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ELSEVIER
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
202
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.
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)
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
204
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 ) ).
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
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
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]
(2)
Li + M o O 3 --*L i M o O 3
(3)
and
(4)
(5)
206
(6)
and
Li+Li[Lil/3Tis/a]O4--*Li2[Lil/3Tis/3]04 ,
(7)
F'\~/r,v
'
(8)
(9)
(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)
(12)
(oh)
/-,.0
3.0
2.0
LU
1.0
dO
d/
d2
d3
Number of
d,~
d~
de
dz
d-electrons
207
208
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
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
210
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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