31] showed high
capacity and a cycle life exceeding 100 cycles.
5. LiNiO 2
LiNiO 2 exists in two structural modifications, of
which only one is electrochemically active [50]. The
theoretical capacity of LiNiO 2, assuming l Li per
NiO 2 unit may be extracted, is close to that of the
LiCoO z compound, i.e. ~ 275 m A h / g . Again, in a
similar fashion to the cobalt system, a significantly
lower capacity is obtained in actual test cells ( # 2 2 -
44). However, the overall reversible specific capaci-
ties reported for LiNiO 2 are typically 10-30 m A h / g
higher than those for LiCoO 2. Fewer cycles have
been reported, but good charge retention is generally
observed after > 100 cycles (#24). Very small par-
ticle size was claimed to be advantageous (#44) in
one report, but unfortunately no electrochemical data
were presented. The cycle life size is strongly depen-
dent on the depth of discharge [127], i.e. high cycle
numbers are achieved when the capacity is restricted
to about 100-120 m A h / g , while only a few cycles
are possible at higher capacities.
 4 R. Koksbang et al./Solid State Ionics 84 (1996) 1-21

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 R. Koksbang et aL / Solid State Ionics 84 (1996) 1-21
In addition, the LiNiO 2 compound appears to be
more difficult to synthesize than the corresponding
cobalt oxide, in a modification which is able to
reversibly insert lithium to any significant extent.
Contrary to LiCoO 2, which can be prepared by
sintering a mixture of almost any Li, Co and O
sources under proper temperature conditions, the
LiNiO2 compound needs to be prepared under
strongly oxidizing conditions. Typical examples in-
clude e.g. hydroxide mixtures annealed in an O z
atmosphere (#22-23, 42), hydroxide and nitrate
(#27, 41) or by the use of Na202 alld an Ni source
(#31), followed by ion exchange with LiNO 3 at
elevated temperature.
The structure of LiNiO 2 is described in [ l 16,128-
130], while the structure of Li2NiO 2 is also dis-
cussed in [128]. The latter paper also discusses
lithium insertion in the approximate range 1 < x < 2
in LixNiO 2, which takes place at about 1.8 V versus
Li. This is in contrast to lithium insertion in LiCoO 2
where no plateau around this voltage is found. At
about 1.1 V versus Li, a large plateau is observed in
the Li/LiCoO~ system, presumably corresponding
to disproportionation of LiCoO 2 to Li20 and Co
metal [128]. The solid state ionic transport properties
of LiNiO2 are discussed in [131] while other physi-
cal/chemical properties are given in a number of
references [ 132-134].
Performance results, comparable to those of liquid
electrolyte systems, were obtained with Li/LiNiO z,
Li/LiMn204, C/LiNiO 2 and C/LiCoO 2 cells [135],
using a PAN based hybrid polymer electrolyte (i.e.
polymer-liquid-salt combination, [136]) at room
temperature. However, a rapid decay of the capacity
with cycling, was observed in the early experiments
with the carbon anode based systems.
Cycle testing [59] of a C/LiNiO 2 cell, slightly
smaller than a " C " size, showed good initial capac-
ity (approximately 1 Ah), and about 40% of this
capacity was retained after 1200 cycles at relatively
high rate.
6. L i M O z (M - Co, Ni) derivatives
Many attempts have been made to improve the
lithium insertion properties of both LiCoOz and
LiNiO 2 by partial substitution of Co or Ni, with
13
another transition metal such as Cr (#45), Mn
(#55-58) and Fe (#59-60), respectively. The most
well-documented approach is the LiNi,Co, _xO., se-
ries of compounds (#46-54), which were initially
[47] investigated because of their lower insertion
potentials compared to that for the pure cobalt oxide
phase. The LiNixCo,_~O 2 compounds were ex-
pected to be oxidatively less demanding on the elec-
trolyte phase. Further, these materials are generally
considered to be simpler to prepare than the pure
nickel oxide. However, no improvement in specific
capacity or in cycle life was observed. Similar syn-
thesis routes to those used for the pure Ni and Co
oxides, have been attempted with near equivalent
results.
Apart from this N i / C o combination, it is apparent
that substitution with other transition metals results
in materials characterized by lower capacities and
less reversible insertion/extraction reactions. Fur-
thermore, as a general trend it appears that as the
concentration of the substitutional metal increases
there appears to be a concurrent negative effect on
the specific capacities of these materials. For exam-
ple, Jones et al. [63] successfully prepared single
phases of Li~,CryCol_rO2 type compounds. The
electrochemical results indicated that as y increased,
the specific capacity declined. The same group un-
successfully attempted to prepare single phase Li.,-
CryNi I_yO z by the same preparative route [63].
7. Other L i M O 2 oxides
Other LiMO z compounds, such as, LiCrO 2
(#63-64), LiVO 2 (#66) and LiCuO 2 (#65), all
have lower reversible capacities than the previously
described compounds of this general stoichiometry.
As an example, the Li~CrO z compound has a theo-
retical capacity of about 295 m A h / g , assuming 1 Li
per CrO 2 unit can be cycled, but the actual reversible
capacity is as low as about 60 mAh/g. Further, the
cycling performance of this material is disappointing.
The capacity of LieRhO 2 seems to be high ( A x =
0.8) [137] but the lithium is re-inserted at potentials
down to 2 V versus Li. LiFeO2 would obviously be
of great interest, but the structure [138] of conven-
tionally prepared LiFeO 2 (rock salt) does not allow
lithium to be extracted reversibly to any significant
degree. Several different approaches have been at-
14 R. Koksbang et a l . / Solid State Ionics 84 (1996) 1-21
tempted in an effort to prepare the layered LiFeO 2
compound, i.e. hydrothermal synthesis [138], ion
exchange of et-NaFeO 2 [139-141] and from FeOCI
[1421.
8. Manganese oxides
Considerable work has been focused on character-
ization and optimization of the iithiated manganese
oxides. Although the reversible specific capacities
for the manganese oxides are lower than the theoreti-
cal specific capacity of the best cobalt and nickel
LiMO 2 compounds, they potentially represent the
least expensive of the available cathode materials.
Much of the available work has concentrated on the
spinel phase Li,Mn204. Although this review is
primarily concerned with the high voltage materials,
i.e. those best suited for the rocking chair batteries,
some materials operating at the 3 V plateau will also
be included. Significant efforts are also underway to
extend the capacity of the 4 V plateau to the 3 V
plateau without significantly compromising the spe-
cific capacity.
The structure of the LiMn204 compound is de-
scribed in [116], and is reviewed together with the
structures of related manganese oxides, as well as
other spinel compounds, in [143-146]. Structural
work on the delithiated spinels is also found in
[147,148]. The LiMn:O 4 spinel is by far the most
extensively investigated manganese oxide, both for
the 3 V plateau (#71, 73-74, 76, 80-82, 88-
89, 105-107), the 4 V plateau (#69-70, 72, 77-
79, 84-87, 91-94, 96-97, 99-103, 108-109), orfor
both plateaus (#75, 83, 95, 98, 104, 110, 112). In a
few cases up to 4 Li per Mn204 unit (#90) have
been cycled. In this particular case the cycling has
been extended to include the lowest voltage plateau
around I V versus Li. The major emphasis in this
review is concentrated on the parent LiMn204 spinel
compound and its derivatives.
9. LiMn204, 4 V plateau
The cycling of 1 Li per Mn204 unit corresponds
to a theoretical material utilization capacity of 148
mAh/g. This figure is somewhat lower than the
corresponding value for the cobalt and nickel LiMO 2
phases mentioned earlier. In most experimental cells,
it is found that the reversible specific capacity of the
4 V range for the LiMn204 is about 120 mAh/g, or
about 81% of the theoretical capacity. The theoreti-
cal capacity may be reached at very low cycling
rates, although extended cycling at these rates is
normally accompanied by a concurrent capacity fade.
The LiMn204 compound is traditionally made by
annealing of the corresponding carbonates in the
approximate temperature range 700-900°C. Other
synthesis routes, primarily encompassing different
low temperature methods based on sol-gel chem-
istry, have been investigated. Sol-gel synthesis of
manganese oxides is discussed in details in [149-
152]. As in the case of the LiMO 2 compounds, only
minor performance improvements in terms of spe-
cific capacity or cycling, (or none at all), are ob-
served. Recently [153-157], lithium insertion in
LiMn20 * was demonstrated from an aqueous elec-
trolyte.
For application purposes it has been necessary to
unequivocally demonstrate long term cycling of the
LiMn204 material without significant capacity fade.
To that end, Tarascon et al. [158] and Sffidi et al.
[ 159] have demonstrated that it is possible to retain a
capacity around 75 mAh/g for LiMn204 after more
than 1000 deep discharge cycles. Furthermore,
Tarascon et al. [23360] have shown a full RCB that
incorporates the spinel cathode coupled to a
petroleum coke anode with over 1300 deep discharge
cycles and only a 36% decline in the battery dis-
charge capacity.
Very recently, a study using a solid inorganic
phosphate electrolyte, which is reported to be stable
above 5 V versus Li [161], indicated that structural
changes which take place at very high potentials, are
in some way beneficial to the capacity at the 4 V
plateau. It was previously shown [23,162,163] that
two reversible redox reactions take place at high
anodic potentials (4.55 and 4.95 V versus Li). The
additional capacity only corresponds to x = 0.06 for
both plateaus.
10. LiMn204, 3 V plateau
Since approximately 1 Li per Mn204 unit can be
inserted over the approximate 3 V voltage plateau,
 R. Koksbang et al. / Solid State Ionics 84 (1996) 1-21
the theoretical specific capacity of this plateau
(#71-72, 77-78), is roughly identical to the capac-
ity of the 4 V plateau, i.e. around 150 mAh/g.
However, the delivered capacity is often significantly
lower than that of the 4 V plateau, and the capacity
fade with cycle number is usually greater. It has been
reported [84,86,164] that the electrode impedance
increases abruptly (almost by a factor of ten) at the
transition between the 4 V and the 3 V plateau,
which then causes lower material utilization and
poor cycling properties. It was concluded [84,86,164]
that the concurrent cubic to tetragonal phase change
which accompanies lithium insertion over this volt-
age range, confers the inferior electrochemical per-
formance on this material. Thackeray and co-workers
[79] also reported the poor cycling of the L i / L i x-
Mn204 cells on the 3 V plateau and attributed this to
an asymmetric lattice expansion/contraction of the
LixMn204 electrode during cycling. They contended
that the lattice distortion resulted from a Jahn-Teller
distortion that occurs around x = 1.08, and trans-
forms the cubic symmetry of the spinel phase to a
tetragonal symmetry.
Methods to stabilize this Jahn-Teller distortion
have been reported. For example, by varying the
synthesis conditions, Tarascon et al. [82,165], showed
that it is possible to control the amount of lithium
which can be reversibly inserted/extracted within
each voltage plateau. However, overall, the total
amount of lithium available in both plateaus remains
approximately constant. Improved performance at
the 3 V plateau was achieved by modification of the
synthesis procedures [166]. The materials were pre-
pared from Li2CO 3 and Mn(CH3COO)2.4H20, to
which a small amount of carbon black powder was
added. The theoretical specific capacity was
achieved, and the capacity decay was smaller than
that of conventionally prepared LiMn204.
Although acceptable cycling performance of cells
covering both the 3 V and 4 V plateaus together is
considered to be difficult, at least one report has
appeared which indicated that this is certainly a
possibility [88] (at least over a restricted number of
discharge/charge cycles). The LiMn204 material
described in [88] was prepared by a proprietary
method and the electrochemical performance com-
pared directly to commercially available LiMn204.
The paper stresses the importance of controlling the
15
processing conditions for obtaining a material with
both high specific capacity and improved reversibil-
ity of the lithium insertion reaction.
In one report the lithium capacity at the 3 V
plateau has been used as a subsidiary lithium source
[167], in order to retain a larger fraction of the
capacity at the 4 V plateau, which would otherwise
be consumed due to the capacity loss often observed
during the initial cycling of the carbon anode [168].
This was achieved by chemically increasing the
lithium content in Li~+xMn204 by the use of LiI
similarly to the methods originally described by
Murphy [ 169].
Finally, scale-up of cells to the AA battery size
has been demonstrated [170]. In this study the 3 V
plateau of Li/LiMn204 cells was cycled more than
100 times but at low material utilization.
11. LiMn204 derivatives
Transition metal substitution (Fe: #115, V:
# 1 1 6 - 1 1 7 , Cr: #118-122, Zn: #126, #Co:
#127, Ni: #128-129, Ti: #130-131) appears to
have little or no influence on the specific capacity or
the cycling performance of the 4 V plateau while
only minor improvements may occur at lower poten-
tials. At higher potentials, the trend is actually to-
wards lower capacities than that of the parent spinel
LiMn204. Similar results were obtained by substitu-
tion with Mg 2+ (#123-125).
Tarascon and co-workers [171] systematically
studied the electrochemical properties of LiMy-
Mn2_yO 4 over the voltage range 3.5-4.5 V versus
Li, in which Mn is substituted with other elements,
(M -- Ti, Ge, Fe, Zn or Ni) and with varying levels
of cation substitution, y. It was reported that replac-
ing Mn with +2 valence cations (Ni, Zn) or +3
valence cations (Fe) reduces the specific capacity,
but apparently does not affect the cycling perfor-
mance.
12. Other ternary manganese oxides
Examples of other ternary manganese oxides
which have been investigated are Li 2Mn#O 9 (# 132)
and Li4MnsOi2 (#133-134), both of which cover
the voltage range 2-3.3 V versus Li, i.e. not at the 4
16 R. Kokz'bang et a l . / Solid State Ionics 84 (1996) 1-21
V plateau [79,80,172,173]. Lithium cannot be ex-
tracted from these oxides since the manganese is
already in the + 4 oxidation state. The synthesis and
structure of several defect spinel manganese oxides
is described in [173,174].
Li.,MnO 2 compounds (#135-143) are also of
interest, since the theoretical specific capacity for
these materials is about twice that of the spinel phase
LiMn204, i.e. about 300 mAh/g. Contrary to the
Li/LiMn204 system, which shows two distinctive
plateaus at around 3 V and 4 V versus Li, these
compounds typically show a sloping voltage curve
over the entire insertion range. The voltage typically
varies from slightly lower potentials (about 3.8 V
versus Li) to about 2 V versus Li. Thackeray and
co-workers [ 175,176] showed that LiMnO 2 cathodes
that contain at least some spinel component give
reasonable electrochemical performance with a gen-
erated specific capacity up to around 160 m A h / g
between voltage limits of 2.0 and 4.4 V versus Li.
Interestingly, the discharge voltage profile of these
cells becomes increasingly spinel-like following mul-
tiple discharge-charge cycles with distinct voltage
plateaus becoming evident around 3 and 4 V
versus Li.
13. Other oxides
The only other known lithium containing transi-
tion metal oxides, which have been described (very
recently) in the literature, are LiNiVO4 (#144) and
LiCoVO4 (#145), both of which have the inverse
spinel structure. The insertion potential of the LiN-
iVO4 compound is around 4.8 V versus Li. This is
the highest potential for any known cathode material
and clearly demonstrates that the lithium is relatively
tightly bound to the host lattice. The potential of the
LiCoVO4 compound is somewhat lower. At present
the measured specific capacities of both compounds
are fairly low, in the range of 40-50 mAh/g. It
should be noted, however, that, with further detailed
evaluation, these materials, particularly with elec-
trolytes with improved oxidative stability, may result
in significantly improved specific capacity.
As an example of other spinel compounds of the
general composition LiM20 ~, LiV204 (#67-68) is
given in Table 1. The potential of LiV204 material
versus Li is somewhat lower than the LiMn20 ~.
Other materials in this group generally have very
low reversible capacities at reasonable rates, e.g.
LiTi204 [177-180], LiV20 ~ [73-74, 177-178, 181],
and LiCo204 [178, 181].
Obviously, the current selection of cathode mate-
rials is rather limited, and in addition the capacities
are small compared to other cathode materials (e.g.
TiS 2, V6013, etc.) and the carbon based anode mate-
rials. Apart from the materials reviewed here, re-
search on molybdenum oxides, and extended to
vanadium and manganese oxides [182, 183]. has lead
to the discovery of a new group of cathode materials.
14. Summary
The reversible capacity of LiCoO 2 falls in the
range from 120-130 m A h / g , and the compound is
most suitable as a cathode material if it is highly
crystalline. The reversibility is dependent on the
amount of lithium removed from the structure. Re-
moval of relatively large amounts, resulting in irre-
versible structural changes, lowers the capacity sig-
nificantly. The capacity is otherwise fairly independ-
ent of the preparation method.
Contrary to LiCoO 2, the lithium insertion proper-
ties of the LiNiO 2 compound and the reversibility of
the reaction, is very dependent on the preparation
conditions. Unless strongly oxidizing conditions are
applied, the electrochemical activity is practically
zero. Only compounds of the electrochemically ac-
tive structure were included in this review. The
capacity is in general slightly higher that of the
LiCoO 2 compound, i.e. in the range 120-150
mAh/g. Again, removal of relatively large amounts
of lithium inducess irreversible structural changes
which reduces the available capacity.
Other LiMO 2 compounds have very limited re-
versible capacities, e.g. the reversible of LiCrO 2 is
less than 60 m A h / g .
Substitution of either Ni or Co for other first row
transition metals generally has a negative effect on
the capacity and possibly also on the reversibility of
the lithium insertion reaction. For example, partial
substitution of Ni with Fe reduces the reversible
capacity to less than I00 mAh/g.
 R. Ko~'bang et al. / Solid State Ionics 84 (1996) 1-21
An exception to the general trend of these data, is
the substitution of Ni for Co or vice versa. In this
case, the results are roughly the same as with the
parent compounds, both in terms of capacity and
reversibility. However, a larger fraction of the capac-
ity is removed at potentials slightly lower than that
of the LiCoO 2 compound (i.e. less demanding for
the electrolyte stability), and the mixed compounds
are far easier to prepare than LiNiO 2.
LiMn204 is able to insert four lithium ions per
formula unit between 1 and roughly 4.3 V versus Li,
but only the two upper plateaus are of interest as
cathode materials for rocking chair batteries. The
theoretical capacity of each of these two plateaus is
about 150 mAh/g. Although the preparation condi-
tions for the LiMn204 compounds are not quite as
demanding as those for LiNiO 2, some adjustment of
the capacity is possible, primarily by varying the
preparation temperature. The precursor seems to be
less important. However, by using a low temperature
synthesis route, it is easier to change the properties
than by applying a conventional solid state annealing
process. Although the capacity ratios of the two
plateaus may be varied, the sum of the capacities of
the two plateaus remains constant.
Practical reversible capacities up to about 130
m A h / g have been reported for each plateau. The
most interesting plateau for rocking chair batteries
(i.e. the 4 V plateau) has been reported to cycle
about 75 m A h / g after about 1100 cycles.
Different types of LiMnO 2 compounds have been
reported to insert large amounts of lithium re-
versibly, but in a wider voltage range. The reversible
capacities (160-180 mAh/g) are far lower than
originally anticipated (theoretically about 285
mAh/g).
As in the LiNiO 2 and LiCoO 2 cases, replacement
of the Mn with another first row transition metal
appears to reduce the reversible capacity. Further-
more, the voltage range was expanded considerably
in these experiments.
L i - M n - O compounds form a large group of
compounds, and apart from the forementioned com-
pounds, the most extensively investigated com-
pounds are Li2Mn4Oz2 and Li4MnsOi2. None of
these compounds has received nearly as much atten-
tion as the LiMn204 compound. The oxidation state
of Mn is + 4 in both compounds, and consequently
17
lithium removal from these compounds is extremely
difficult. At the lower plateau, lithium may be in-
serted in approximately the same amounts as in
LiMn204.
A couple of new cathode materials (LiNiVO: and
LiCoVO 4) have recently been discovered. Apart from
a capacity of about 45 m A h / g and a high potential
versus Li, very few details regarding their lithium
insertion properties are presently available.
Second and third row transition metal oxides are
not considered in this review since they tend to insert
lithium at potentials below 3 V versus Li.
Finally, it should be noted that the thermal stabil-
ity of LixCoO 2, LixNiO 2 and LixMnO 2 in air is
excellent for x = 1 [184]. However, for x < 1, the
stability decreases both in air and in inert atmo-
sphere. The delithiated compounds release oxygen
during heating and the stability decreases in the
order Li,NiO 2 < Li~CoO 2, < LixMnO 2 [184]. An-
other study, in which the thermal characteristics of
carbon/LiNiO 2 (AA cells) was carried out as func-
tion of the capacity balance ratio of the electrodes,
confirmed the previous findings [185].
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