Solid State lort]cs 5 (1981) 375 378

North-Holla:ad PublishingCompany

Li2FeS2, A CATHODIC MATERIAL FOR LITHIUM SECONDARY BATTERY

A. Dugast x, R. Brec ;~, G. Ouvrard ~ and J. Rouxel ~

~ L a b o r a t o i r e de Chimie des Soil des - Facult6 des Sciences

2, rue de la Houssini6re - 44072 Nantes C 6 ~ x , France
~R~kaboratoires de M a r c o u s s i s - Route de Nozay - 91460 M a r c o u s s i s , France
In Li 2 F e S 2 ( ~ ) , l i t h i u m can be removed either- c h e m i c a l l y or e l e c t r o c h e m i c a l l y t o
o b t a i n non s t o i c h i o m e t r i c Li x FeS2 phases (0 < x 4 2). R e - i n t e r c a l a t i o n o f l i t h i u m
in the s t r u c t u r e a l l o w s t o use [he o x i d i z e d Li~FeS2 m a t e r i a l as p o s i t i v e in a non
aqueous e l e c t r o l y t e l i t h i u m cel , X-Ray analys~s and open c i r c u i t v o l t a g e curves
versus l i t h i u m c o n c e n t r a t i o n of: Li x FeS 9 samples i n d i c a t e the occurence o f t h r e e
d i f f e r e n t phases in the 0 < x d 2 eomposTtion range, Good c y c l i n g p r o p e r t i e s o f the
LixFeS 2 p o s i t i v e are observed in the hole composition range used (0,25< x< 1,~),

1. INTRODUCTION TABLE

Many c a t h o d i c materials have been used Compounds I,S, - a E/2 Q.S.

in non aqueous e l e c t r o l y t e lithium cells in mm/s mm/s
the l a s t ten years. These compounds are layered
dichalco9enides (1-4), ternary sulfides (5, L i2 FeS2(a ) 0.50 0.31
6), layered chalcogenophosphates ( 7 - 9 ) , o x i h a - 0.49 0,73
Iogenides (10,11) or o x i d e s (12) o f t r a n s i t i o n
elements. A l l these compounds are o x i d i z i n g Li~ reSz(T ) 0.3S 0.69
phases which are reduced by l i t h i u m d u r i n 9 0.4S 0.41
an i n t e r c a l a t i o n process.
L i0.14 FeS2 0.30 0.34
As i t is the case l'or VS2 (4), layered FeS2 0.34 0.38
c a n n o t be o b t a i n e d from d i r e c t s y n t h e s i s , whe-
r e a s i t s l i t h i a t e d d e r i v a t i v e Li 2 F e S 2 ( a ) can L iFeS2(~) 0.40 O.70
e a s i l y be made (13). A f t e r p a r t i a l or f u l l
l i t h i u m d e s i n t e r c a l a t i o n , LixFeS 2 ( O < x < 2 ) p h a -
IS : r e s p e c t i v e t o Fe at 300 K
s e s can be used as p o s i t i v e s in s e c o n d a r y non
aqueous e l e c t r o l y t e l i t h i u m c e l l s . Such p r e l i -
minary desintercalations were carried out from MSssbauer s p e c t r a o f Li B FeS2(a) present (Table
Li 2FeS2 e i t h e r in a b a t t e r y L i 2 F e S 2 / D i o x o l a n e I) (15) two o v e r l a p p i n g quadrupole d o u b l e t s
(LICIO 4 2M)/Li or by means o f an o x i d i z i n g corresponding t o two d i s t i n c t ion s i t e s . The
agent l i k e iodine in a c e t o n i t r i l e , This l i t h i u m isomer s h i f t (IS) observed is c o n s i s t e n t with
removal leads t o non s t o i c h i o m e t r l c LixFeS 2 sam- Fe2+high s p i n ions in an octahedral s u l f u r e n v i -
p i e s . We present in t h i s a r t i c l e some data ronment.
about the p r o p e r t i e s of the above secondary
c e l l and about the LixFeS 2 phases. At room temperature, o x i d a t i o n o f LioFeS2(a) by
aeetonitrile iodine s o l u t i o n s according t o t h e
2. RESULTS AND DISCUSSION reaction

L i 2 F e S 2 ( a ) is t h e s t a r t i n g m a t e r i a l from which Li 2FeS 2 + x / 2 I 2 ~ xLil + Li2_ xFeS 2

a l l t h e LixFeS 2 samples were o b t a i n e d by o x i d a -
t i o n . It was s y n t h e s i z e d by h e a t i n g , a t S50C
For two weeks, s t o i c h i o m e t r i e p r o p o r t i o n s of
Li 2 S and FeS. The powder samples were placed
in v i t r o u s carbon tubes c o n t a i n e d in evacuated
silica tubes.
X Ray a n a l y s i s performed on s i n g l e c r y s t a l
i n d i c a t e t h a t Li2FeS2(G) p r e s e n t s an hexagonal
~ a t t i c e with a 10 x 3 . 9 0 8 ( 2 ) ~ and c - 6 . 2 7 9 ( 4 )
A (14). From the values of these parameters,
i t may be assumed t h a t t h e s t r u c t u r e d e r i v e s
From a Cdl 2 l i k e s t r u c t u r e , t h e l i t h i u m ions
o r d e r i n g between or w i t h i n the FeS2 l a y e r s ,
and bein 9 r e s p o n s i b l e For the observed super-
structure.
allows to prepare samples oF various lithium
concentration in the 0 < x < 2 range. Little modi-
Fication on the crystal parameters is observed
upon lithium desintercaletion. However, the
parameters and c e l l volume v a r i a t i o n s versus
l i t h i u m c o n t e n t a l l o w t o d i s t i n g u i s h two domains
The f i r s t one corresponds t o 1.09< x < 2, w i t h
the occurence o f e s i n g l e t y p e of spectrum which
can be indexed From t h e p~rameters o f t h e sub-
c e l l o f Li 2 FeS 2 (a ~ 3.9 A and e = 6.2 A). The
second one appears t o be a biphased r e g i o n c o r -
responding t o Lix=l.O9FeS2 and L i ~ o F e S 2, T h e ~
mer compound opresents t h e h%xagonel paromet#rs
a = 3.877(2) A, e = 6.222(7) A and V = 80.99 A3.
For Lix=oFeS 2 on hexagonal c e l l can be a l s o

0 167-2738/81/0000-0000/$02.75 North-Holland Publishing Company

376 A. Dugast et al. / Li2FeS 2

used ~o index t h e pow&ter s p e c t r u m , w l t h d g 1.4g6 s t u d y made under q u a s i e q u i l i b r i u m p o t e n t i a l

(2) A, c = 5 . 8 3 ( 1 ) A and V = 6 1 . 4 ( 6 ) ~S, b u t around t h i s r'eqior~ on two b u t t o n - t y p e b a t t e l i t s
d much b e t t e r agreement is Peached {'ram a mona 7 does not show art', p l a t e a u ("i.qur'e 2),
cl i n i c c e l l ~itt~ a = 6 . 0 4 4 ( 2 ) ~, b = 3.4S2(2)~k
c = 5 925(4) ~ , ~ = 9 1 . 2 5 ( 5 ) and V = 2x62..~5(5)~ 4. The L i x F e S ' 2 s)stem pro~ed rather" complex, ~ i t h
at l e a s t t h r e e phases ira the O< -,4 '2 i n t e , ' ~ a l .
They dr," : a l i t h i u m r i c h compound LixFeS 2 (c)
with 1.~1 < x .< 2, d Li x FeS2 (~) phase c o r r e s p o n -
E(volt) d i n g t o liO()`< \ < l , 5 and a hi.qhl) o x i d i : e d phase
kixgeS 2 I x ) ~ i t h x < C . 0 2 .
k
2,5
I",,l
2.0 E(volt)
[~i]
I P

l
1.5

"i\f
i
I I i i 2.
0 0,5 1.0 1,5 2.0 x in Lix FeS2

Figure I : Quasi equi I i b r rum p o t e n t i a l o f tire

LixFeS 2 system (0 < x < 2) o b t a i n e d
|ram chemical ly o , i di zed sampl as.
t5[ o.,5 1.,s 2:o_
The above r e s u l t s about the domains observed x in LixFeS 2
From c h e m i c a l l y oxidized samples and t h e i r
X Ray a n a l y s i s ape c o n s i s t e n t w i t h the ctuasi
equ i I i bp ium e I ectrochem i ca I o x i d o r e d u c t i on study. F i g u r e ,~ : F i r s t quasi equilibrium p o t e n t i a l c ~ c l e
S t a r t i n g from Li 1 lRFeSo and Li~ laFeS? samples v e r s u s x in LixFeS, ? o b t a i n e d From
resu It i n9 t rum them i ca I o N ~d a t I on ~y Iod ine Lio.14FeS 2 (B) a n d - L i o F e S , ) ( a ) ( * ) .
in a c e t o n i t r i l e , we have o b t a i n e d two i d e n t i c a l
open c i r c u i t v o l t a g e c u r v e s v e r s u s x in LixFeSo
One quasi e q u i l i b r i u m p o t e n t i a l c y c l e has been
( f i g u r e 1 ) . Tile two p r e v i o u s l y d e t e c t e d domains
a r e found, but in ttae 1 . 0 9 < x < 2 c o m p o s i t i o n pet" f:ermed front ahem i r a I ( y o b t a i n e d L i O. 14 FeS'~
sample ( f i g u r e .~). The o x i d a t i o n cur ve s i t u a t e d
ranDe , a sharp drop o f 0.1~ v o l t is r e c o r d e d
a r o u n d 0 . 2 v o l t above t h e r e d u c t i o n one c o r r e s -
For x ~ 1.5. T h i s can be a t t r i b u t e d t o a change
in t h e c a r r i e r s i n t e r a c t i o n s with the setting ponds t o a small h y s t e r e s i s phenomenon, Whereas
t h e b r e a k in t h e cur ve tier x ~ 1 is a g a i n Found,
o f a long o r s h o r t d i s t a n c e o r d e r riot d e t e c t e d
t h e p o t e n t i a I change t:Ol" X ~ l I g i S l]()t ()[~S{} I " V('{{
on t i l e c e l l p a r a m e t e r s of- t h e [_ix FeS2 phases.
durin 9 the oxidation process.
T h i s phase t r a n s i t i o n impl ies the occurence,
a r o u n d t h e c o m p o s i t i o n L i l i s F e S 2 , o f a narrow
biphased region. A d e t a i led e l e c t r o c h e m i c a l On t h e same t ' i g u r e , we h a \ e r e p o r t e d the o x i d e -
r e d u c t i o n e q u i l i b r i u m c u r v e v e r s u s x in LixFeS,,
o b t a i ned From t h e s t a r t i tag Li2 Fe?/~ (a) nlater i a-I .
E (volt) T h i s t i m c , the shape o f t h e cur~e is q u i t e d i l -
2.5 l ' t r e n t o f t h a t obser ved p r e v i o u s l y From chemi-
cal ly oxi di zed samples. AIthough b r e a k s i n t h e
cur~e a r e found a t x ~ 1 a n d x ~ 1 , ~ , they do
not s e p a r a t e t h e same k i n d o f domains. Moreover
the surface of the cycle indicates a reorganisa-
t ion ener9y much b i g g e r when the s t a r t i n g mate-
rial is L i 2 F e ~ ( a ) than when i t is e i t h e l " t h e
chemical Ix o x i d i z e d Li O14FeS2 or Lil.1)FeS2O~a.~,s.
Thi s would t e n d t o pr[~'ve t h a t a chem'ica I o x i d a -
t i o n st~ould 9 i r e b e t t e r r e v e r s i b i l i t y Clual i t i e s
t o the Li x FeS2 m a t e r i a l as c o n f i r m e d b> k i n e t i c
studies (16).
!.5
1~1 1.,3 1.,5 17 P
K i n e t i c work h a s been p e r f o r m e d by , : y c l i n g ,
f o r example, from t h e c h e m i c a l l y o x i d i z e d sample
x in LixFeS 2
Li 0 ldFeS,~ in t h e t h r e e f o l l o w i n g c o m p o s i t i o n
F i g u r e 2 : Quasi e q u i l i b r i u m p o t e n t i a l study r a n g e 0 ~5 4 \ 4 0 . $ 5 , 0 7.< x.< 1.3 and 12,< x4 1..~.
around the c o m p o s i t i o n L i l . 5 F e S 2 The c u r r e n t d e n s i t y was '2 mA.em- g , t h e i n i t i a l
 A. Dugast et al. / Li2I~'S 2 377

sample being s l o w l y brought e l e c t r o c h e m i c a l l y

t o the lower l i t h i u m c o n c e n t r a t i o n o f the chosen
domain o f c y c l i n g . E (volt) from Li14FeS2
m =62 mg/cm2
from Li14FeS 2 (13.3 mAh/Li )
20:3',0 i= 2 mA/cm 2
E (volt) m = 62 mg'/cm 2 40~.- .~. "'.~.
(13.3 mAh/Li)
2.5 ,~ " . --~. \
i = 2 mA/cm 2

"-f:-.._._ ,, ~ *,%
2.5 ~ c l e 5 ~'~. \ ~,~
"~-<~. ~ " - . \
" .~T~.-.. ~ ~

"'%.: .. \ \

;~,, "x,,'\20
",',
zo \ . . 40 N "%.'.
~,.,~""" ~...~. ~ .

1,2 1,4 1.6 1.8

I I i I ID
0.2 0.4 0.6 0.8
I I I I -- X in L i x F e S 2
XinLixFeS 2
Figure 4c : Vat i at ion of" t h e p o t e n t i a I under a
c u r r e n t d e n s i t y o f 2mA,cm-2 up t o 40
c y c l e s in the L i l . g F e q g - L i l . g F e S 2
Figure 4a : V a r i a t i o n of t h e p o t e n t i a l under a interval .
c u r r e n t d e n s i t y o f 2mA,cm- 2 up o 40
c y c l e s in the ki~ o~geS,.-ki . . . . FeS,~ The charge and discharge curves up t o Forty
interval, u.=3 4 u.3b
cyc I e s a r e r e p r e s e n t e d on F i g u r e s qta, 4b, and
4 c . The ohmic [:a ] [ c o r r e s p o n d s e s s e n t i a I ly t o
the e l e c t r o l y t e rest stance and is Found t o be
E (volt) from Li.14FeS 2 equal t o 160 mY.
m = 62 mg/cm 2
(13.3 mAh/Li )
i= 2 mA/cm 2 O(voft) from Li.14FeS 2 i= 2 mA.cm -2
-~':~:~'~..~ .
2.51
2.5
~'charge

",,::\% 2.0
~'. -',- \. "%,.
N4~ ,.:\3\
discharge
1.5 =X
0'.5 1: 1;s 2. -

1.5
11 RI ":-,.',,~,,12
",~ "-20
Figure ~ : P o t e n t i a l v l e l d o f t h e secondary b a t -
t e r y versus c y c l i n g domain.
"':',"30
'40 Tile e f f i c i e n c y o__F ehe c y c l i n g can be s_tuKied
0;7 019 111 113 = by d r a w i n g b o t h Ud ~ f ( x ) , tic = F(x) and Ud/!]c =
f ( x ) where lid and Uc a r e h a l f - c h a r g e and h a l f -
X in L i x F e S 2 discharge potentials, x being the lithium con-
t e n t , F i g u r e s ~ and 6 show t h a t t h e e n e r g y y i e l d
Figure 4b : V a r i a t i o n o f t h e p o t e n t i a l under a loss is constant throughout the composition
c u r r e n t d e n s i t y of 2mA.cm- 2 up t o 40 r a n g e , w h e r e a s t h e a v a i l a b l e power is s l i g h t l y
h i g h e r when t h e s e c o n d a r y b a t t e r y o p e r a t e s around
c y c l e s in the Lio.7oFeS2-Lil.3oFeS 2 the LilFeS 2 composition.
interval.
378 A. Dugast et al ,I Li)FeS)

[71 t e Mehacltd, A., 0 u v r a r d , g . , Brec, R. and

~d Rouxel, ,I., Mar. Res. B u l l . 12 (1077) IlC)l -
Uc I 107.
,.o! from Li.14Fe S2 i = 2 m A , cm"2 !~] Brae, R., S c h i e i c h , p.M., l o u i s y , A. and
Rouxel, ,I., Aim. Chim. Fi'..~ (107n~ ;~47-2~Z.
[0] Brec, R., Schleicl~, D.M., Ou~,-ard, G.,Loui~:,,
0.9.
A. and Rouxel, ,I., Inorg. Chem. IX (I070)
I<14-1ql~.
0.8, [lO]Armand, M., CoTe, I . , Pal~adeau, P. and
Rouxel, ,I., ,I. Power Sources ,~ ( l q 7 ~:) I.]7-144.
0.7, r l l j V 6 n i e n , ,I.P., Palvadeau, P., S c h l e i c h , P.M.
and Rouxel, ,I., Mat. Rc,s. B u l l . 14 (1070)
0.6 ~,01-x,07,
[12]Mur,phy, D.W., ('hris~iar;, P.A., I"i S a l \ o , .I.F.
,Jtv.{ Carides, ,I.N., ,I. Elecfrochvm, Sou. IL'U
0.'s i. 1.'5 7. ( lq70).
[l~]Sharnk~, R.A., ,I. Clecrt~ochem. Sot'. IZI~(I~t7U)
F i guPe 6 : Moan charge and d i scharge p o t e n t ia I s 44 ~-S4.
versus cycl in 9 domains. [14]Brec, R., Dugasf, A. and Le Mc,hautd,,A., Mat.
l?,es. B u l I I 15 (IO'KO) 610-62S.
MossbatieP s p e c t r a on some chemical l~ d e s i n t e n - [IS]MeI~'ndres, C.A. and lani, B., ,I. Phys. Ohm'm.
c a l a t e d LiFeS 2 samples (0,14 < ' . ~ 2) were vocal'- x2 (IQ7X) 2XSO - 2~$2.
dad al; room tomper'atur'e. Both L i 2[e S0( ~ ) ( 1 ~) <lid [lO]Dugast, A., Ing. Ihoct. l h e s i s , Nantes I l n i x .
LilFeS,~ (~) present t~o o ~ e r l a p p i n g quadrupole IApri I lC)~l ).
double~s c o r r e s p o n d i n g t o t~,o d i s t i n c t iron [ 1 7 ] T a i ' t , k'.A., na Cuhna, S . F . , IX, Souza, N.G.and
s i t e s (see t a b l e 1 For isomeP strife (l.S.) and Ftlt-tad,,,,N.C., ,], Phys. Chem. S o l i d s 41 (I*Y'O,~
quadi"upole spl i t t i n 9 (Q.S) v a l u e s ) . These r e s u l t s 01-62.
ape o be compared w i t h the Mossbauer c-haract;e-
ristics of LiFoS 2 ( 6 ) (177 obt-ained by high
t e m p e P a t unct d i r e c t synt has i s J'rom a mi x t tlPe
o f Li .~ S, PeS'2 and FoS One o f the s i t e in ACI~OW%EDG]9~t:N]
LilFeS.7 (~) t,as IS and OS s i m i l a r ' t o tile unique
d e t e c t e d iron s i t e of" t h e LiFeS 2 ( 6 ) compotsnd. We t h a n k tile D. R, E. T. For f i n a n c i a l support
The l i t h i u m ~x'*~l'sample Li 0 14feS,~ has a l s o two
quadrupole d o u b l e t s , b u t "lowor-OS and IS, The
lower IS i n d i c a t e s a change d e n s i t ~ at the nti-
c l e u s hi.qher t-hart tt~at in L i l P e S 2 ( 7 ) .

3. CONCLIISION

The L ixFeS9 systenl shows a I'athei" complex beha-

viotlr with-the occurenc'e of various phase t r a n -
s if- ions. The FeS 2 s~ructul-aI Erame, which i s
l ' e t a i rlc'd throu9t~out the compos i t i on Pange
0 < \ 4 2 , is oF t h e Cdl 2 type,. The LixPeS 2 s y s t e m
I~ehavc's I ikc' a good secondapv p o s i t i v e e l e c t r o d e
~,it-h a c'apac:if~ o f ~50 Ah.k9 -1 and a slo~, aginct
over cycl in/g, M6ssbauer a n a l y s i s indicat,., an
inci'ease a t t-he iron charge f o r deereasin,q l i -
thium c o n t e n t in fhe LixFoS 2 sampl~,s.

REFERENCES

[I] Oaine~, L.H., Francis, R.W., Newman, O.H.and

Rao, B.M,L., Int-ersoc. Energy Con~ers. Enq,
t o n i ' . 11 (1076) 41~,-423".
[1!] Winn, D,A., Shemi I% .I.M. and S t e e l e , B.C.H.,
Mat. Res. B u l l . I1 (1976) S5c)-566,
[,'~] Whiti-itxqham, M.S,, S c i e n c e 102 (1076) 1 1 2 6 -
1127.
[~] Munphy, D.W., C a r i d e s , J . N . , Di Salvo, P.,I.,
Ores, C. and Waszczak, ,J.V., Mat. Res. tRull.
12 (lO77) g2S - x30.
[ ~) ,laeot~son, A,,I. and Mac Candl ish, L . E . , .I.So-
lid S t a t e Cheln, 20 (1979) 3 5 5 - 365.
[(/] ,Jat'obsol~ A..I., Whittingham, Mi S i and Rich,
S.M., ,I. Electrochem. Soc. 126 (1079)SR7-~ql.