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Solid State Ionics69 (1994) 201-211

Why transition metal (di)oxides are the most attractive materials


for batteries
Tsutomu Ohzuku, Atsushi Ueda
Electrochemistry and Inorganic Chemistry Laboratory, Department of Applied Chemistry, Faculty of Engineering,
Osaka City University, Sugimoto 3-3-138, Sumiyoshi, Osaka 558, Japan

Abstract

Recent developments of materials for rechargeable lithium batteries are highlighted. The reactions using advanced batteries
consist of lithium ion insertion into and extraction from a solid matrix without the destruction of core structures, (called topotactic reaction) enable us to study systematically battery materials. By applying a hard-sphere model the optimum chemical
composition and element in terms of volumetric capacity in Ah.cm -~ are indicated to be DMeO2 or LiMeOz (Me = transition
metal elements). The calculated values, assuming one electron transfer per a transition metal ion, are in the range 1.15-1.5
Ah.cm-3 for both nMeO2 and LiMeO2 using available structural data, which is alone merely attainable using transition metal
dioxides. The approximate operating voltages for the reaction Li+ DMeO2~LiMeO2 are pictured against the number of delectrons. The order of operating voltages of transition metal (di)oxides is approximately; 3d > 4d > 5d and d" < d" + ~ (n = 0 to
6) distributed in the voltage between 0.5 and 4.5 V versus a lithium electrode. From these results, we discuss why transition
metal (di)oxides are the most attractive materials for advanced lithium batteries. The specificproblems in developingthe insertion materials based on metal (di)oxides further are also discussed.

1. Introduction

Battery technology has been developed mainly by


the experience-based or curiosity-based researches
during the past 100 years. In the early stage of investigations, almost every organic and inorganic material had been examined in aqueous solutions and the
possible candidate materials were selected. Many of
them, however, did not survive due to the natural or
artificial selection. Cathode materials which are still
used and will not be ruined in batteries are:
(1) manganese (di)oxide (MnO2) in primary
batteries, such as zinc-carbon (Leclanch6L zinc
chloride, and alkaline manganese dioxide cells;
(2) nickel oxyhydroxide (NiOOH) in secondary
alkaline batteries, i.e., nickel/cadmium or recent
nickel/metal hydride cells, and

(3) lead dioxide (PbO2) in lead acid batteries.


These cells, especially manganese dioxide cells and
lead acid batteries, have long long histories. Of these,
nickel oxyhydroxide may be referred to as hydrogenated nickel dioxide although no one called it the reduction product of hypothetical nickel dioxide in a
proton-electron reaction. These batteries are highly
advanced and widely used all over the world. However, innovation in terms of high energy density batteries is almost hopeless in the current form because
of the thermodynamic limitation of water ( 1.23 V of
decomposition voltage at 25C).
Recent demands towards the high energy density
batteries stimulate the materials research for nonaqueous lithium batteries~ Since the late 1960's, many
materials, such as metal chlorides, bromides, fluorides, oxides, sulfides, selenides, etc., have been ex-

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202

T. Ohzuku, A. Ueda / Solid State lonics 69 (1994) 201-211

amined in nonaqueous lithium cells [1,2]. Several


materials have been proposed and some of them have
been already demonstrated. The success in primary
lithium batteries, L i / ( C F ) ~ and Li/MnO2, as power
sources for electronic devices (mainly fully automatic camera) in the early 1980's is a milestone in
the high energy density lithium batteries. Ambient
temperature rechargeable lithium cells have also been
investigated because of increased energy density over
conventional rechargeable batteries. The rechargeable lithium batteries, such as Li/TiS2, Li/MoS2, Li/
NbSe3, Li/MnO2, Li/vanadium oxides, etc., have
been advanced and already demonstrated in prototype cells. High-volume rechargeable lithium cells for
consumer use, however, have not been succeeded yet
for a couple of reasons. Of these, V205, Nb2Os and
MnO2 are used in low-volume coin-type rechargeable
lithium cells, i.e., LiV2Os/Nb205 [3] and Li-Al/
MnO2 [4], for the use of memory back-up.
More recently, an innovative secondary system
called the lithium-ion (shuttlecock) cell or rocking
chair cell [ 5] has been developed and commercialized as power sources for handy video cameras, wireless telephones and other electronic devices [ 6 ]. The
cell consists of LiCoO2 and a carbon.
As it was described briefly above, transition metal
(di) oxides seem to be essential in fabricating batteries including the conventional and advanced batteries although the materials selection has been done independently through the empirical approaches.
Systematic and fundamental studies on battery materials would be necessary to assess the previous decision on the selection of battery materials and to
promote the materials researches for advanced batteries. In this paper, we settle some fundamentals on
the electrochemistry of battery materials and give a
rational reasoning on why transition metal (di)oxides
are the most attractive materials for batteries.

2. Key parametric factors in considering the battery


materials
Almost every organic and inorganic material shows
more or less redox (reduction-oxidation) properties
in appropriate electrolytes. However, "materials show
redox properties" is only a necessary condition in applying the materials to batteries. We have to consider

what are the key parametric factors in selecting materials even in a basic research.
Energy density is a common measure in evaluating
battery systems. Energy stored in a battery is measured by discharging a battery at an appropriate current. The energy in Watt-hour (Wh) is the product
of average operating voltage in Volt (V) and discharge capacity in Ampere-hour (Ah). Accordingly,
higher operating voltage and larger capacity give
higher energy density. The operating voltage is the
derivative of the Gibbs free energy change for a cell
reaction. The discharge capacity follows the Faraday
law. The voltage (intensive quantity) and capacity
(extensive quantity) are independent and not interchangeable. When the weight and volume of a battery
is known, we can easily calculate energy density. The
energy density, however, is not an abstract form in
evaluating battery systems [ 7 ]. Suppose two AA-size
cells having the same energy density. One is 1 V of
operating voltage and 1 Ah of capacity, and another
is 4 V and 0.25 Ah. When an electronic device requires the voltage above 3.5 V, the former cannot deliver electricity to the device unless the four cells are
connected in series, while the latter can be used in a
single cell. A risk in connecting a number of cells in
series is well known among the battery community
people [8]. Conversely, when a device requires the
voltage just above 0.8 V, one-Volt cells having 1 Ah
of capacity are superior to four-Volt cells having only
0.25 Ah, because the higher voltage above 0.8 V is
useless, i.e., the energy mainly consumes the generated heat. Such a characteristic feature makes it impossible to design batteries for general purposes.
For practical batteries the cell dimensions are specified, so that space rather than weight is limited in
designing batteries. In other words, the volumetric
capacity in Ah.cm-3 for the materials is more important parametric factor than the gravimetric capacity
in considering the battery materials. Therefore, we
discuss the factors affecting the volumetric capacity
of materials and the operating voltage separately.

3. Volumetric capacity of insertion materials


The electrochemical reactions consisting of electrons and foreign ions insertion into/extraction from
a solid matrix without the destruction of the core

T. Ohzuku, A. Ueda / Solid State lonics 69 (1994) 201-211

structure of a solid matrix are called topotactic reactions and the materials in which such reactions proceed are generally called the insertion materials. Since
the core structures retain during the electrochemical
reactions, topotactic reactions are basically reversible and applicable to rechargeable or secondary batteries, and also a systematic and basic research on the
battery materials become possible by characterizing
the insertion materials.
To construct insertion materials we need anions,
such as F - , CI-, O 2-, S2-, SeE-, etc., together with
cations to fix the anions and to form a rigid solid matrix. The cations require electron acceptor and donor
capability. A solid matrix must be able to accommodate foreign cations in order to compensate the excess charge when electrons are injected into or extracted from a matrix. Ionic radii of anions are
normally larger than those of cations, so that the volume of insertion materials is mainly determined by
the size of anions and their packing forms. Monovalent anions hardly give insertion materials because
of the movement of monovalent anions and poor redox capability of cations, usually divalent/monovalent cations [ 9 ].
A hard-sphere model [9,10] leading to an optimum chemical composition and the elements suggests that the volumetric capacities of insertion materials are optimized when the following
electrochemical reaction proceeds in a topotactic
manner;
[] MeO2 + L i ~ Li MeO2
(oct) (oct) (ep)

(1)

(oct) (oct) (cp)

in which (oct) indicates the octahedral sites in a


close(st) packed oxygen array denoted by (cp) and
[] represents the vacant octahedral sites. In leading
such a basic line on the materials research we
assumed:
( 1 ) the reaction consists of electrons injection and
foreign cations insertion into a solid matrix without
the destruction of a core structure (topotactic
reaction );
(2) the framework structure of a solid matrix consists of the close (st) packing of divalent anions;
(3) transition metal ions are located at the octahedral sites in the close (st) -packed anion array, and
(4) inserted foreign cations are accommodated at
the octahedral sites.

203

Possible divalent anions applicable to the construction of a matrix are 0 2 - (ionic radius; 1.40 A
( C N = 6 ) ) , S2- (1.84 A ( C N = 6 ) ) , Se2- (1.98 A
( C N = 6 ) ) , and Te 2- (2.21 A ( C N = 6 ) ) [ 11 ] among
the chemical elements, where CN indicates the coordination number. When the divalent anions are closest-packed, the sizes of cations to fit at the octahedral
holes are calculated to be 0.58 A, 0.76 A, 0.82 A and
0.92 A for the closest packing of O 2-, S 2-, Se 2- and
Te 2-, respectively. The ionic radii of the transition
metals (Me 3+ and Me 4+ ) are in the range between
0.5 and 0.7 A, so that many transition metal ions can
be situated at the octahedral sites in the close(st)
packing of anions. However, monovalent cations to
be inserted into and/or extracted from a matrix seem
to be only protons (ionic radius; 0.0 A) and lithium
ions (0.74 A ( C N = 6 ) ) , because sodium ions (1.02
A ( CN = 6 ) ), potassium ions ( 1.38 A (CN = 6 ) ), rubidium ions (1.49 A ( C N = 6 ) ) , and cesium ions
( 1.70 A (CN = 6) ) are too large to be transported and
accommodated in a solid matrix based on divalent
anions.
We calculate the molar volume of LiMeO2, LiMeS2, LiMeSe2, and hypothetical LiMeTe2 in order
to estimate the volumetric capacities of these materials. In calculating the molar volumes we assume that
lithium and transition metal ions are located in suitable sizes at the octahedral sites in the closest packing
of these anions. Consequently, the problem is reduced to calculate the volume of two moles of anions
being in the closest packing.
Hexagonally closest-packed hard spheres having a
radius r A can be assigned to be a hexagonal lattice
with unit cell parameters a = 2.r and c = 3.226.r having a space group P3ml in which hard spheres are
located at 2 (d) sites with a positional parameter 0.75.
The unit cell volume is calculated from 11.313.r 3. By
calculating the unit cell volume and multiplying the
Avogadro's number, we have the molar volumes 18.7
cm 3 for LiMeO2, 42.4 cm 3 for LiMeS2, 52.9 cm 3 for
LiMeSe2, and 73.5 cm 3 for LiMeTe2. Since one mole
of LiMeX2 ( X = O 2-, S2-, Se2- and Te 2- ) is capable
to store 26.8 Ah of electricity forming I-]MeX2, the
volumetric capacities of these materials are obtained
to be 1.43 Ah.cm -3 for LiMeO2, 0.63 Ah.cm ~3 for
LiMeS2, 0.51 Ah.cm -3 for LiMeSe2, and 0.36
Ah.cm -3 for LiMeTe 2. The results were obtained using a hexagonally closest packing. Another packing is

T. Ohzuku, A. Ueda I Solid State lonics 69 (1994) 201-211

204

possible, so-called cubic closest packing. The results,


however, are the same, because the hard spheres in
the cubic closest packing are similarly characterized
by a hexagonal lattice with unit cell parameters a = 2. r
and c=4.899.rhaving a space group R3 in which the
hard spheres are located at 3 (a) sites.
As described above, the volumetric capacity which
is one of the most important parametric factors is in
the order
LiMeO2 >> LiMeS2 > LiMeSe2 > LiMeTe2.
We may conclude that LiMeO2 or DMeO2 is the candidate material for battery applications if such materials are available and exhibit electrochemical reactivity in appropriate electrolytes containing lithium
ions.
This is better illustrated in Fig. 1. The molar volumes of MeOy are calculated from the available
structural data. Parts of structural data on [2MeO2
2.0

to/trade/tire, VO.~(R)

\ / ///~i;o;~,,
////,m..o.ea,

1.,,~6 A ~ . c m - 3

~-Mnoa

r~o~..

1 . 5 - "L'43 Ah.m"
v

<

~ 1.0-

rls~

0 . 6 3 Ah.cm- 3
r.t. t M e s R ; ~ ' t . ,
(LIA

o.sL ~ M e ~ system

10
20
Molar volume of MeOy

30
/ cm 3

40

Fig. 1. The volumetric capacity in A h . c m -3 versus the molar volu m e of MeOy in cm 3 for transition metal (di)oxides. MoS2 and
TiS2 are also shown in comparison. Horizontal lines at 1.56
Ah'crn -3 and 1.43 A h . c m -3 show the calculated values from a
hard-sphere model for DMeO2 ( 0 2 - 1.40 A. ( C N = 3 ) ) and
LiMeO2 ( 0 2 - 1.40 ,~ ( C N = 6 ) ) . The arrow at 0.63 A h ' c m -3
shows the value for LiMeS2 ( S 2- 1.84 A (CN = 6 ) ).

and LiMeO2 are listed in Tables 1 and 2. A necessary


condition of the crystal structures of FqMeO2 is that
all vacant octahedral sites in DMeO2 should be linked
with each other forming the one-dimensional tunnel,
channel, or two-dimensional triangular lattice space
to transport and accommodate lithium ions. Since
FqMeO2 and LiMeO2 are interchangeable via the topotactic reaction, many crystal structures suitable for
this purpose can be found in structural reports on inorganic compounds if one looks for the structures
from quite different angles. In Table 1 DMeO2
(Me=Ti, Cr, Mn and Ru) having a space group P42/
mnm is called rutile structure [26], and FqMeO2
(Me=V, Mo and W) is called distorted rutile structure, in which vacant octahedral sites form a one-dimensional tunnel, called a [ 1 X 1 ]-tunnel structure.
Titanium dioxide having a space group I41/amd is
called anatase in which vacant octahedral sites form
a three-dimensional channel. Vanadium dioxide
having a space group C2/m is called VO2(B) [ 14].
Manganese dioxides listed in Table 1 are pyrolusite
(P42/mnm; [ 1 X 1 ]-tunnel structure), ramsdellite
(Pnam; [2X2]-tunnel structure), -MnO2 (I4/m;
[ 2 2 ] -tunnel structure ), and X-MnO2 (Fd~m; threedimensional channel structure) [ 27 ]. Nickel dioxide
is a CdCl2-structural type in which vacant octahedral
sites form a triangular lattice space [ 19 ]. Iron dioxide and cobalt dioxide have not been confirmed yet,
but a layered form of these materials seems to be quite
possible in nonaqueous environment although stoichiometric FqFeO2 or FqCoO2 may not be thermodynamically stable. Table 2 shows lithium transition
metal (di)oxides in which octahedral lithium ions can
supposedly move from one site to another. Of these,
the preparation of LiTiO2 has not been succeeded yet,
because of its extreme reactivity with even a trace of
oxygen or water [28]. The structure of LiFeO2 is
classified as a, ~, and 7 forms [29]. None of them
does satisfy the structural requirements to act as the
insertion materials. A new structural form of LiFeO2
would be necessary.
In calculating the theoretical volumetric capacities
in Ah.cm -a, wc assumed one electron transfer per a
transition metal ion. In Fig. 1, V205, Nb2Os, MoOa,
MoS2 and TiS2 are also plotted in comparison. The
results obtained from a hard-sphere model are shown
in horizontal arrows at 1.56 Ah.cm -3 for OMeO2
( 0 2 - 1.36 A ( C N = 3 ) ) , 1.43 Ah.cm -3 for LiMeO2

T. Ohzuku, A. Ueda / Solid State lonics 69 (1994) 201-211

205

Table 1
Transition metal dioxides ([]MeO2) in which vacant octahedral sites are linked together forming the one-dimensional tunnel, channel,
or two-dimensional triangular lattice space.
Materials

d"

Space
group

Lattice constant
a(A)

[]TiO2

3d

[]VO2

3d I

[]CrO2
[TMnO2

3d 2
3d 3

[]FeO2
[]CoO2
[]NiO2
[] MoO2
[] RuO2
[]WO2

3d 4
3d 5
3d 6
4d 2
4d 4
5d 2

P42/mnm
I41/amd
P21/c
C2/m
P42/mnm
P42/mnm
Pnam
I4/m
Fd~m
C2/m(?)
C2/m(?)
R3m
P21/c
P42/mnm
P2t/C

Capacity

b(A)

4.596
3.782
5.750
12.059
4.418
4.396
9.332
9.865
8.054
5.26
4.91
2.814
5.611
4.491
5.563

c(A)

fl(*)

2.960
9.505
5.380
6.420
2.916
2.870
2.843
2.851

4.529
3.694

4.428

2.90
2.82
4.586
4.896

(mAh.g - I ) (Ah.cm -3)


335.5

122.60
106.99

323.2
319.1
308.3

5.90
5.02
13.470
5.629
3.106
5.663

Rcf.

109
111.4
120.95
120.47

305.1
294.7
295.5
209.5
201.4
124.2

1.424
1.309
1.509
1.305
1.564
1.605
1.515
1.283
1.363
1.38
1.446
1.433
1.421
1.339

[12]
[13]
[121
[14]
[12]
[121
121
15]
161
17]
18]
19]
12]

[2o]
[21]

Table 2
Lithium transition metal dioxides (LiMeO2) in which lithium ions at octahedral sites are supposed to be mobile from one octahedral
site to another. Li [Lil/3Tis/3 ] 04 may not be adequate to list here because this is an oxidized form containing tetravalent titanium ions
(3d ) while the others are the reduced forms of corresponding transition metal dioxides [] MeO2.
Materials

d"

Space
group

Lattice constant

a(A)
Li4/3Tis/304
LiTiO2
LiVO2
LiCrO2
LiMnO2

3d
3d ~
3d 2
3d 3
3d4

LiFeO2
LiCoO2
LiNiO2
LiMoO2
LiRuO2
LiWO2

3d5
3d 6
3d ~
4d 3
4d 5
5d 3

Fd~m
(ortho.)
R3m
R3m
Pm2m
I41/amd
?
Rim
Rim
P21/c
Pnnm
P2Jc

8.365
4.08
2.836
2.897
2.802
5.645
2.819
2.882
5.570
5.055
5.534

Capacity

b(A)

c(A)

3.82

9.05
14.767
14.495
4.567
9.186
14.066
14.194
5.861
2.774
6.032

5.743

5.211
4.954
5.074

(02- 1.40 A ( C N = 6 ) ) , and 0.63 Ah.cm -3 for


LiMeS2 (S 2- 1.84 A (CN=6)). As can be seen in
Fig. l, the materials having the chemical compositions of [-]MeO2 and LiMeO2 show higher volumetric capacities than other materials. The calculated
volumetric capacities of V205, MOO3, and Li
[Li~/3Tis/3]O4 are 0.99, 0.88, and 1.01 Ah.cm -3, respectively, for the assumed reactions

fl()

118.79
118.26

Ref.

(mAh-8-t)

(Ah.cm-3)

175.1
308.6
298.2
294.7
285.5

1.014
1.26
1.298
1.267
1.211
1.216
1.379
1.308
1.152
1.281
1.193

282.8
273.9
274.5
198.7
191.4
120.3

[22]
[ 13 ]
[22]
[12]
[23]
[16]
[18]
[19]
[24]
[20]
[25]

2Li + V205 ~ Li2V205,

(2)

Li + M o O 3 --*L i M o O 3

(3)

and

]Li+ Li [Lil/aTis/3 ] O4 ~Li3Tis/3 O4.

(4)

However, generally accepted reactions [9,30] are


Li+ V2Os-)LiV205

(5)

206

T. Ohzuku, A. Ueda / Solid State lonics 69 (1994) 201-211

in the operating voltage above 3 V,


Li+ MoO3--,Li3/2MoO3

(6)

and
Li+Li[Lil/3Tis/a]O4--*Li2[Lil/3Tis/3]04 ,

(7)

so that the volumetric capacities of these materials


must be corrected to be 0.50 Ah.cm -3 for V205, 1.32
Ah.cm -3 for MOO3, and 0.58 Ah.cm -3 for
Li [Li~/3Tis/3] 04 in applying these values in Fig. 1 to
the preliminary evaluation of materials with respect
to volumetric capacity. Although the volumetric capacity of Li [Lit/3Tis/3 ] 04 is not so high, this material exhibits an interesting character in considering
the insertion materials as will be described after.
The calculation described above is perhaps the most
instructive accomplishment of the hard-sphere model
of the insertion materials, from which we conclude
that the materials of transition metal dioxides,
[]MeO2 and LiMeO2, alone merely possess the highest possible volumetric capacities ranging from 1.15
Ah.cm -a to 1.50 Ah.cm -3.

4. Operating voltage of transition metal (di)oxides in


nonaqueous lithium cells
The electrode potential E ( y ) for an insertion electrode is generally represented [ 31,32 ] by
1 (OAG(y)~
E(y) =-

F'\~/r,v

'

(8)

where AG(y) is the Gibbs free energy change for a


reaction
[]MeO2 +yLi~LiyMeO2.

(9)

Eq. (8) states that the value of a formation energy of


[] MeO2 does not affect the electrode potential and
that the change in the Gibbs free energy of the formation of Li~MeO2 per ultimate change in composition y reflects upon the electrode potential which is
observable. A theoretical approach to predict E ( y )
for any insertion electrode would be necessary in developing the solid state electrochemistry. Such a predictable theory, however, has not been matured yet,
so that we discuss quantitatively on the operating
voltages of the insertion electrodes. We consider the

elementary steps of the insertion reaction (9), which


are
( l ) to pick up an electron from 2s-orbital of lithium to form a lithium ion, i.e.,
Li~Li + +e-,

(10)

(2) to transfer an electron to 3d-orbital of a transition metal located at an octahedral site in a closepacked oxygen array, i.e.,
MeWO~ - + e--,MemO~ - ,
(oh)

( 11 )

(oh)

(3) to transfer a lithium ion into an octahedral hole


in a close-packed oxygen array, i.e.,
[] + Li+--,Li +
(oh)

(12)

(oh)

and (4) to distribute electrons and lithium ions at


octahedral sites in a solid matrix.
The overall reaction is represented by Eq. (9). In
describing the elementary steps, a process to solvate
lithium ions is not necessary, which is one of the
characteristic features of the lithium-ion insertion
electrodes when a lithium electrode is used. The energy required to step ( 1 ) is known to be 5.4 eV. The
electronic structures of MEOW- (oh) and MeO 9(oh) clusters appearing in step (2) may be calculated by using a function density theory [33]. The
energy required in step (3) may also be calculated by
the Ewald method, for example, for a specific structure. Step (4) can be solved by using a lattice gas
model with or without the interaction between
charged species [ 34 ].
According to Eq. (8), steps ( 1 ) through ( 3 ) mainly
determine the level of operating voltage and step (4)
mainly affects the shape in voltage as a function of y
in LiflVleO2 [ 18 ], because AG(y) = A H ( y ) - T A S ( y )
and AH(y) is usually in the form y.AHo for a system.
In bravery we assume that
(1) the electrostatic environment at octahedral
holes is the same over [] MeO2 regardless of the transition metal elements, and
(2) the crystal field splitting of 3d-orbitals in a local symmetry oh is negligibly small, such that the order of 3d-orbital binding energies does not change.
Since an average size of oetahedral holes or lithium-ion sites is almost the same in series of M e O 2
and LiMeO2 (Me; 3d-transition element) as shown

T. Ohzuku, A. Ueda / Solid State lonics 69(1994) 201-211

in Fig. 1, these assumptions seem to be valid for the


first insight into the operating voltage of insertion
electrodes of 3d-transition metal dioxides. Then, the
level of operating voltages of insertion electrodes is
proportional to the differences in orbital binding
energies between 2s-orbital of lithium and 3d-orbitals of transition metals. The order of the absolute values of orbital binding energies [35] are
Li(2s) < [Cr(3d) ] < Ti(3d) < V(3d) < Mn(3d) <
[O(2p) ] <Fe(3d) < C o ( 3 d ) <Ni(3d). Therefore,
almost the same order of operating voltages of 3dtransition metal dioxides would be expected.
Fig. 2 shows the approximate operating voltages of
transition metal (di)oxides in nonaqucous lithium
cells. The solid lines are used to guide the eyes. The
upper and lower lines indicate 3d- and 4d-transition
metal (di) oxides, respectively. The relation between
the operating voltage and d-electron character can be
seen clearly as expected. The operating voltage is approximately in the following order: 3d-transition
metal di(oxide) >4d-metal (di)oxide> 5d-metal
5.0

/-,.0

3.0

2.0
LU

1.0

dO

d/

d2

d3

Number of

d,~

d~

de

dz

d-electrons

Fig. 2. Approximate operating voltages of transition metal


(di)oxides in nonaqueous cells. Solid lines are used to guide the
eyes. Upper and lower lines indicate 3d and 4d transition metal
(di)oxides, respectively. Relation between the operating voltages and the number of d=electrons can clearly be seen.

207

(di)oxide, and TiO2(3d/3dl)<VO2(3dl/3d 2)


< [CrO2(3d2/3d 3)] < MnO2(I)(3d3/3d 4) <
MnO2(II)(3da/3d 4) >_- CoO2(3dS/3d 6) >- NiO2
(3d6/3dV).
Of these, manganese (di)oxide shows two levels of
operating voltages at 3 and 4 V, denoted by (I) and
(II). The dotted curve in Fig. 2 is the expecting range
for iron dioxide, whose reactivity including reversibility of a reaction has not been confirmed yet. The
curve for LiVO2 is pictured for the oxidation of LiVO2
to Li2/aVO2 (not a topotactic reaction) [22].
V2Os(3d),
Nb2Os(4d),
MoOa(4d),
and
Li [ Lil/aTis/3 ] 04 (3d ) are also shown in Fig. 2. These
materials together with TiO2 (3d ) have no conduction electrons in a solid matrix, so that they show
white in color and insulating electrical properties except V205. Insulators seem to be useless in batteries.
However, these materials can be used as cathode materials in nonaqueous lithium batteries. Electrons injected into a solid matrix supply conduction electrons with an aid of lattice vibration (thermal
energy), so that partially reduced samples appear blue
in color and highly conductive. These materials have
transmission lines throughout a matrix in terms of
lithium-ion transportation. These two factors make
the insulating materials use in rechargeable lithium
batteries.
In dividing reaction (9) into four elementary steps,
we simply describe a solid state redox reaction as Eq.
( 11 ). However, the observations described above
strongly suggest that a theory to fill a gap between
electrochemistry and solid state physics is inevitably
necessary in developing solid state electrochemistry,
through which we can count the problems as to the
collective electrons versus localized electrons together with cooperative Jahn-Teller effects and the
one-phase versus two-phase, and with which we can
predict what level of operating voltage and how much
reversible capacity are expectable for the targeting
materials. The treatment described here is oversimplified, but our simplification is adequate for a first
look at the operating voltages of the insertion materials based on transition metal (di)oxides. As can be
seen in Fig. 2, we can expect operating voltages from
0.5 V to 4.5 V for insertion materials of transition
metal (di)oxides in nonaqueous lithium batteries.

T. Ohzuku, A. Ueda / Solid State l onics 69 (1994) 201-211

208

5. Factors affecting capacity failure of insertion


materials in rechargeable batteries

[ 15,16,18-20,36 ], so that stress is induced by strain


due to a dimensional mismatch between regions having different degree of reaction. Stress may be proportional to the differences in both lattice dimensions and the thickness of a gradient region in terms
of the concentrations of electrons and lithium ions in
a unit cell level. When local stress exceed certain elastic limit of a matrix, crack appears and grows mechanically in actual particles in order to release stress
induced by the insertion reaction. Larger difference
in dimension between unreacted and reacted matrixes, i.e., VqMeO2 and LiMeO2, and smaller thickness of the gradient region induce higher stress in the
region, whose thickness depends on the current applied and the transfer rate of lithium ions in a solid
matrix. Transition metal (di)oxide ceramics are usually fragile, so that crashing to fine powder is quite
easy. Therefore, when one of the lattice dimensions
changes more than 15% during an insertion or extraction reaction, it is almost impossible to show topotactic reactions and their rechargeable properties.
Empirical approach suggests that maximum strain
allowed in the observable topotactic reactions is about
12/o as can be seen in r-qRuOz/LiRuO2 [20] and

Rechargeable characters of insertion materials are


applicable to a function of either positive or negative
electrodes for rechargeable lithium batteries. However, "materials show rechargeable characters" is one
thing, and "materials show sufficient capacity retention for extended cycles" is another thing. One can
not tell cell performance in advance, especially cycle
life, out of the basic research results unless prototype
cells are fabricated and tested. In this section we
briefly discuss the factors affecting the cycle life of
the insertion materials from a fundamental point of
view.
Electrochemical charge and discharge is usually accompanied by the change in lattice dimensions of a
solid matrix. When rqMeO2 is reduced in nonaqueous lithium cells, electrons are injected from the outside of a solid matrix and lithium ions are inserted
into a solid matrix via a solid/liquid interface in order to compensate excess charge. The degree of reaction distributes locally in a solid matrix from the surface to the bulk of a matrix. The lattice dimensions
are usually a function of the degree of reaction
S.C

S.0

S.C

4.0

4.0 - -

:!

&C

3.0

3.(

i,

.a

I O0 mAh-g-/

125 mAh'g - I

uJ 2,[

ua

,c

I.C

,~

,'

n~1~.g" I

,;o

[ LiCoO2

L0

~o

200

SO

1
I

5.0

510

150

150 mAh'g-I

ua 2.0

200

I--o 1
I

5O

I~

ml.~g "1

150

i n ~ ' g -I

S.O

40

3.0

iOOmAh-g - /

Z.0

izJ

3.0

zot
r

125 mAtt.g-~

50

150

I00
CI

mAh 9-I

200

"

~ ZO

50

11

100
Q

3.0

'

150

ZOO

150 m~h.g -I t

"[I L'N'" I

1.0

-~

1S0
mAh.9 "1

ZOQ

'
511

IQO

mAl'l.C3"t

Fig. 3. Charge and discharge curves of LiCoO2 and LiNiO2 at a rate of 0.17 rnA.cm -2 at 30C in nonaqueous lithium cells. Electrolyte
used was 1 M LiC104 dissolved in propylene carbonate. The cells were discharged at constant current to 2.5 V after the constant capacity
charge at 100, 125, or 150 mAh.g -1 based on the sample weight.

209

T. Ohzuku, A. Ueda / Solid State lonics 69 (1994) 201-211

LiMn204/Li2Mn204 [ 16 ]. However, rechargeable


capacity fades rapidly during cycles.
Fig. 3 shows the charge and discharge curves of
LiCoO2 and LiNiO2 having layered structures. The
structure of LiCoO2 and also LiNiO2 has a space
group R3m in which transition metal ions and lithium ions are located at octahedral 3(a) and 3(b)
sites, respectively, in a cubic close-packed oxygen array. The unit cell dimensions of LiCoO2 and LiNiO2
are usually described in hexagonal setting, i.e.,
a=ca.2.8 A and c=ca. 14 A. Change in the c-axis dimensions of these materials during charge and discharge is within 5% depending on the depth of charge
[ 18,19 ]. Layered materials may be easy to release internal stress induced by the insertion or extraction of
lithium ions compared with the materials having onedimensional tunnel structure [36-38] or three-dimensional framework structure [ 16 ]. Capacity loss
during cycles is inevitable due to the fracture of an
active solid matrix Unless strain is zero, such that the
lattice dimensions do not change during charge and
discharge. A careful preparation of the electrodes and
application of pressure onto the electrodes, called a
bobbin pressure in our laboratory, are necessary to
minimize the capacity loss and extend cycle life. Such
a mechanical factor will be reduced by applying ceramics techniques including powder or thin-layer
technology [39-41 ] in materials science in preparing the insertion materials and processing the
electrodes.
Zero-strain insertion materials are perhaps ideal for
the long-life rechargeable batteries. Fig. 4 shows the
charge and discharge curves of Li [ Lil/3Ti5/3 ] 04 together with LiNiO2. The crystal structure of
Li[Lil/3Tis/3]O4 is a cubic having a space group
Fd3m [42] in which lithium ions are located at octahedral 16 (c) sites with occupancy 1/2 or at tetrahedral 8(a) sites, lithium ions and tetravalent titanium ions are statistically distributed at octahedral
16 (d) sites by the ratio Li/Ti = 1/ 5, and oxygen ions
are located at 32 (e) sites with a positional parameter
0.26_2 [ 12]. The reaction undergoes with one-electron transfer per a formula unit, i.e.,
Li [Lil/3Tis/3] 04 +Li + e 16(c)

16(d)

32(e)

Li, [Lil/3Tis/3] 04
16()

16(d)

32(e)

(13)

5.0

I"

(a)
z..0

> 3.0

(b)

2.0
tlJ
--

1.0

I
50
Q

I
100
I
mAh.g -!

I
150

200

Fig. 4. Charge and discharge curves of (a) LiNiO2 and (b)


Li [Lit/3Ti5/3]04 at a rate of 0; 17 mA.em-2 at 30"Cin nonaqueous lithium cells. Li[Lim/3Tis/3]O4is a zero-straininsertion material, so that loss of reehargeablecapacity cannot be seen even
after 50 cycles.The combinationof LiNiO2and Li[Lil/3Tis/3]O4
gives a lithium-ion (shuttlecock)battery showingabout 2 V of
operatingvoltage.
Theoretical capacity is calculated to be 175 mAh.g- 1
or 0.61 Ah.cm -3 for Li[Lil/3Tis/3]O4. It should be
noted that the reduction product Li2 [Lil/3Tis/3 ] 04
has still tetravalent titanium ions to be able to accept
electrons, but no vacant oetahedral sites. Accordingly, the capacity of Li [ L i t / 3 T i s / 3 ] 0 4 is limited by
the number of available octahedral sites to accommodate lithium ions, called lithium-ion site-limited
capacity [ 9 ].
The lattice dimension a=8.365 ~ is invariable
during charge and discharge in the range between 1.2
V and 3.5 V [22 ]. Since the reaction is of zero-strain
insertion and extraction of charged species, capacity
loss cannot be seen even after 50 cycles. The operating voltage is just above 1.5 V against a lithium metal.
The combination of LiNiO2 and Li [ Li~/3Ti5/3 ]O 4 in
Fig. 4 gives a lithium-ion (shuttlecock) battery having about 2 V of operating voltage, which does not
contain metallic lithium. LiNiO2 can be replaced by
LiCoO2 [43], LiNil/2Col/202 [18,44], LiMn204
[ 16,40,41 ], or LiMnO2 [23], and Li[Lil/3Tis/3]O4
is also substituted by Nb205 [45 ], petroleum coke,
or natural graphite [8,46]. To select the insertion
materials, mainly transition metal (di)oxides, one
can design the operating voltage effectively applied
to the electronic devices.
The result of a zero-strain insertion material indi-

210

T. Ohzuku, A. Ueda / Solid State lonics 69(1994) 201-211

cates the validity o f arguments described above and


the possibility to reduce or erase mechanical fracture
o f the insertion materials.

6. Concluding remarks
In this p a p e r we have described why transition
metal ( d i ) o x i d e s are the most attractive materials for
batteries in terms o f historical background, volumetric capacity, operating voltage, a n d availability o f
materials. In discussing several aspects o f the insertion materials we used mostly our own works. However, throughout our theoretical a n d experimental
works we owe a lot to other workers through literature over generation a n d all are worth a credit. Although we have not stated capacity failure due to
electrolyte decomposition, o x i d a t i o n a n d also reduction resistant a n d highly conductive electrolytes are
inevitably necessary in o r d e r to develop the advanced batteries. Recent progress on the materials for
a d v a n c e d batteries requires a stable electrolyte in the
voltage range o f at least 0 - 5 V against a metallic lithium electrode. Electrolyte is not~necessarily based on
organic solvents whose heat o f c o m b u s t i o n is always
exothermic. Inorganic solvents or lithium-ion conductive solid electrolytes, hopefully l i t h i u m - m e t a l oxygen system, m a y be a possible replacement for the
present electrolyte, with which we m a y expect high
voltage window ( 0 - 5 V versus L i ) a n d safety operation even for the high-volume rechargeable batteries.
Cooperative researches a m o n g electrochemists, organic and inorganic chemists, material scientists, and
applied physicists are extremely i m p o r t a n t to develop the battery materials. Such interdisciplinary
researches will provide a new field in materials science for advanced batteries. The present authors hope
that fundamental a n d a p p l i e d researches will grow
through the studies outlined herein in the near future.

Acknowledgements
One o f us ( T . O ) wishes to t h a n k Dr. Taketsugu
Hirai, Professor Emeritus from Osaka City University, for his suggestions throughout the research. The
present work was partially s u p p o r t e d by a Grant-in-

A i d for Scientific Research from the Ministry o f Education, Science and Culture, Japan.

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