investigation of thionyl chloride decomposition and open-circuit potential in lithium-thionyl...

2 7 9 4 J. Electrochem. Soc., Vo l . 136, No . 10, O c t o b e r 1 9 8 9 �9 The Electrochemical Society, Inc.

Chemis t ry ," Vol. I, p. 358, G. Brauer, Editor, Aca- demic Press, N e w York (1963).

14. B. R. Karas, This Journal, 132, 1261 (1985). 15. R. F. Bacon and R. Fanelli , J. Am. Chem. Soc., 65, 639

(1943).

16. M. P. J. Brennan , Electrochim. Acta, 24, 529 (1979). 17. D. S. Park and D. Chatterji , Thin Solid Films, 83, 429

(1981). 18. N. K. Gup ta and R. P. Tischer, This Journal, 119, 1033

(1972).

Investigation of Thionyl Chloride Decomposition and Open- Circuit Potential in Lithium-Thionyl Chloride Cells

Jean Boyd Bailey* Eveready Battery Company, Incorporated, Westlake, Ohio 44145

A B S T R A C T

The open-c i rcui t potent ia l of l i th ium-th ionyl ch lor ide cells increases as cells age and as s torage t empera tu re increases. The cell e lec t ro lyte was s tudied us ing gas ch roma tog raphy and gas ch romatography-mass spect roscopy. It was demon- s t ra ted that sulfur monochlor ide , $2C12, and sulfur dioxide, SO2, are genera ted in und i scha rged cells. S ince Li-S2C12 has a h igher potent ia l than Li-SOC12 the increase in potent ia l can be accoun ted for by the in situ genera t ion of $2C12. A small s teady-state concen t ra t ion of SzC12 was measu red in a d ischarg ing cell. No ev idence of SC12 was found.

The potent ia l or open-circui t voltage, OCV, of undischarged Li-SOC12 cells increases as cells age. The vol tage is 3.64V one day after manufacture . I f the cells are s tored at ambien t t empera tu re the OCV increases to 3.68V over the first six weeks. I f fresh cells are s tored at 71~ the OCV increases to 3.76 over six months . The changes observed in OCV wi th cell age at these s torage t empera tu res are shown in Fig. 1. The purpose of this s tudy is to inves t igate the cause of the OCV increase. This has been accompl i shed by de te rmin ing the compos i t ion of the e lec t ro lyte inside cells as a func t ion of cell age and s torage tempera ture . Sea led glass ampuls of the e lec t ro lyte were also prepared and s tudied as a control exper iment . Gas chromatography , GC, and GC-mass spectroscopy, GC-MS, were used for posi t ive ident if icat ion of all the compounds . The compos i t ion of the e lec t ro lyte as a funct ion of dep th of d ischarge was also studied.

Experimental High pur i ty 1.5M LiA1C14-SOC12 was p repared by re-

f luxing A1C13 (Fluka, puriss, grade) and LiC1 (Alpha, an- hydrous ul t rapure) in SOC12 (Mobay, 99.6%) wi th 5% ex- cess LiC1 to insure neutra l izat ion of the A1CI~. The mois tu re con ten t was verif ied by measu r ing the infrared absorbance in a 1 cm path length quar tz cell on a Perkin- E lmer 1320 infrared spec t rophotometer . There was no absorbance at 3360 cm -1 f rom the a l u m i n u m hyd roxy species and the HC1 absorbance at 2750 cm -1 was 0.038 (<5 ppm). This batch o f e lec t ro lyte was the s tar t ing mater ia l for each e x p e r i m e n t descr ibed in this paper.

Smal l cyl indrical 1.3 Ah bobb in cells wi th a ball and bush ing ven t cons t ruc t ion were used in the study. These cells were previous ly descr ibed by J o h n s o n et al. (1). To avoid mois tu re con tamina t ion dur ing e lec t ro lyte analysis, the cells were opened inside an argon filled dry box wi th a d e w poin t of -65~ The ven t ball was forced into the cell and the cell was p laced into a vial wi th a Teflon-l ined sep- turn cap. The vials were t ransferred to an argon-fi l led glove bag enc los ing the GC inject ion port. A p la t inum need le GC syr inge was used to punc tu re the s ep tum and wi thd raw a sample of e lec t ro lyte f rom the cell for di rect in jec t ion on the GC column. This t e chn ique has two advantages ; it is rapid and mois tu re con tamina t ion is v i r tual ly e l imina ted so HC1 and SOs artifacts f rom sample hand l ing are pre- vented . When elect rolyte analyses were carr ied out with- out these t echn iques HC1 con tamina t ion was seen. Three cells were opened for each analysis and three or more in- j ec t ions were m a d e per cell.

The GC analyses were carr ied out using a Tracor 565 equ ipped with a thermal conduc t iv i ty detector. The col-

*Electrochemical Society Active Member.

u m n s were 2 m x 4 m m id glass tubing. The packing was 10% QF-1 ( tr if luoropropyl silicone) on 80/100 mesh Chro- mosorb G HP. The carr ier gas was ul t rahigh puri ty hel ium. The flow rate was 40 cm:Vmin. The inject ion port temperature was 150~ I t is impor tan t to keep the in ject ion port t empera tu re as low as possible to avoid the rmal decomposi t ion of the SOC12. The GC oven t empera tu re was held cons tan t at 70~ The GC detec tor response was cal ibrated for SO2, S..,CI=,, SOCI,,, and SC12 us ing special ly prepared s tandard solutions. The GC-MS analyses were carr ied out wi th a F innigan 4000 GC-MS using the GC c o l u m n and condi t ions descr ibed above. GC-MS analyses were done on a representa t ive select ion of samples to verify the peak identif icat ions from the GC analyses.

Results and Discussion The start ing electrolyte, exc lud ing the salt, was 99.6~

SOCI2 with t races of SOz, SCI~, and S..,C1._,; the GC chromatogram is shown in-Fig. 2. The mass spectral results f rom GC-MS are repor ted in Table I. The f ragmenta t ion pat tern of each c o m p o u n d is compared to a s tandard spectra f rom the E P A / N I H Mass Spect ra l Data Base N S R D S - N B S (1980). In the case of SOs, SC12, and S=,CI=, there is exce l len t agreement . In the case of SOClz the s tandard spec t rum in- c ludes all of the peaks for HC1 and SO.,, the hydrolys is p roducts of SOC12. These are absen t in the p resen t work because of the GC separat ion that p recedes the MS analysis. In addit ion, mois tu re was r igorously exc luded as shown by the absence of HC1 in the GC analysis in Fig. 2.

The compos i t ion of the e lect rolyte as a funct ion of cell age is shown in Fig. 3. The concent ra t ions of S~C12 and SO2

3.76 - _-0 . . . . . . . . . . . . . . ~ - .

0 3.74- c

P 71C V 5.72 - ~ ROOM TEMP V 0 3.7-

L T 3 . ~ 8 - ~ > K x< s ~

3.66 -

3 .64 . . . . . . , , , , ,

4 8 ,2 ,~ 20 24 28 32 3~ 40 44 ~ 52 AGE (WEEKS)

Fig. 1. Open-circuit voltage of undischarged Li-SOCl2 cells as a function of cell age and storage temperature.

) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.217.227.3Downloaded on 2014-07-09 to IP

http://ecsdl.org/site/terms_use

J. Electrochem. Soc., V o l . 136, No . 10, O c t o b e r 1 9 8 9 �9 The E lec t rochemica l Society , Inc. 2 7 9 5

[, Argon SCI S02

] 80012

2

Fig. 2. GC chromatogram of 1 .5M LiAICI4-SOCI2 starting material

6 w:l E I G H T

P E R2 C E~ N

o

/ . / .~ . . . . . . . . . . . :--~

~-~ a ' " " -4- $2CI2 71C

~:~_:S_~---/~ . . . . . . . . -0- S02 71C /

/;' S02 21C

, ~ $2CI2 21C

•

i i i i i i i i i i i i i 4 8 12 16 20 24 28 52 56 40 44 48 52

AGE (WEEKS)

Fig. 3. Composition of electrolyte in undischarged Li-SOCI2 cells as a function of cell age and storage temperature. The balance of the vola- t i le portion not shown is SOCI2.

w e r e f o u n d to i n c r e a s e w i t h a g e a n d e l e v a t e d t e m p e r a t u r e . F o r e x a m p l e , a f t e r s t o r a g e for 1 y r a t r o o m t e m p e r a t u r e t h e c o n c e n t r a t i o n s o f $2C12 a n d SO2 in t h e ce l l s w e r e 0.85 a n d 1.3 +_ 0.01 w e i g h t p e r c e n t (w/o), r e s p e c t i v e l y . A f t e r a g i n g t h e ce l l s fo r 1 y r a t 71~ t h e c o n c e n t r a t i o n s o f $2C12 a n d SO2 w e r e 4.9 a n d 4.8 +_ 0.29 w/o. T h e p o t e n t i a l o f t h e Li-S2C12 c o u p l e w a s c a l c u l a t e d to b e 3.92V. T h i s is g r e a t e r t h a n t h e p o t e n t i a l o f Li-SOC12 t h u s t h e i n c r e a s e in cel l p o t e n t i a l c a n b e a c c o u n t e d for b y t h e in si tu g e n e r a t i o n o f $2C12. T h e cel l p o t e n t i a l i n c r e a s e s a s a f u n c t i o n o f t h e c o n c e n t r a t i o n o f 82C12.

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

6 W E 1 5 - O

H 4 - T

3- P E R2~ C E1 N T

0

~ 502 21C

502 71C

52CI2 21C

52CI2 71C

J ~ l ~ r ~ -~- . . . . . . . . . _~_ . . . . .

4 8 12 16 20 24 28 52 56 40 44 48 52 ACE (WEEKS)

Fig. 4. Composition of electrolyte in sealed glass ampuls as a function of age and storage temperature.

Table I. Mass spectra from GC-MS of 1 .5M LiAICI4-SOCI2 starting material shown in Fig. 2

% Relative abundance Library

M/E Sample s tandard a A s s i g n m e n t

SO2 40 1.2 0 Ar 48 51.0 49.1 SO 49 0 0.4 33SO 50 1.7 2.3 3%0 64 100.0 99.8 SO2 65 0.3 0.9 3~SO2 66 0.3 4.8 34SO2 83 4.4 0 SOCP

SC12

35 19.2 18.3 C[ 36 18.8 0 CI H 37 4.9 5.7 :'7C1 38 6.9 0 :';CI H 40 37 0 Ar 48 15 0 SO 51 0 4.0 52 0 2.6 64 6.8 7.0 Sz 66 0 0.7 :'4S:'zS 67 190.0 94.6 SCI 68 0 0.8 :':'SCI 69 30.2 34.9 S:';CI 70 0 4.2 :':'S:'~CI 71 0 1.4 :'4S:'~C1 72 0 2.4 :I~'CI:~TCI 83 1.7 0 SOCP

102 77.3 70.2 SC12 103 0 6 3aSC12 104 53.5 60.2 $37CIC1 106 2.4 11.7 $37CP7C1

SOC12

32 17.0 0 S 35 19.5 40.9 CI 36 0 69.9 HCI 37 7.0 13.4 :~CI 38 0 22.6 H:'TCI 48 32.0 100.0 SO 50 2.0 4.8 :14SO 64 2.8 46.3 SO2 66 0 2.3 :'4SOz 67 8.0 8.9 SCI 69 3.0 3.3 S:'7C1 80 0 8.3 SzO 83 100.0 97.8 SOCI 85 38.0 36.2 SO:';CI 87 2.0 O :'~SO:~7C1

118 25.0 9.8 SOCIz 120 16.0 6.8 SO:';CIC1 122 3.0 1.3 SO:'7C12

82C12'

35 4.8 5.0 :~'~CI 37 1.8 1.6 :~;Cl 64 6.0 18.9 S., 66 0.4 1.8 :~2S-:~4S 67 6.8 6.7 :"~CIS 69 2.3 2.5 :nCIS._, 99 100.O 96.8 :~r'CIS2

1 O0 0 1.7 :~5C PS:~2S 101 40.4 40.7 :nClS2 103 1.1 3.1 :nCl:'4S:~ZS 134 76.3 75.3 SzCl._, 136 56.3 5.51 S~:':'CO:nCI 138 10.4 12.5 $237C12

"EPA/NIH Mass Spectral Data Base NSRDS-NBS (1980). i, SOCI f ragment probably from thermal decomposi t ion of SOCI2. ~' The spec t rum of SOCI2 has been subtracted from that of SzCl2

s ince S=,Clz elutes on the tail of the SOC12 peak.

c e l l s a n d t h e y w e r e o p e n e d for a n a l y s i s a t t h e s a m e a g e in- t e r v a l s . T h e e l e c t r o l y t e c o m p o s i t i o n in t h e a m p u l s d i d n o t c h a n g e a t r o o m t e m p e r a t u r e o r 71~ as s h o w n in Fig. 4. T h u s , s i m p l e t h e r m a l d e c o m p o s i t i o n o f t h e e l e c t r o l y t e is n o t r e s p o n s i b l e for t h e c h a n g e s o b s e r v e d in a c t u a l ce l l s .

T h e c a u s e o f SOC12 d e c o m p o s i t i o n i n ce l l s w a s d e t e r - m i n e d b y i s o l a t i n g v a r i o u s ce l l c o m p o n e n t s in s e a l e d g l a s s a m p u l s o f e l e c t r o l y t e . A l i s t o f t h e c o m b i n a t i o n s is g i v e n in T a b l e II. T h e r a t io o f c o m p o n e n t s to e l e c t r o l y t e w a s t h e s a m e as in a l ive cell . T w o s e t s o f a m p u l s w e r e p r e p a r e d for s t o r a g e a t r o o m t e m p e r a t u r e a n d a t 71~ A f t e r f o u r w e e k s t h e y w e r e o p e n e d a n d t h e e l e c t r o l y t e w a s a n a l y z e d b y GC.



2 7 9 6 J. Electrochem. Soc., Vo l . 136, No . 10, O c t o b e r 1 9 8 9 �9 The E lec t rochemica l Society , Inc.

Table II. Summary of cell components tested for compatibility in SOCI2 electrolyte

Ampul Contents

A B C D E F G

H I J K L M

Control, electrolyte only Lithium Carbon collector Carbon black Expanded metal T-30B (dried Teflon emulsion) Carbon collector, lithium and expanded metal, glass separator Lithium, carbon collector Lithium, carbon black Lithium, T-30B [dr ied Teflon emulsion) Carbon collector, lithium and expanded metal Lithium and expanded metal Expanded metal, carbon collector

A n inc rease in t he c o n c e n t r a t i o n of SO2 and 82C12 was f o u n d in e lec t ro ly te f rom all of t he a m p u l s t h a t h a d con- t a i n e d Li. The c o n c e n t r a t i o n of $2C12 and SO2 in t h e s e s a m p l e s is cha r t ed in Fig. 5 and 6. T he a m o u n t of SO= in a m p u l s G a n d I, Fig. 6, is less at 71~ t h a n at 21~ This does no t agree w i th t he resu l t s f rom o the r a m p u l s a n d is be l i eved to be an error. Poss ib l e causes m i g h t be a poor seat o n t he a m p u l or loss of vola t i le SOz on t r a n s f e r r i n g t he s a m p l e f rom a n a m p u l to a s e p t u m vial for GC analysis . The c o m p o s i t i o n of e lec t ro ly te f rom a m p u l s t h a t had no t c o n t a i n e d Li was u n c h a n g e d f rom t he s t a r t ing mater ia l . T h e r e was also no c h a n g e in t he con t ro l a m p u l s t h a t con- t a i n e d on ly e lectrolyte . T he reac t ion of Li a n d SOCI= is be- l ieved to be t h e s a m e w h e t h e r it is Li pa s s iva t i on occu r r i ng in an a m p u l or an u n d i s c h a r g e d cell or t he e l e c t r ochemica l r e d u c t i o n of SOCl~ in a d i s c h a r g i n g cell. T he reac t ion of Li a n d SOC12 gene ra t e s SO~ a n d $2C12. In a d i s c h a r g i n g cell t he S=C12 is f u r t he r r e d u c e d to S a n d LiC1 b u t in cells on s to rage or in t he a m p u l s the ra te is s low e n o u g h for S2Cl~ to d i f fuse away f rom t h e Li su r face a n d accum ul a t e .

T h e e lec t ro ly te was t h e n s tud ied as a f u n c t i o n of cell dis- c h a r g e to fol low c h a n g e s in the c o n c e n t r a t i o n of S.,CI=. Cells c o n t a i n i n g 1.5M LiA1CI~-SOCI= e lec t ro ly te were dis- c h a r g e d at 21~ at 6 m A / c m 2 to 25, 50, 75, and 100% of t he i r n o m i n a l capac i ty and the i r e l ec t ro ly t e was analyzed. The re su l t s are g r a p h e d in Fig. 7. T he c o n c e n t r a t i o n of SO= in- c reases sha rp ly d u r i n g d ischarge . T he so lubi l i ty of SO2 in t he e lec t ro ly te is a b o u t 11% by w e i g h t at a m b i e n t t e m p e r a - ture ; no a t t e m p t was m a d e to quan t i t a t i ve l y m e a s u r e t he SO= c o n t e n t a b o v e t he so lubi l i ty l imi t la te r in d i scharge . T h e c o n c e n t r a t i o n of $2C1~ inc reased slowly; the maxi - m u m was a b o u t 0.6 w/o at 100% discharge . Thus , S=CI= ap- pea r s to b e g e n e r a t e d in d i s c h a r g i n g cells as wel l as und i s - c h a r g e d cells. The s t a r t ing e lec t ro ly te c o n t a i n e d a t race of SCl= bu t th i s d i s a p p e a r e d in t he b e g i n n i n g of d i s cha rge a n d n o n e could be de t ec t ed s u b s e q u e n t l y . S ince SCl= is easi ly de t ec t ed at low c o n c e n t r a t i o n s if any was fo rmed it m u s t h a v e b e e n c o n s u m e d immedia te ly .

A n a n a l o g o u s s t u d y was m a d e us ing cells filled wi th 1.5M LiA1CI~'-SOCI~ c o n t a i n i n g 18 w/o S.,CI~ a n d 4 w/o SO.,.

11- w E 10: I 9- G 81 H 7- T

6- P 5- s

4 R C 3 E 2 N 1 T

o

S~CI~ ~ ~

* = ampoules containing ~, lithium %

/,

N A B* C D E F G* H* I* J* K* L* M

AMPOULE (see Table 2)

Fig. S. Concentration of SzCI2 in ampuls of electrolyte containing cell components after storage for four weeks at 21 ~ or 71~

11- W io: E I 9 G 8 H 7 T

6, P 5: E 4- R C 3 : E21 N 1 T

S02

* = ampoules containing lithium

A B* C D E F

AMPOULE

G* H* I* J* K* L* M

(see Table 2)

Fig. 6. Concentration of SO2 in ampuls of electrolyte containing cell components after storage for four weeks at 21 ~ or 71 ~

T h e s e cells were also d i s c h a r g e d at 21~ T h e s e resu l t s are s h o w n in Fig. 8. The S.,Clz c o n c e n t r a t i o n d r o p p e d s teadi ly d u r i n g the first ha l f of d ischarge . The ave rage capac i ty of t h r e e of t h e s e cells was 0.77 _+ 0.04 Ah to a 2.7V cu tofs Based on two F a r a d a y s per mole the a m o u n t of S=Clz per cell is e q u i v a l e n t to 0.29 Ah. S ince t he S~Ctz was not de- p le t ed un t i l 0.39 Ah the re m u s t be c o d i s c h a r g e of the S2Clz and SOCl> Again , SCI~ could not be de t ec t ed in par t ia l ly or c o m p l e t e l y d i s c h a r g e d cells. A poss ib le e q u a t i o n for the r eac t ion of Li wi th SOClz is

6Li + 4SOCI.,--, 6LiC1 + 2SO._, + S.,CI~

D u r i n g d i s cha rge t he S,CI., can be r e d u c e d to S and LiCl

2Li + SzClz --, 2LiC1 + 2S

g iv ing an overal l r eac t ion for the c h e m i c a l a n d electro- c h e m i c a l s t eps of

4Li + 2SOCI., -~ 4LiCl + SO._, + S

Thus , t he se two s teps are e q u i v a l e n t to the genera l ly ac- c e p t e d d i s c h a r g e r eac t ion for SOCI,,.

The p r e s e n c e of re la t ively h igh c o n c e n t r a t i o n s of SzCl= in u n d i s c h a r g e d cells is u n e x p e c t e d . B l o m g r e n et al. (2) and Car te r et al. (3) have p rev ious ly ident i f ied S._,CI~ by GC in par t ia l ly d i s c h a r g e d or d i s c h a r g e d cells. Ne i the r cou ld iden t i fy SC12 t h o u g h b o t h p r o p o s e it as an i n t e r m e d i a t e in the r e d u c t i o n of SOCI~ to gene ra t e S.,C1._,. Hayes et al. (4) ident i f ied S._,CI., in u n d i s c h a r g e d cells and s u g g e s t e d t h a t it o r ig ina t ed as a c o n t a m i n a n t in t he e lectrolyte , T h e y d id no t ana lyze the s t a r t ing e lect rolyte , however , h a v i n g pur- c h a s e d c o m m e r c i a l l y m a n u f a c t u r e d cells for t he i r s tudy. While t races of SzC12 are p r e s e n t in f resh SOCI., e lec t ro ly te the c o n c e n t r a t i o n does not a p p r o a c h t ha t found in ac tua l cells. In the p r e s e n t work, the SOCI~ raw mate r ia l is c lear ly no t t he sou rce of S~C1._,.

800

,00 I* I

200

0 J J i r , ~ , i ~ , . . . . . . . . . . . . . . . . . . ,

10 20 30 40 50 60 70 80 gO lO0 % OF DISCHARGE TO 2.70V

Fig. 7. Composition of electrolyte as a function of depth of cell discharge at 6 mA/cm z and 21 ~ The starting electrolyte is 1.5M LiAICI4- SOCI2. The balance of the volatile portion not shown is SOCIz. The sample size is 3 I~liter.



J. Electrochem. Soc., Vol. 136, No. 10, October 1989 �9 The Electrochemical Society, Inc. 2797

1200

1000

8oo "\\ I0 \ ' \ ~< 6| \ \

2OO

0 , , ~ , , ' ~ , ~ - - - - - . . . . : - - '~--T-- . - - - 10 20 30 40 50 60 70 80 90 100

% OF DISCHARGE TO 2.70V

Fig. 8. Composition of electrolyte as a function of cell discharge at 6 mA/cm 2 and 21~ The starting electrolyte is 1.5M LiAICI4 in mixed solvent of 78 w/o SOCI2, 18 w/o $2CI2, and 4 w/o SO~. The balance of the volatile portion not shown is SOCI~. The sample size is 3 I*liter.

dling to avoid generating HC1 and SO., from moisture con- tamination. Carter's peak assignment of SCI2 likewise needs to be confirmed by a method in addition to GC.

Summary and Conclusions These experiments have demonstrated that S.,C1., and

SO2 are generated in undischarged Li-SOC12 cells from the reaction of Li and SOCI.,. The increase in OCV of undischarged cells can be accounted for by in situ generation of S._,CI.,. Since S.,CI,, has a higher potential it is reduced in preference to SOCI.,.

Acknowledgment I would like to acknowledge Mr. James E. Rafter for his

careful GC analyses.

Manuscript submitted Nov. 4, 1988; revised manuscript received Feb. 3, 1989. This was Paper 495 presented at the Philadelphia, PA, Meeting of the Society, May 10-15, 1987.

Eveready Bat tery Company . Incorporated. assisted in meeting the publicat ion costs o f this article.

Venkatasetty and Saathoff (5) carried out cyclic voltam- metry studies on various additives to a Li-SOCI,, system, they found that the addition of S.,C!._, or SC1._, raised the OCV. Evans et al. (6), Dey (7), and Chua et al. (8) each reported that SOCI,, will react with S. Chua et al. (8) iden- tified the products as SO._, and S~C1._, using infrared spectroscopy. Evans et al. (6) reported ShCl., and SO., were generated from SOC12 plus S only at temperatures greater than 130~ While a trace of S could be present in undischarged cells, the maximum cell storage temperature was only 71~ so this reaction is unlikely to be the source of S.,C12 in the present work.

Carter et al. (9) used GC to analyze electrolyte in fresh Li- SOCI., cells. They found SO., and S2CI,,; however, there was no speculation on whether it originated in the electrolyte or was generated in the cells. They also analyzed the electrolyte from a 50% discharged cell and reported finding Cl.,, SCI.,, SO._,, and SOCI.,. In the present work only SO.,, SOC1._,, and S.,C12 were found. Since the retention times of C1., and HC1 in the GC are similar, positive identification by an- other method such as GC-MS is needed to confirm the re- sult. CI~ is not expected to be present since it should react with Li. However, HCI is a ubiquitous artifact in SOC1.., analyses caused by contact of the sample with any trace of moisture. Strict precautions must be taken in sample han-

REFERENCES 1. D. H. Johnson, A. D. Ayers, R. L. Zupancic, V. S. Al-

berto, and J. C. Bailey, J. Power Sources, 12, 61 (1984). 2. G. E. Blomgren, V. Z. Leger, T. Kalnoki-Kis, M.L.

Kronenberg, and R. J. Brodd, ibid.. 7, 583 (1979). 3. B. J. Carter, R. M. Williams, A. Rodriquez, S. Kim, M. M.

Evans, and H. Frank, This Journal, 132, 525 (1985). 4. C. A. Hayes, S. L. Gust, M. D. Farrington, J. L. Lock-

wood, and G.J . Donaldson, Abstract 30, p. 45, The Electrochemical Society Extended Abstracts, Vol. 86-2, San Diego, CA, Oct. 19-24, 1986.

5. H. V. Venkatasetty and D. J. Saathoff, This Journal, 128, 773 (1981}.

6. M. M. Evans, S. Subba Rao, and B. J. Carter, Abstract 148, p. 226, The Electrochemical Society Extended Ab- stracts, Vol. 84-2, New Orleans, LA, Oct. 7-12, 1984.

7. A. N. Dey, in "Proceedings of the 28th Power Sources Conference," Atlantic City, N J, June 12-15, 1978, The Electrochemical Society, Inc., p. 251 (1979).

8. D. L. Chua, S. L. Deshpande, and H. V. Venkatasetty, Abstract 59, p. 163, The Electrochemical Society Ex- tended Abstracts, Vol. 78-2, Pittsburgh, PA, Oct. 15-20, 1978.

9. B. J. Carter, S. Subba Rao, R. Williams, M. Evans, S. Kim, and F. D. Tsay, in "Proceedings of the 31st Power Sources Conference," Cherry Hill, N J, June 11-14, 1984, The Electrochemical Society, Inc., p. 400 (1985).



investigation of thionyl chloride decomposition and open-circuit potential in lithium-thionyl...

Documents