artigo why transition metal (di)oxides are the most attractive materials for batteries

8/10/2019 ARTIGO Why transition metal (di)oxides are the most attractive materials for batteries

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ELSEVIER Solid State Ionics69 (1994) 201-211

W h y t r a n s it io n me t a l d i ) o x i d e s a r e t h e m o s t a t tr a c t iv e m a t e r ia l s

for bat ter ies

T s u t o m u O h z u k u A t s u sh i U e d a

Electrochemis try and Inorganic Chem is try Laboratory Department o f Appl ied Chem is try Facul ty of Engineer ing

Osaka City Univers i ty 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 topo-

tactic 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

DMeO 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 d-

electrons. 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 specific problems in developing he inser-

tion materials based on metal (di)oxides further are also discussed.

1 Introduct ion

Battery technology has been developed mainly by

the experience-based or curiosity-based researches

during the past 100 years. In the early stage of inves-

tigations, almost every organic and inorganic mate-

ria l 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 l ong long histories. Of these,

nickel oxyhydroxide may be referred to as hydrogen-

ated nickel dioxide although no one called it the re-

duction product of hypothetical nickel dioxide in a

proton-electr on reaction. These batteries are highly

advanced and widely used all over the world. How-

ever, innova tion in te rms o f high energy density bat-

teries is almost hopeless in the current form because

of the t hermodynamic limitation o f water ( 1.23 V of

decomposition voltage at 25C).

Recent demands towards the high energy density

batteries stimulate the materials research for non-

aqueous lithium batteries~ Since the late 1960's, many

materials, such as metal chlorides, bromides, fluor-

ides, oxides, sulfides, selenides, etc., have been ex-

0167-2738/94/$07.00 @ 1994 Elsevier Science B.V. All rights reserved

S S D I 0167-2738 ( 94 ) 00030-V


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202 T. Oh z u k u , A . U e d a / S o l id S ta t e lo n ic s 6 9 1 9 94 ) 2 0 1 -2 1 1

a m i n e d i n n o n a q u e o u s l i t h i u m c e l l s [ 1 , 2 ] . S e v e r a l

m a t e r ia l s h a v e b e e n p r o p o s e d a n d s o m e o f t h e m h a v e

b e e n a l r e a d y d e m o n s t r a t e d . T h e s u c c e ss i n p r i m a r y

l it h i u m b a tt er ie s , L i / ( C F ) ~ a n d L i / M n O 2 , a s p o w e r

sources fo r e l ec t ron i c dev ices (ma in ly fu l l y au to -

mat i c camera ) i n t he ea r ly 1980 ' s i s a m i l e s tone in

t h e h i g h e n e r g y d e n s i t y l it h i u m b a t te r i es . A m b i e n t

t empe ra tu re recha rgeab le l i t h ium ce ll s have a l so been

i n v e s ti g a t ed b e c a u s e o f i n c r e a s e d e n e r g y d e n s i t y o v e r

conven t iona l recha rgeab le ba t t e r i e s . The recha rge -

a b l e l it h i u m b a t t e ri e s , s u c h a s L i / T i S 2 , L i / M o S 2 , L i /

N b S e 3 , L i / M n O 2 , L i / v a n a d i u m o x i d e s , e t c . , h a v e

b e e n a d v a n c e d a n d a l r e a d y d e m o n s t r a t e d i n p r o t o -

type ce ll s. H igh-vo lume recha rgeab le l i t h ium ce l ls fo r

c o n s u m e r u s e, h o w e v e r , h a v e n o t b e e n s u c c e e d e d y e t

fo r a coup le o f reasons . Of t hese , V205, Nb2Os a nd

MnO 2 a re used in l ow-vo lum e co in - type recha rgeab le

l i t h ium ce ll s, i. e ., L iV2O s/Nb205 [3 ] a nd L i -A l /

M n O 2 [ 4 ] , f o r t h e u s e o f m e m o r y b a c k -u p .

M o r e r e c e n t l y , a n i n n o v a t i v e s e c o n d a r y s y s t e m

ca l l ed t he l i t h ium-ion ( shu t t l ecock) ce l l o r rock ing

cha i r cel l [ 5 ] has been deve loped and com mer c i a l -

i z e d a s p o w e r s o u r c e s f o r h a n d y v i d e o c a m e r a s , w i r e -

l ess t e l ephones and o the r e l ec t ron i c dev ices [ 6 ] . The

ce ll cons i s ts o f L iCoO2 an d a ca rbon .

As i t was desc r ibed b r i e f ly above , t ran s i t i on m e ta l

(d i ) ox ides seem to be e ssen t i a l i n fab r i ca t i ng ba t t e r -

i es i n c l u d in g th e c o n v e n t i o n a l a n d a d v a n c e d b a t t e r -

i e s a l t hough the ma te r i a l s se l ec t i on has been do ne in -

d e p e n d e n t l y t h r o u g h t h e e m p i r i c a l a p p r o a c h e s .

S y s t e m a t i c a n d f u n d a m e n t a l s t ud i e s o n b a t t e r y m a -

t e r i a ls wou ld be necessa ry t o a ssess t he p rev iou s de -

c i s io n o n t h e s e l e c ti o n o f b a t te r y m a t e r i a ls a n d t o

p r o m o t e t h e m a t e r i a ls r e s e a rc h e s f o r a d v a n c e d b a t -

t e r ie s . In th i s pape r , we se t t l e som e fund am en ta l s on

t h e e l e c t r o c h e m i s t r y o f b a t t e r y m a t e r i a l s a n d g i v e a

r a t io n a l r e a s o n in g o n w h y t r a n s i t i o n m e t a l ( d i ) o x i d e s

a re t he m os t a t t rac t i ve m a te r i a l s fo r ba t te r i e s .

2 Key parametric factors in considering t he battery

materials

wh at a re t he key pa ram et r i c fac to rs i n se l ec ti ng ma-

t e r i a ls even in a bas i c re sea rch .

E n e r g y d e n s i t y is a c o m m o n m e a s u r e i n e v a l u a t i n g

ba t t e ry sys t ems . Energy s to red in a ba t t e ry i s mea-

su red by d i scha rg ing a ba t t e ry a t an a ppro pr i a t e cu r -

r e n t . T h e e n e r g y i n W a t t - h o u r ( W h ) i s t h e p r o d u c t

o f a v e r ag e o p e r a t in g v o l ta g e i n V o lt ( V ) a n d d i s-

c h a r ge c a p a c i t y i n A m p e r e - h o u r ( A h ) . A c c o r d i n g ly ,

h igher ope ra t i ng vo l t age and l a rge r capac i ty g ive

h igher ene rgy dens i ty . The opera t i ng vo l t age i s t he

de r iva t ive o f the G ibbs f ree ene rgy change fo r a ce l l

r e a c t io n . T h e d i s c h ar g e c a p a c i t y f o ll o w s th e F a r a d a y

l a w . T h e v o l t a g e ( i n t e n s i v e q u a n t i t y ) a n d c a p a c i t y

( e x t e n si v e q u a n t i t y ) a r e i n d e p e n d e n t a n d n o t i n t e r -

c h a n g e ab l e . W h e n t h e w e i g h t a n d v o l u m e o f a b a t t e r y

i s known , we can eas i l y ca l cu l a t e ene rgy dens i ty . The

energy dens i ty , however , i s no t an abs t rac t fo rm in

eva lua t ing ba t t e ry sys t em s [ 7 ] . Suppose two AA -s ize

ce ll s hav in g the same ene rgy dens i ty . On e i s 1 V o f

o p e r a t i n g v o lt a g e a n d 1 A h o f c a p a c it y , a n d a n o t h e r

i s 4 V and 0 .25 Ah . When an e l ec t ron i c dev ice re -

qu i res t he vo l t age above 3 .5 V , the fo r me r canno t de -

l i ve r e l ec t r i c it y t o t h e dev ice un l ess t he fou r ce l ls a re

conn ec t ed in se r i e s , wh i l e t he l a t t e r can be use d in a

s ingl e ce ll . A r i sk i n conne c t ing a n um ber o f ce l ls i n

s e ri e s is w e ll k n o w n a m o n g t h e b a t t e r y c o m m u n i t y

peop le [8 ] . Converse ly , wh en a dev ice requ i res t he

vo l t age j u s t above 0 .8 V , one -Vol t ce ll s hav ing 1 Ah

of capac i ty a re supe r io r t o fou r -Vo l t ce ll s hav ing on ly

0 .25 Ah , because t he h ighe r vo l t age above 0 .8 V i s

use l ess , i. e ., t he ene rgy ma in ly co nsum es the gener -

a t ed hea t . Such a cha ra c t e r i s t i c fea tu re ma kes i t im-

poss ib l e t o des ign ba t t e r i e s fo r genera l pu rposes .

For p rac t i ca l ba t t e r i e s t he ce ll d imens io ns a re spec -

i f i ed , so t ha t space ra the r t han we igh t i s l im i t ed i n

des ign ing ba t t e r ie s . In o the r words , t he vo lum et r i c

c a p a c i ty i n A h . c m - 3 f o r t h e m a t e r i a ls is m o r e i m p o r -

t a n t p a r a m e t r i c f a c t o r t h a n t h e g r a v i m e t r i c c a p a c it y

in cons ide r ing the ba t t e ry ma te r i a l s . There fo re , we

d i scuss t he fac to rs a f fec t i ng the vo lu me t r i c capac i ty

o f ma te r i a l s an d the ope ra t i ng vo l tage sepa ra t e ly .

Alm os t eve ry o rgan ic and ino rgan ic ma te r i a l shows

m o r e o r le ss r e d o x ( r e d u c t i o n - o x i d a t i o n ) p r o p e r t i e s

in appropr i a t e e l ect ro ly t es . How ever , ma te r i a l s show

r e d o x p r o p e r t i e s i s o n l y a n e c es s a r y c o n d i t i o n i n a p-

p ly ing the m a te r i a l s t o ba t t e r i e s . We hav e to cons id e r

3 Volumetric capacity o f insert ion materia ls

The e l ec t rochemica l reac t ions cons i s t i ng o f e l ec -

t r o n s a n d f o r e ig n io n s i n s e r t io n i n t o / e x t r a c t i o n f r o m

a s o l i d m a t r i x w i t h o u t t h e d e s t r u c t i o n o f th e c o r e


3/11

T . Oh z u k u , A . Ue d a / S o l id S ta t e lo n ic s 6 9 1 9 94 ) 2 0 1 -2 1 1 203

s t r u c t u r e o f a s o l i d m a t r i x a r e c a l l e d t o p o t a c t i c r e a c -

t i o n s a n d t h e m a t e r i a l s i n w h i c h s u c h r e a c t i o n s p r o -

ceed a r e gene ra l ly ca l l ed the in s e r t ion ma te r i a l s . S ince

t h e c o r e s tr u c t u r e s r e t a i n d u r i n g t h e e l e c t r o c h e m i c a l

r e a c t i o n s , t o p o t a c t i c r e a c t i o n s a r e b a s i c a l l y r e v e r s i -

b l e a n d a p p l i c a b l e t o r e c h a r g e a b l e o r s e c o n d a r y b a t -

t e r ie s , a n d a l s o a s y s t e m a t i c a n d b a s i c r e s e a r c h o n t h e

b a t t e r y m a t e r i a l s b e c o m e p o s s i b l e b y c h a r a c t e r i z i n g

t h e i n s e r t i o n m a t e r i a l s .

T o c o n s t r u c t i n s e r t i o n m a t e r i a l s w e n e e d a n i o n s ,

s u c h a s F - , C I - , O 2 - , S 2 - , SeE - e t c ., t o g e t h e r w i t h

c a t i o n s t o f i x t h e a n i o n s a n d t o f o r m a r i g i d s o li d m a -

t ri x . T h e c a t i o n s r e q u ir e e l e c t r o n a c c e p t o r a n d d o n o r

c a p a b i l it y . A s o l i d m a t r i x m u s t b e a b l e to a c c o m m o -

d a t e f o r e i g n c a t i o n s i n o r d e r t o c o m p e n s a t e t h e e x -

c e s s c h a r g e w h e n e l e c t r o n s a r e i n j e c t e d i n t o o r e x -

t r a c t e d f r o m a m a t r i x . I o n i c r a d i i o f a n i o n s a r e

n o r m a l l y l a r g e r t h a n t h o s e o f c a t i o n s , s o t h a t t h e v o l -

u m e o f i n s e rt i o n m a t e r ia l s is m a i n l y d e t e r m i n e d b y

t h e s i ze o f a n i o n s a n d t h e i r p a c k i n g f o rm s . M o n o -

v a l e n t a n i o n s h a r d l y g i v e i n s e r t i o n m a t e r i a l s b e c a u s e

o f th e m o v e m e n t o f m o n o v a l e n t a n io n s a n d p o o r r e -

d o x c a p a b i l i ty o f c a ti o n s, u s u a l ly d i v a l e n t / m o n o v a -

l en t ca t ions [ 9 ].

A h a r d - s p h e r e m o d e l [ 9 , 1 0 ] l e a d i n g t o a n o p t i-

m u m c h e m i c a l c o m p o s i t i o n a n d t h e e l e m e n t s s ug -

g e st s th a t t h e v o l u m e t r i c c a p a c i t ie s o f i n s e r t i o n m a -

t e r i a l s a r e o p t i m i z e d w h e n t h e f o l l o w i n g

e l e c t r o c h e m i c a l r e a c t i o n p r o c e e d s i n a t o p o t a c t i c

m a n n e r ;

[ ] M e O 2 + L i ~ L i M e O 2 ( 1 )

oct) oct) ep) oct) oct) cp)

i n w h i c h ( o c t ) i n d i c a t e s t h e o c t a h e d r a l s i t e s i n a

c l o s e ( s t ) p a c k e d o x y g e n a r r a y d e n o t e d b y ( c p ) a n d

[ ] r e p r e s e n t s t h e v a c a n t o c t a h e d r a l s i te s . I n l e a d i n g

s u c h a b a s i c l i n e o n t h e m a t e r i a l s r e s e a r c h w e

a s s u m e d :

( 1 ) t h e r e a c t i o n c o n s i s ts o f e l e c t r o n s i n j e c t i o n a n d

f o r e i g n c a t i o n s i n s e r t i o n i n t o a s o l i d m a t r i x w i t h o u t

t h e d e s t r u c t i o n o f a c o r e s t r u c t u r e ( t o p o t a c t i c

r e a c t i o n ) ;

( 2 ) t h e f r a m e w o r k s t r u c t u re o f a s o l id m a t r i x c o n -

s i st s o f t h e c l o s e ( s t ) p a c k i n g o f d i v a l e n t a n i o n s ;

( 3 ) t r a n s i t i o n m e t a l i o n s a r e l o c a t e d a t t h e o c t a -

h e d r a l s i te s i n t h e c l o s e ( s t ) - p a c k e d a n i o n a r r a y , a n d

( 4 ) i n s e rt e d f o re i g n c a t i o n s ar e a c c o m m o d a t e d a t

the oc tahe d ra l s i t es .

P o s s i b l e d i v a l e n t a n i o n s a p p l i c a b l e t o t h e c o n -

s t r u c t i o n o f a m a t r i x a r e 0 2 - ( i o n i c r a d i u s; 1 .4 0 A

( C N = 6 ) ) , S 2 - ( 1 .8 4 A ( C N = 6 ) ) , S e2 -

1 . 9 8 A

( C N = 6 ) ) , a n d T e2 - ( 2 .2 1 A ( C N = 6 ) ) [ 11 ] a m o n g

t h e c h e m i c a l e l e m e n t s , w h e r e C N i n d i c a t e s th e c o o r -

d i n a t i o n n u m b e r . W h e n t h e d i v a l e n t a n i o n s a r e c lo s -

e s t - p a c k e d , t h e s i z es o f c a t i o n s t o f i t a t t h e o c t a h e d r a l

h o l e s a re c a l c u l a t e d t o b e 0 . 5 8 A , 0 . 7 6 A , 0 . 8 2 A a n d

0 . 9 2 A f o r t h e c l o s e s t p a c k i n g

o f O 2 - S 2 - S e 2 -

a n d

T e2 - , r e s p e c ti v e l y . T h e i o n i c r a d i i o f t h e t r a n s i t i o n

m e t a l s ( M e 3 + a n d M e 4 + ) a r e i n t h e r a n g e b e t w e e n

0 . 5 a n d 0 . 7 A , s o t h a t m a n y t r a n s i t i o n m e t a l i o n s c a n

b e s i t u a t e d a t t h e o c t a h e d r a l s i t e s i n t h e c l o s e ( s t )

p a c k i ng o f a n i o ns . H o w e v e r , m o n o v a l e n t c a t i on s t o

b e i n s e rt e d i n to a n d / o r e x t r a c t e d fr o m a m a t r i x s e e m

t o b e o n l y p r o t o n s ( i o n i c r a d iu s ; 0 .0 A ) a n d l i t h i u m

i o n s ( 0 . 7 4 A ( C N = 6 ) ) , b e c a u s e s o d i u m io n s ( 1 .0 2

A ( CN = 6 ) ), po tas s ium ions ( 1.38 A (C N = 6 ) ) , r u -

b i d i u m i on s ( 1 .4 9 A ( C N = 6 ) ) , a n d c e si u m i on s

( 1 .70 A ( CN = 6 ) ) a r e too l a rge to be t r ans po r ted and

a c c o m m o d a t e d i n a s o l i d m a t r i x b a s e d o n d i v a l e n t

an ions .

W e c a l c u la t e t h e m o l a r v o l u m e o f L iM e O 2 , L i -

M e S2 , L i M e S e 2, a n d h y p o t h e t i c a l L i M e T e 2 in o r d e r

t o e s t i m a t e t h e v o l u m e t r i c c a p a c i t i e s o f th e s e m a t e -

r ia l s. I n c a l c u la t in g t h e m o l a r v o l u m e s w e a s s u m e t h a t

l i t h i u m a n d t r a n s i t i o n m e t a l i o n s a r e l o c a t e d i n s u it -

ab le s i zes a t t he oc tahe d ra l s i t e s in the c lo s es t pack ing

o f th e s e a n i o n s . C o n s e q u e n t l y , t h e p r o b l e m i s re -

d u c e d t o c a l cu l a te t h e v o l u m e o f t w o m o l e s o f a n i o n s

be ing in the c lo s es t pack ing .

H e x a g o n a l l y c lo s e s t -p a c k e d h a r d s p h e r e s h a v i n g a

r a d i u s r A c a n b e a s s i g n e d t o b e a h e x a g o n a l l a tt i c e

w i t h u n i t c el l p a r a m e t e r s a = 2 . r a n d c = 3 . 2 2 6 . r h a v -

i n g a sp a c e g r o u p P 3 m l i n w h i c h h a r d s p h e r e s a r e

loca ted a t 2 (d ) s i te s w i th a pos i t iona l pa ram ete r 0 .75 .

T h e u n i t c e l l v o l u m e i s c a l c u l a t e d f r o m 1 1 . 3 1 3 . r 3. B y

c a l c u l a t in g t h e u n i t c e l l v o l u m e a n d m u l t i p l y i n g th e

A v o g a d r o s n u m b e r , w e h a v e t h e m o l a r v o l u m e s 1 8. 7

c m 3 f o r L i M e O 2 , 4 2 . 4 c m 3 f o r L i M e S 2 , 5 2 . 9 c m 3 f o r

L i M e S e 2 , a n d 7 3 .5 c m 3 f o r L i M e T e 2 . S i n c e o n e m o l e

o f L iM e X 2 ( X = O 2 - , S 2 - , S e2 - a n d T e 2 - ) i s capa b le

to s to r e 26 .8 A h o f e l ec t r i c i ty fo rm ing I - ]M eX 2 , the

v o l u m e t r i c c a p a c i t ie s o f t h e s e m a t e r i a l s a r e o b t a i n e d

t o b e 1 .4 3 A h . c m - 3 f o r L i M e O 2 , 0 . 6 3 A h . c m ~ 3 f o r

L i M e S 2 , 0 .5 1 A h . c m - 3 f o r L i M e S e 2 , a n d 0 . 3 6

A h . c m - 3 f o r

L i M e T e 2 .

T h e r e s u l t s w e r e o b t a i n e d u s -

i n g a h e x a g o n a l l y c l o s e st p a c k i n g . A n o t h e r p a c k i n g i s


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2 0 4

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

pos s ib le , s o -ca l led cub ic c lo s es t pack ing . T he r e s u l t s,

h o w e v e r , a r e t h e s a m e , b e c a u s e t h e h a r d s p h e r e s i n

t h e c u b i c c l o s es t p a c k i n g a r e s i m i l a r l y c h a r a c t e r i z e d

by a hexagona l l a t t ice w i th un i t ce l l pa ram ete r s a = 2 . r

a n d c=4 899 rhaving a s p a c e g r o u p R 3 i n w h i c h t h e

hard s pheres a r e loca ted a t 3 ( a ) s i te s .

A s d e s c r i b e d a b o v e , t h e v o l u m e t r i c c a p a c i t y w h i c h

is o n e o f t h e m o s t i m p o r t a n t p a r a m e t r i c f a c t o r s is i n

t h e o r d e r

L i M e O 2 > > L i M e S 2 > L i M e S e 2 > L i M e T e 2 .

W e m a y c o n c l u d e t h a t L i M e O 2 o r D M e O 2 i s t h e c a n -

d i d a t e m a t e r i a l f o r b a t t e r y a p p l i c a t i o n s i f s u c h m a -

t e r ia l s a r e a v a i l a b l e a n d e x h i b i t e l e c t r o c h e m i c a l re a c -

t i v i t y in a p p r o p r i a t e e l e c t r o l y t e s c o n t a i n i n g l i t h i u m

ions .

T h i s i s b e t t e r i l l u s tr a t e d i n F i g . 1. T h e m o l a r v o l -

u m e s o f M e O y a re c a l c u l a t e d f r o m t h e a v a i l a b l e

s t r u c t u r a l d a ta . P a r t s o f st r u c t u r a l d a t a o n [ 2 M e O 2

2 0

~ 1 . 5 - '

~

5 d - m e ta l

/- .0

3.0

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2.0

1 .0

0

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5.0

d / d 2 d 3 d ~ d ~ d e d z

N u m b e r o f d e l e c t r o n s

F i g . 2 . A p p r o x i m a t e o p e r a t i n g v o l t a g e s o f t r a n s i t i o n m e t a l

d i ) o x i d e s i n n o n a q u e o u s c e l ls . S o l id l i n e s a r e u s e d t o g u i d e t h e

e y e s . U p p e r a n d l o w e r l i n e s i n d i c a te 3 d a n d 4 d t r a n s i t io n m e t a l

d i ) o x i d e s , r e s p e c t i v e l y . R e l a t i o n b e t w e e n t h e o p e r a t i n g v o l t -

a g e s a n d t h e n u m b e r o f d = e l ec tr o n s c a n c l e a r l y b e s e e n .

d i ) o xi d e , a n d T i O 2 3 d / 3 d l ) < V O 2 3 d l / 3 d 2 )

< [ C r O 2 3 d 2 / 3 d 3 ) ] < M n O 2 I ) 3 d 3 / 3 d 4 ) _- Co O2 3dS /3 d 6 ) >- N iO2

3d6 /3dV) .

O f th e s e , m a n g a n e s e d i ) o x i d e s h o w s tw o le v e ls o f

o p e r a t i n g v o l ta g e s a t 3 a n d 4 V , d e n o t e d b y I ) a n d

I I ) . Th e d o t t ed cu rve i n F ig . 2 i s t he expec t ing range

fo r i ron d iox ide , whose reac t iv i t y i nc lud ing reve rsi -

b i l it y o f a r e a c t io n h a s n o t b e e n c o n f i r m e d y e t. T h e

curve fo r L iVO2 i s p i c tu red fo r t he ox ida t ion o f L iVO2

to Li2/ aVO2 no t a t opo tac t i c reac t ion ) [22 ] .

V 2 O s 3 d ) , N b 2 O s 4 d ) , M o O a 4 d ) , a n d

Li [ Li l /aTis/3 ] 04 3d ) are a lso sho wn in F ig . 2 . These

m a t e r i a l s to g e t h e r w i t h T iO 2 3 d ) h a v e n o c o n d u c -

t i on e l ec t rons i n a so l id ma t r ix , so t ha t t hey show

whi t e i n co lo r and in su l a t i ng e l ec tr i ca l p roper t i e s ex -

cep t V205 . In su l a to rs seem to be use l ess i n ba t t e r ie s .

H o w e v e r , t h e s e m a t e r i a l s c a n b e u s e d a s c a t h o d e m a -

t e r i a ls i n non aqu eou s l i t h ium ba t t e r i e s . E l ec t rons i n -

j ec t ed in to a so l id ma t r ix supp ly conduc t ion e l ec -

t r o n s w i t h a n a i d o f l a t ti c e v i b r a t i o n t h e r m a l

ene rgy) , so t ha t p a r t i a l l y reduced sam ples appea r b lue

i n c o l o r a n d h i g h l y c o n d u c t i v e . T h e s e m a t e r i a l s h a v e

t r a n s m i s s i o n l i n e s t h r o u g h o u t a m a t r i x i n t e r m s o f

l i t h iu m - i o n t r a n s p o r t a t i o n . T h e s e t w o f a c t o r s m a k e

the i n su l a t i ng ma te r i a l s u se i n recha rgeab le l i t h ium

bat ter ies .

In d iv id ing reac t ion 9 ) i n to fou r e lem en ta ry s t eps ,

we s imp ly desc r ibe a so l id s t a t e redox reac t ion as Eq .

11 ) . Ho wev er , t he o bse rva t ions desc r ibed a bove

s t rong ly sugges t t ha t a t heo ry to f i l l a gap be tween

e lec t rochem is t ry an d so l id s ta t e phys i cs is i nev i t ab ly

necessa ry i n deve lop ing so l id s t a t e e l ec t rochem is t ry ,

t h r o u g h w h i c h w e c a n c o u n t t h e p r o b l e m s a s t o t h e

co l l ec t i ve e l ec t rons ve rsus l oca l i zed e l ec t rons t o -

g e t h e r w i t h c o o p e r a t i v e J a h n - T e l l e r e f f e ct s a n d t h e

o n e - p h a s e v e r s u s tw o - p h a s e , a n d w i t h w h i c h w e c a n

p r e d i c t w h a t l e v el o f o p e r a t in g v o l ta g e a n d h o w m u c h

revers ib l e capac i ty a re expec t ab l e fo r t he t a rge t ing

m a t e r i a ls . T h e t r e a t m e n t d e s c r i b e d h e r e i s o v e rs i m -

p l i f ied , bu t ou r s im p l i f i ca t i on i s adeq ua te fo r a f i r s t

l o o k a t t h e o p e r a t i n g v o l ta g e s o f t h e i n s e r t i o n m a t e -

r i al s b a s e d o n t r a n s i t i o n m e t a l d i ) o x i d e s . A s c a n b e

seen in F ig . 2 , we can exp ec t ope ra t i ng vo l t ages f rom

0 .5 V to 4 .5 V fo r i n se r t i on ma te r i a l s o f t rans i t i on

m e t a l d i ) o x i d e s in n o n a q u e o u s l it h i u m b a t te r i e s.


8/11

2 8 T . Ohz uk u , A . Ue da / So l i d S t a t e l on i c s 69 1994 ) 201 - 211

5 . F a c t o r s a f f e c t i n g c a p a c i t y f a il u r e o f i n s e r t i o n

m a t e r i a l s i n r e c h a r g e a b l e b a t t e r i e s

R e c h a r g e a b l e c h a r a c t e r s o f i n s e r t i o n m a t e r i a l s a r e

a p p l i c a b l e t o a f u n c t i o n o f e i t h e r p o s i t i v e o r n e g a t i v e

e l e c t r o d e s f o r r e c h a r g e a b l e l i t h i u m b a t t e r i e s . H o w -

e v e r , m a t e r i a l s s h o w r e c h a r g e a b l e c h a r a c t e r s i s o n e

t h i n g , a n d m a t e r i a l s s h o w s u f f i c i e n t c a p a c i t y r e t e n -

t i o n fo r e x t e n d e d c y c l es i s a n o t h e r th i n g . O n e c a n

n o t t e ll c el l p e r f o r m a n c e i n a d v a n c e , e s p e c i a l ly c y c l e

l if e , o u t o f t h e b a s i c r e s e a rc h r e s u l ts u n l e s s p r o t o t y p e

c e l l s a r e f a b r i c a t e d a n d t e s t e d . I n t h i s s e c t i o n w e

b r i e f l y d i s c u s s t h e f a c t o r s a f f e c t i n g t h e c y c l e l i f e o f

t h e i n s e r ti o n m a t e r ia l s f ro m a f u n d a m e n t a l p o i n t o f

v i e w .

E l e c t r o c h e m i c a l c h a r g e a n d d i s c h a r g e i s u s u a l l y a c -

c o m p a n i e d b y t h e c h a n g e in l a tt ic e d i m e n s i o n s o f a

s o l id m a t r ix . W h e n r q M e O 2 is r e d u c e d i n n o n a q u e -

o u s l i t h i u m c e l ls , e l e c tr o n s a r e i n j e c t e d f r o m t h e o u t -

s i d e o f a s o l i d m a t r i x a n d l i t h i u m i o n s a r e i n s e r t e d

i n t o a s o l i d m a t r i x v i a a s o l i d / l i q u i d i n t e r fa c e i n o r -

d e r t o c o m p e n s a t e e x c e s s c h a r g e . T h e d e g r e e o f r e a c-

t i o n d i s t r i b u t e s l o c a l ly i n a s o l i d m a t r i x f r o m t h e s u r -

f a c e to t h e b u l k o f a m a t r i x . T h e l a t ti c e d i m e n s i o n s

a r e u s u a l l y a f u n c t i o n o f t h e d e g r e e o f r e a c t i o n

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[ 1 5 , 1 6 , 1 8 - 2 0 , 3 6 ] , s o t h a t s tr e s s i s i n d u c e d b y s t r a i n

d u e t o a d i m e n s i o n a l m i s m a t c h b e t w e e n r e g i o n s h a v -

i n g d i f fe r e n t d e g r e e o f r e a c t i o n . S t r e ss m a y b e p r o -

p o r t i o n a l t o t h e d i f f e r e n c e s i n b o t h l a t t i c e d i m e n -

s i o n s a n d t h e t h i c k n e s s o f a g r a d i en t r e g i o n i n t e r m s

o f t h e c o n c e n t r a t i o n s o f e l e c tr o n s a n d l i th i u m i o n s i n

a u n i t c e l l le v e l . W h e n l o c a l s tr e ss e x c e e d c e r t a in e l a s -

t i c l i m i t o f a m a t r i x , c r a c k a p p e a r s a n d g r o w s m e -

c h a n i c a l l y i n a c t u a l p a r t i c le s i n o r d e r t o r e le a s e s t r e s s

i n d u c e d b y t h e i n s e r t i o n r e a c t i o n . L a r g e r d i f f e r e n c e

i n d i m e n s i o n b e t w e e n u n r e a c t e d a n d r e a c t e d m a -

t r i x e s , i .e . , V q M e O 2 a n d L i M e O 2 , a n d s m a l l e r t h i c k -

n e s s o f t h e g r a d i e n t r e g i o n i n d u c e h i g h e r s t re s s i n t h e

r e g io n , w h o s e t h i ck n e s s d e p e n d s o n t h e c u r r en t a p -

p l i e d a n d t h e t r a n s f e r r a t e o f l i t h i u m i o n s i n a s o l i d

m a t r ix . T r a n s i t i o n m e t a l ( d i ) o x i d e c e r a m i cs a r e u s u -

a l l y fr a g il e, s o t h a t c r a s h i n g t o f i n e p o w d e r i s q u i t e

e a sy . T h e r e f or e , w h e n o n e o f th e l a t ti c e d i m e n s i o n s

c h a n g e s m o r e t h a n 1 5% d u r i n g a n i n s e r t i o n o r e x t r a c-

t i o n r e a c t i o n , i t i s a l m o s t i m p o s s i b l e t o s h o w t o p o -

t a c t i c r e a c t i o n s a n d t h e i r r e c h a r g e a b l e p r o p e r t i e s .

E m p i r i c a l a p p r o a c h s u g g e s t s t h a t m a x i m u m s t r a i n

a l l o w e d i n t h e o b s e r v a b l e t o p o t a c t i c r e a c t io n s i s a b o u t

1 2 /o a s c a n b e s e e n i n r - q R u O z / L i R u O 2 [ 2 0 ] a n d

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0 I mAl ' l .C3t

F i g . 3 . C h a r g e a n d d i s c h a r g e c u r v e s o f L i C o O 2 a n d L i N i O 2 a t a r at e o f 0 . 1 7 r n A . c m - 2 a t 3 0 C i n n o n a q u e o u s l i t h iu m c e ll s . E l ec t r o ly t e

u s e d w a s 1 M L i C 1 0 4 d i s s o l v e d i n p r o p y l e n e c a r b o n a t e . T h e c e l l s w e r e d i s c h a r g e d a t c o n s t a n t c u r r e n t t o 2 . 5 V a f t e r t h e c o n s t a n t c a p a c i t y

c h a r g e a t 1 0 0 1 2 5 o r 1 5 0 m A h . g - 1 b a s e d o n th e s a m p l e w e ig h t .


9/11

T. Ohzuku, A . Ueda / Sol id State lonics 69 1994) 201-2 11 209

L i M n 2 0 4 / L i 2 M n 2 0 4 [ 1 6 ] . H o w e v e r , r e c h a r g e a b l e

c a p a c i t y f a d e s r a p i d l y d u r i n g c y c l e s .

F i g . 3 s h o w s t h e c h a r g e a n d d i s c h a r g e c u r v e s o f

L i C o O 2 a n d L i N i O 2 h a v i n g l a y e r e d s t r u c t u r e s . T h e

s t r u c t u r e o f L i C o O 2 a n d a l s o L i N i O 2 h a s a s p a c e

g r o u p R 3 m i n w h i c h t r a n s i t i o n m e t a l i o n s a n d l i t h -

i u m i o n s a r e l o c a t e d a t o c t ah e d r a l 3 ( a ) a n d 3 ( b )

s i te s , r e s pec t ive ly , in a c ub ic c lo s e -packe d oxygen a r -

r a y . T h e u n i t c e l l d i m e n s i o n s o f L i C o O 2 a n d L i N i O 2

are u s ua l ly des c r ibed in hexagona l s e t t ing , i . e . ,

a = c a . 2 . 8 A a n d c = c a . 1 4 A . C h a n g e i n t h e c - ax is di -

m e n s i o n s o f th e s e m a t e r i a l s d u r i n g c h a r g e a n d d i s -

c h a r ge i s w i th i n 5 % d e p e n d i n g o n t h e d e p t h o f c h a rg e

[ 18 ,1 9 ]. L a y e r e d m a t e r i a l s m a y b e e a s y t o r e l e a s e i n -

t e r n a l s tr e s s i n d u c e d b y t h e i n s e r t i o n o r e x t r a c t i o n o f

l i t h iu m i o n s c o m p a r e d w i t h t h e m a t e r i a l s h a v in g o n e -

d i m e n s i o n a l t u n n e l s tr u c t u r e [ 3 6 - 3 8 ] o r t h re e - d i-

m e n s i o n a l f r a m e w o r k s t r u c t u r e [ 1 6 ] . C a p a c i t y l o s s

d u r i n g c y c l e s i s i n e v i t a b l e d u e t o t h e f r a c t u r e o f a n

ac t ive s o l id ma t r ix U n les s s t r a in i s ze ro , s uch tha t th e

l a t t i c e d i m e n s i o n s d o n o t c h a n g e d u r i n g c h a r g e a n d

d i s c h ar g e . A c a r e f u l p r e p a r a t i o n o f t h e e l e c t r o d e s a n d

a p p l i c a t i o n o f p re s s u r e o n t o t h e e l e c t r o d e s , c a l l e d a

b o b b i n p r e s s u r e i n o u r l a b o r a t o r y , a r e n e c e s s a r y t o

m i n i m i z e t h e c a p a c i t y lo s s a n d e x t e n d c y c l e l if e . S u c h

a m e c h a n i c a l f a c t o r w il l b e r e d u c e d b y a p p l y i n g c e -

r a m i c s t e c h n i q u e s i n c l u d i n g p o w d e r o r t h i n - l a y e r

t e c h n o l o g y [ 3 9 - 4 1 ] i n m a t e r i a l s s c i e n c e in p r e p a r -

i n g t h e i n s e r t i o n m a t e r i a l s a n d p r o c e s s i n g t h e

e lec t rodes .

Zero - s t r a in in s e r t ion ma te r i a l s a r e pe rhaps idea l f o r

the long - l i f e r echa rgeab le ba t t e r i e s . F ig . 4 s how s the

c h a r g e a n d d i s c h a r g e c u r v e s o f L i [ L i l /3 T i 5 /3 ] 0 4 t o -

g e t h e r w i t h L i N i O 2 . T h e c r y s t a l s t r u c t u r e o f

L i [ L i l / 3 T i s / 3 ] O 4 i s a c u b i c h a v i n g a s p a c e g r o u p

F d 3 m [ 4 2 ] i n w h i c h l i t h i u m i o n s a r e l o c a t e d a t o c -

t a h e d r a l 1 6 ( c ) s i te s w i t h o c c u p a n c y 1 / 2 o r a t te t r a -

h e d r a l 8 ( a ) s it e s, l i th i u m i o n s a n d t e t r a v a l e n t t it a -

n i u m i o n s a r e s t a t i s t i c a l l y d i s t r i b u t e d a t o c t a h e d r a l

1 6 ( d ) s i te s b y t h e r a t i o L i / T i = 1 5 , a n d o x y g e n io n s

a r e l o c a t e d a t 3 2 ( e ) s i te s w i t h a p o s i t i o n a l p a r a m e t e r

0 .26_2 [ 12 ] . T he r eac t ion un dergo es w i th one -e lec -

t r o n t r a n s f e r p e r a f o r m u l a u n i t , i . e .,

L i [ L il /3 T i s/ 3 ] 0 4 + L i + e -

16 c) 16 d) 32 e)

L i , [ L i l / 3 T i s / 3 ] 0 4 ( 1 3 )

16 ) 16 d) 32 e)

5.0

z..0

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5 0 1 0 0 1 5 0 2 0 0

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Fig. 4. C harge and d ischarge curves of (a) LiNiO2 and (b)

Li [ Lit/3Ti5/3 0 4 at a rate o f 0; 17 mA .em -2 at 30 C n nonaqu e-

ous lithium cells. Li[Lim/3Tis/3]O4 s a zero-strain nsertion ma-

terial, so that loss of reehargeablecapacity cannot be seen even

after 50 cycles.The combinationof LiNiO2 and Li[Lil/3Tis/3]O4

gives a lithium-ion (shuttlecock) battery showing about 2 V of

opera ting voltage.

T h e o r e t i c a l c a p a c i t y is c a l c u l a t e d t o b e 1 75 m A h . g - 1

o r 0 . 61 A h . c m - 3 f o r L i [ L i l / 3 T i s / 3 ] O 4 . I t s h o u l d b e

n o t e d t h a t t h e r e d u c t i o n p r o d u c t L i2 [ L i l /3 T i s / 3 ] 0 4

h a s s t il l t e t r a v a l e n t t i t a n i u m i o n s t o b e a b l e t o a c c e p t

e l e c t r o n s , b u t n o v a c a n t o e t a h e d r a l s i t e s . A c c o r d -

i n g ly , t h e c a p a c i t y o f L i [ L i t / 3 T i s / 3 ] 0 4 i s l i m i t e d b y

t h e n u m b e r o f a v a i l a b l e o c t a h e d r a l s it e s t o a c c o m -

m o d a t e l i t h i u m i o n s , c a l l e d l i t h i u m - i o n s i t e - l i m i t e d

capa c i ty [ 9 ] .

T h e l a t ti c e d i m e n s i o n a = 8 . 3 6 5 ~ i s i n v a r ia b l e

d u r i n g c h a r g e a n d d i s c h a r g e in t h e r a n g e b e t w e e n 1 .2

V a n d 3 .5 V [ 2 2 ]. S i n c e t h e r e a c t i o n i s o f z e r o - s t ra i n

i n s e r t i o n a n d e x t r a c t i o n o f c h a r g e d s p e c i e s, c a p a c i t y

l o ss c a n n o t b e s e e n e v e n a f t e r 5 0 c y c l e s. T h e o p e r a t -

ing vo l tage i s ju s t abov e 1 .5 V aga ins t a l i t h ium meta l .

T h e c o m b i n a t i o n o f L i N i O 2 a n d L i [ L i~ /3 T i5 /3 ] O 4 i n

F ig . 4 g i v e s a l i t h i u m - i o n ( s h u t t l e c o c k ) b a t t e r y h a v -

i n g a b o u t 2 V o f o p e r a t i n g v o l t a g e , w h i c h d o e s n o t

c o n t a i n m e t a l l i c l i t h i u m . L i N i O 2 c a n b e r e p l a c e d b y

L i C o O 2 [ 4 3 ] , L i N i l / 2 C o l / 2 0 2 [ 1 8 , 4 4 ] , L i M n 2 0 4

[ 1 6 ,4 0 ,4 1 ] , o r L i M n O 2 [ 2 3 ] , a n d L i [ L i l / 3 T i s / 3 ] O 4

i s a l s o s u b s t i t u t e d b y N b 2 0 5 [ 4 5 ] , p e t r o l e u m c o k e ,

o r n a t u r a l g r a p h i t e [ 8 , 4 6 ] . T o s e l e c t t h e i n s e r t i o n

m a t e r ia l s , m a i n l y t r a n si t i o n m e t a l ( d i ) o x i d e s , o n e

c a n d e s i g n t h e o p e r a t i n g v o l t a g e e f f e c t i v e ly a p p l i e d

t o t h e e l e c t r o n i c d e v i c e s.

T h e r e s u l t o f a z e r o - s t r a i n i n s e r t i o n m a t e r i a l i n d i -


10/11

210

T . Oh z u k u , A . Ue d a / S o l id S ta t e lo n ic s 6 9 1 9 9 4 ) 2 0 1 -2 1 1

c a t es th e v a l i d i t y o f a r g u m e n t s d e s c r i b e d a b o v e a n d

t h e p o s s i b i l i t y t o r e d u c e o r e r a s e m e c h a n i c a l f r a c t u re

o f t h e i n s e r t i o n m a t e r i a ls .

A i d f o r S c i e n t if i c R e s e a r c h f r o m t h e M i n i s t r y o f E d -

u c a t i o n , S c i e n c e a n d C u l t u r e , J a p a n .

6 . C o n c l u d i n g re m a r k s

I n t h is p a p e r w e h a v e d e s c r i b e d w h y t r a n s i t io n

m e t a l d i ) o x i d e s a r e t h e m o s t a t t r a c t iv e m a t e r i a l s f o r

b a t t e r i e s i n t e r m s o f h i s t o r i c a l b a c k g r o u n d , v o l u m e t -

r i c c a p a c it y , o p e r a t i n g v o l t a g e , a n d a v a i l a b i l i t y o f

m a t e r i a l s . I n d i s c u s s i n g s e v e r a l a s p e c ts o f t h e i n s e r -

t i o n m a t e r i a ls w e u s e d m o s t l y o u r o w n w o r k s . H o w -

e v e r , t h r o u g h o u t o u r t h e o r e t i c a l a n d e x p e r i m e n t a l

w o r k s w e o w e a l o t t o o t h e r w o r k e r s t h r o u g h l i te r a -

t u r e o v e r g e n e r a t i o n a n d a l l a r e w o r t h a c r e d i t . A l -

t h o u g h w e h a v e n o t s t a t e d c a p a c i t y f ai l u r e d u e t o

e l e c t ro l y t e d e c o m p o s i t i o n , o x i d a t i o n a n d a l s o r e d u c -

t i o n r e s i s t a n t a n d h i g h l y c o n d u c t i v e e l e c t ro l y t e s a r e

i n e v i t a b l y n e c e s s a r y i n o r d e r t o d e v e l o p t h e a d -

v a n c e d b a t t e r i e s . R e c e n t p r o g r e s s o n t h e m a t e r i a l s fo r

a d v a n c e d b a t t e r i e s r e q u i r e s a s t a b l e e l e c t r o ly t e in t h e

v o l t a g e r a n g e o f a t l e a s t 0 - 5 V a g a i n s t a m e t a l l i c l it h -

i u m e l e c t r o d e . E l e c t r o l y t e i s n o t ~ n e c e s s a r i ly b a s e d o n

o r g a n i c s o l v e n t s w h o s e h e a t o f c o m b u s t i o n i s a l w a y s

e x o t h e r m i c . I n o r g a n i c s o l v e n t s o r l i t h i u m - i o n c o n -

d u c t i v e s o l i d e l e c tr o ly t e s, h o p e f u l l y l i t h i u m - m e t a l -

o x y g e n s y s t em , m a y b e a p o s s i b l e r e p l a c e m e n t f o r t h e

p r e s e n t e l e c t ro l y t e , w i t h w h i c h w e m a y e x p e c t h i g h

v o l t a g e w i n d o w 0 - 5 V v e r s u s L i ) a n d s a f e ty o p e r a -

t i o n e v e n f o r th e h i g h - v o l u m e r e c h a r g e a b l e b a tt e r i es .

C o o p e r a t i v e r e s e a rc h e s a m o n g e l e c t r o c h e m i s t s , o r -

g a n i c a n d i n o r g a n i c c h e m i s t s , m a t e r i a l s c i en t i st s , a n d

a p p l i e d p h y s i c i s t s a r e e x t r e m e l y i m p o r t a n t t o d e -

v e l o p t h e b a t t e r y m a t e r i a l s . S u c h i n t e r d i s c i p l i n a r y

r e s e a r c h e s w i l l p r o v i d e a n e w f i e l d i n m a t e r i a l s s c i -

e n c e fo r a d v a n c e d b a t t e ri e s . T h e p r e s e n t a u t h o r s h o p e

t h a t f u n d a m e n t a l a n d a p p l i e d r e s e a r c h e s w i l l g r o w

t h r o u g h t h e s t u d i e s o u t l i n e d h e r e i n i n t h e n e a r f u t u re .

A c k n o w l e d g e m e n t s

O n e o f u s T . O ) w i s h e s t o t h a n k D r . T a k e ts u g u

H i r a i , P r o fe s s o r E m e r i t u s f r o m O s a k a C i t y U n i v e r -

s i t y , f o r h i s s u g g e s t io n s t h r o u g h o u t t h e r e s e a r c h . T h e

p r e s e n t w o r k w a s p a r t i a l ly s u p p o r t e d b y a G r a n t - i n -

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artigo why transition metal (di)oxides are the most attractive materials for batteries

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