Battery Model

University of South Carolina
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Chemical Engineering, Department of
1-1-1989
A Mathematical Model of a Lithium/Thionyl

Chloride Primary Cell
T. I. Evans
Texas A & M University - College Station
T. V. Nguyen
Texas A & M University - College Station
Ralph E. White
University of South Carolina - Columbia, white@cec.sc.edu
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Journal of the Electrochemical Society, 1989, pages 328-339.
The Electrochemical Society, Inc. 1989. All rights reserved. Except as provided under U.S. copyright law, this work may not be
reproduced, resold, distributed, or modified without the express permission of The Electrochemical Society (ECS). The archival
version of this work was published in the Journal of the Electrochemical Society.
http://www.electrochem.org/
DOI: 10.1149/1.2096630
http://dx.doi.org/10.1149/1.2096630
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J. Electrochem. Soc., Vol. 136, No. 2, February 1989 9 The Electrochemical Society, Inc.
328
Table A-I. Concentration,density,and mole fraction of LiAICI4-SOCI2

solutionsat 25~ basedon the experimentof Venkatasettyand
Saathoff (5)
Concentration
(mol/liter)
Density
(g/cm~)
0.00249
0.00997
0.03046
0.04985
0.0997
0.200
0.35
0.50
0.65
0.75
0.90
1.00
1.50
1.6438
1.6443
1.6451
1.64599
1.64820
1.6525
1.65903
1.66555
1.67206
1.6764
1.68293
1.68727
XLiAIC14a
0.00018
0.00072
0.00220
0.00360
0.00722
0.01450
0.02540
0.03633
0.04729
0.054395
0.06561
0.07296
1,7090
0.109895
aCalculated by iteration as explained in the text.
Ib H e n r i k s e n s F o n d are t h a n k e d for p r o v i d i n g the financial basis of this work.
Manuscript submitted Nov. 30, 1987; revised manuscript

received June 28, t988.
N o t e a d d e d in proof: R e c e n t m e a s u r e m e n t s (16) agree
well w i t h our m e a s u r e m e n t s also at h i g h concentrations.
APPENDIX
To facilitate c o m p a r i s o n s w i t h the literature, data g i v e n
by V e n k a t a s e t t y and S a a t h o f f (5) for the density of the
SOC12 solution vs. t h e molar LiA1C14 c o n c e n t r a t i o n h a v e
b e e n u s e d to e s t i m a t e a p p r o x i m a t e concentrations. T h e
calculations w e r e based on their data points (see Table
A-I), u s i n g an iterative method. We a s s u m e d p g r a m s of
LiA1C14 per m o l e of SOC12. Thus, p = C . 175.732 (118.9894 +
p)/1000 9 p, w h e r e C is the m o l a r LiA1C14 concentration, p is
the density, and the n u m b e r s s h o w n are the m o l a r masses
of LiA1C14 and SOC12. F r o m p values calculated iteratively,
the m o l a r fraction of LiA1Ch is easily o b t a i n e d for each of
t h e g i v e n concentrations. T h e n the C and p data w e r e
t r e a t e d by regression v s . XLiAIC]4 to give linear dependencies
(C 0.0025) = (13.7007 0.0143) 9XLiAlC14 (R ~ = 0.999987)
and
(p +_ 0.0001) = (0.594484 0.000934). XLjAlCI4

+ (1.64388 --+ 0.00004) (R 2 = 0.99997)
T h e s e lines are valid in the range 0 < XLIA~C14< 0.11, 0 < C
< 1.50 mol/liter and 1.64 < p < 1.71 g/cm ~ and at 25~ At
h i g h e r c o n c e n t r a t i o n s linear extrapolation cannot be d o n e
w i t h confidence. Therefore the c o n c e n t r a t i o n s in Table II
are s h o w n w i t h few digits.
It s h o u l d be n o t e d that t h e e q u a t i o n for t h e density does
not extrapolate to t h e generally a c c e p t e d r o o m t e m p e r a ture v a l u e 1.629 g/cm 3 for SOC12 (17).
REFERENCES
1. " L i t h i u m Battery T e c h n o l o g y " , H. V. Venkatasetty,
Editor, The E l e c t r o c h e m i c a l Society and J o h n Wiley
& Sons, Inc., N e w Y o r k (1984).
2. J. J. Auborn, K. W. French, S. I. L i e b e r m a n , C. K.
Shah, and A. Heller, This Journal, 120, 1613 (1973).
3. M. S o l o m o n , ibid., 128, 233 (1981).
4. H. V. Venkatasetty and W. B. Ebner, in P r o c e e d i n g s of
the 29th P o w e r Sources Conference, Atlantic City,
N J, J u n e 9-12, 1980, The E l e c t r o c h e m i c a l Society,
Inc., p. 122 (1981).
5. H. V. V e n k a t a s e t t y and D. J. Saathoff, This Journal~
128, 773 (1981).
6. H. V. Venkatasetty and S. Szpak, J. Chem. Eng. Data,
28, 47 (1983).
7. S.Szpak and H. V. Venkatasetty, This Journal, 131, 961
(1984).
8. A. N. Dey and J. Miller, ibid., 126, 1445 (1979).
9. R. W. Berg, H. A. Hjuler, and N. J. B j e r r u m , Inorg.
Chem., 23, 557 (1984).
10. F. W. P o u l s e n and N. J. Bjerrum, J. Phys. Chem., 79,
1610 (1975).
11. G. J o n e s and B. C. Bradshaw, J. Am. Chem. Soc., 55,
1789 (1933).
12. J. O. B e s e n h a r d and G. Eichinger, J. Electroanal.
Chem., 68, 1 (1976).
13. F. Birkeneder, R. W. Berg, H. A. Hjuler, and N . J .
Bjerrum, Z. Anorg. AUg. Chem., Accepted.
14. Statistical Analysis System, P r o c e d u r e s
GLM,
R S Q U A R E CP, and G3D, S A S I n s t i t u t e Inc., Cary,
NC 27511.
15. P . A . Mosier-Boss, J, J. Smith, and S. Szpak, P a p e r 496,
p. 711, The E l e c t r o c h e m i c a l Society E x t e n d e d Abstracts, Vol. 87-1, Philadelphia, PA, May 10-15, 1987.
16. J . W . B o y d and G. E. B l o m g r e n , Abs. 9, p. 14, T h e Elect r o c h e m i c a l Society E x t e n d e d Abstracts, Vol. 88-1,
Atlanta, GA, May 15-20, 1988.
17. S. T. B o w d e n and A. R. Morgan, Phil. Mag., 29, 367
(1940).
A Mathematical Model of a Lithium/Thionyl Chloride
Primary Cell
T. I. Evans,* T. V. Nguyen,* and R. E. White**
Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843
ABSTRACT
A o n e - d i m e n s i o n a l m a t h e m a t i c a l m o d e l for the lithium/thionyl chloride, p r i m a r y cell has b e e n d e v e l o p e d to investigate m e t h o d s of i m p r o v i n g its p e r f o r m a n c e and safety. T h e m o d e l includes m a n y of t h e c o m p o n e n t s of a typical lithium/
thionyl chloride cell such as the porous lithium chloride film w h i c h forms on the lithium a n o d e surface. T h e g o v e r n i n g
e q u a t i o n s are f o r m u l a t e d from f u n d a m e n t a l c o n s e r v a t i o n laws using porous e l e c t r o d e t h e o r y and c o n c e n t r a t e d solution
theory. T h e m o d e l is u s e d to predict one-dimensional, t i m e d e p e n d e n t profiles of concentration, porosity, current, and potential as well as cell t e m p e r a t u r e and voltage. W h e n a certain discharge rate is required, the m o d e l can be u s e d to determ i n e t h e design criteria and operating variables w h i c h yield h i g h cell capacities. M o d e l predictions can be u s e d to establish operational and design limits w i t h i n w h i c h the t h e r m a l r u n a w a y p r o b l e m , i n h e r e n t in t h e s e cells, can be avoided.
T h e lithium/thionyl chloride (Li/SOC12) cell is an attractive p r i m a r y energy source b e c a u s e of its h i g h e n e r g y density (1, 2). H o w e v e r , researchers h a v e o b s e r v e d that the
Li/SOCI~ cell is a serious safety hazard u n d e r certain conditions (2). H i g h discharge rates and h i g h t e m p e r a t u r e s
p r o m o t e t h e r m a l r u n a w a y w h i c h can result in the v e n t i n g
*Electrochemical Society Student Member.
**Electrochemical Society Active Member.
of toxic gases and explosion. A m a t h e m a t i c a l m o d e l of this

battery has been d e v e l o p e d to investigate the operational
and design characteristics w h i c h can be a d j u s t e d to yield
efficient, yet a c c e p t a b l y safe Li/SOC12 cells.
Description of a Li/SOClz Cell

T h e m o d e l describes t h e Li/SOCI~ cell illustrated in
Fig. 1. T h e four cell regions are t h e lithium c h l o r i d e (LiC1)
film w h i c h forms on the anode surface, the separator (usu-
Downloaded 13 Jun 2011 to 129.252.106.20. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp
ally a glass matting), the electrolyte reservoir, and the porous c a r b o n cathode. The a n o d e surface and cathode current collector are the b o u n d a r i e s of t h e m o d e l region. The
electrolyte consists of l i t h i u m t e t r a c h l o r o a l u m i n a t e
(LiA1C14) in thionyl chloride (SOC12). The Li/SOC12 cell is a
c o m p l e x c h e m i c a l and e l e c t r o c h e m i c a l s y s t e m i n v o l v i n g
an u n k n o w n n u m b e r of reactions (2). The overall reactions
w h i c h s e e m m o s t i m p o r t a n t to i n c l u d e in m o d e l i n g are:
t h e o x i d a t i o n of l i t h i u m at the a n o d e
Li -+ Li + + e-
[1]
t h e r e d u c t i o n of SOC12 at the cathode

2SOC12 + 4e- --+ 4C1- + S02 + S
[2]
and the f o r m a t i o n of the LiC1 film on the a n o d e and the

p r e c i p i t a t i o n of LiCI on the pore surfaces of the c a t h o d e
d u r i n g discharge by the following reaction
Li + + C1- ~ LiCl(s)
[3]
D u e to the low solubility of t i C 1 in the SOCI~ + LiAIC14 solv e n t (3), reaction [3] is a s s u m e d to occur c o m p l e t e l y and instantaneously. Thus, reactions [2] and [3] can be c o m b i n e d
to yield one overall reaction r e p r e s e n t i n g the processes occ u r r i n g w i t h i n t h e porous c a t h o d e
4Li + + 4e- + 2SOC12-+ 4LiC1 + SO~ + S
[4]
F o u r species are i n c l u d e d in the model: Li +, A1CI(, SOC12,

and LiC1. S i n c e the c h l o r i d e ion, CI-, does n o t a p p e a r in reaction [4] it is not i n c l u d e d in the model. Later, this species
m a y be i n c l u d e d b e c a u s e of its influence on species transport (4). In addition, SO2 and S are not i n c l u d e d in t h e
m o d e l for simplicity. It is a s s u m e d that t h e y dissolve into
t h e electrolyte due to their h i g h e r solubilities (3). T h e s e ass u m p t i o n s are m a d e to simplify the m o d e l d e v e l o p m e n t ;
the m o r e species considered, the m o r e c o m p l e x and c u m b e r s o m e t h e transport e q u a t i o n s b e c o m e . The species S
and SO~ m a y be i n c l u d e d at a later t i m e b e c a u s e researchers h a v e s h o w n that SO2 is the m a j o r c o m p o n e n t in t h e
v a p o r p h a s e and that S precipitates w i t h t h e LiC1 in t h e porous c a t h o d e (5).
S z p a k and V e n k a t s e t t y (6) state that m o d e l i n g t h e
Li/SOC12 cell is difficult due to the c o m p l e x i t y of this physical system. T h e y o b s e r v e that as the cell discharges, t h e
t e m p e r a t u r e and p r e s s u r e of the cell change, t h e v o l u m e of
electrolyte decreases, the electrolyte c o m p o s i t i o n varies,
and n e w phases appear. H o w e v e r , m u c h can be l e a r n e d
f r o m a t t e m p t i n g to d e s c r i b e t h e s e p h e n o m e n a t h r o u g h
m a t h e m a t i c a l modeling.
Models of the Li/SOCI2 Cell

P r e v i o u s workers h a v e p r e s e n t e d m a t h e m a t i c a l m o d e l s
of the Li/SOCl~ cell (4, 7-14) as well as m a t h e m a t i c a l m o d els of similar e l e c t r o c h e m i c a l systems (15-19). The
Li/SOC12 cell m o d e l d e v e l o p e d by Tsaur and Pollard (7) is
b a s e d on c o n s e r v a t i o n of mass and charge and is u s e d to
--
+
Current
- -
Collectors - ""- ~ - - - ~ "
, ,i5,i55,il
t ~l , l l r l
I ....
Separator
LiCI
[m
,~ ,51
i
i i i iiiiitl I
(Cathode)
I I I lllll{I
Reservoir
iiii IIii ill *llji

~
Electrolyte
(fiOCl~ + IAA1CI4)
Porous Carbon
i I f llJllllfl
I 1~llllll
,5q5551I
I,,,pl,,[
I * 1 ~i i1i1i i1 1 1
Lithium Foil
(Anode)
N':'
llll~fllllllll
1Ill~l,
5 5 5 , 1 1 , 5 51
I ,
,,d
,',,5! g,,
}I
>X
\\
\~\\ \
329
d e t e r m i n e the c o n c e n t r a t i o n and reaction rate profiles in

the cell. Other Li/SOC12 cell m o d e l s (10-14) are based on
c o n s e r v a t i o n of e n e r g y and are u s e d to d e t e r m i n e the thermal b e h a v i o r of the cell.
Tsaur and Pollard (4, 7, 8) p r e s e n t a o n e - d i m e n s i o n a l
m o d e l of the Li/SOC12 cell. T h e y use porous electrode
t h e o r y (20, 21) and c o n c e n t r a t e d solution t h e o r y (22-24) to
d e v e l o p this model, and t h e n use their m o d e l to predict
c o n c e n t r a t i o n profiles, reaction rate distributions in t h e
porous electrode, distributions of LiC1 precipitate in t h e
pores of the porous electrode, and cell utilization. However, in their m o d e l d e v e l o p m e n t Tsaur and Pollard (4, 7, 8)
a s s u m e that the reservoir is a well m i x e d solution of constant concentration, w h i c h m a y not be a valid a s s u m p t i o n
as s h o w n by G u et al. (15). Also, t h e y treat t h e LiC1 film in a
simplified m a n n e r by e n d i n g their finite difference m e s h
at the LiC1 film/separator interface. This w o r k s h o w s the
i m p o r t a n c e of i n c l u d i n g the film region in the m o d e l i n g as
e v i d e n c e d b y t h e large c o n c e n t r a t i o n gradients in t h e film
and the effect of film porosity on cell performance.
S e v e r a l m o d e l s (10-14) h a v e b e e n p r e s e n t e d to d e s c r i b e
the t h e r m a l b e h a v i o r of Li/SOC12 cells. Parnell and S z p a k
(10) p r e s e n t a t h e r m a l m o d e l for the Li/SOC12 cell in one dim e n s i o n . T h e y c o n s i d e r h e a t g e n e r a t i o n d u e to t h e polarization of the electrodes and internal cell resistance. T h e i r
m o d e l is u s e d to s h o w that as the rate of d i s c h a r g e is increased, the t e m p e r a t u r e increase is p r o p o r t i o n a l to t h e increase in cell current. S z p a k et al. (11) p r e s e n t a t h e r m a l
model, similar to the m o d e l by Parnell and S z p a k (10),
w h i c h a c c o u n t s for catastrophic t h e r m a l runaway. Their
m o d e l (11) is f o r m u l a t e d based on the fact that therm~il
r u n a w a y is associated w i t h ignition and burning, via one
or m o r e cell defects, rather t h a n explosion. The m o d e l is
u s e d to predict the t i m e and position d e p e n d e n t t e m p e r a t u r e and c o n c e n t r a t i o n profiles. T h e m o d e l p r e d i c t i o n s
c o m p a r e favorably to w h a t is physically o b s e r v e d w h i c h
m a y indicate that the reactions causing t h e r m a l r u n a w a y
are initiated by localized heat sources d e v e l o p e d f r o m defective cells and/or cell c o m p o n e n t s . Cho and Halpert (12)
h a v e p r e s e n t e d a s i m p l e t h e r m a l m o d e l for Li/SOC12 prim a r y cells. U s i n g e x p e r i m e n t a l data for a specific cell disc h a r g e to d e t e r m i n e a h e a t g e n e r a t i o n rate term, t h e y use
their m o d e l to predict the cell t e m p e r a t u r e as it changes
w i t h time. This i n f o r m a t i o n can be u s e d to d e t e r m i n e safe
o p e r a t i n g limits for a particular cell. Cho and H a l p e r t (13)
and Cho (14) have t a k e n the m o d e l i n g one step further by
d e v e l o p i n g a m e a n s to calculate the h e a t g e n e r a t i o n rate
t e r m in their m o d e l (12) u s i n g e x p e r i m e n t a l l y d e t e r m i n e d
resistances. T h e s e t h e r m a l m o d e l s (10-14) are s i m p l e m o d els w h i c h d e s c r i b e the cell u s i n g a small set of equations,
u n k n o w n s , and parameters. T h e s e m o d e l s are limited as
far as their ability to predict cell b e h a v i o r as a f u n c t i o n of
various design criteria b e c a u s e t h e y do not i n c l u d e m a n y
features of the physical system. F o r e x a m p l e , the m o d e l s
do not i n c l u d e the effects of m i g r a t i o n on species transport, t h e effect of t h e precipitating LiC1 in t h e porous elect r o d e on reaction kinetics, and the effects of current and
potential on t h e e l e c t r o c h e m i c a l reaction rates. These
m o d e l s c a n n o t be used to predict certain key d e s i g n criteria, such as the porosity distribution in the porous cathode.
Models of similar e l e c t r o c h e m i c a l systems, s u c h as the
m o d e l s of the lead acid battery (15-17) and the lithiuma l u m i n u m / i r o n sulfide battery (18, 19), w e r e f o u n d to be
useful in the d e v e l o p m e n t of the m o d e l p r e s e n t e d here.
T h e s e models, like T s a u r and P o l l a r d ' s m o d e l (7), are
b a s e d on c o n s e r v a t i o n of mass and charge and e m P l o y
c o n c e n t r a t e d solution t h e o r y as well as porous e l e c t r o d e
theory. S o m e of the m o d e l e q u a t i o n s h e r e are similar to
t h o s e p r e s e n t e d by others; however, t h o s e p r e s e n t e d by
others c a n n o t be u s e d to m o d e l t h e Li/SOC12 cell b e c a u s e
t h e y do not i n c l u d e all the various regions in the Li/SOC12
cell n o r do t h e y i n c l u d e certain physical p h e n o m e n a specific to t h e Li/SOC12 cell, such as the LiCI film f o r m e d on the
l i t h i u m a n o d e surface.
Model Development
Fig. 1. Schematicrepresentationof a lithium/thionyl chloride cell
The g o v e r n i n g e q u a t i o n s p r e s e n t e d n e x t d e s c r i b e conservation of mass and current, species transport, and reac-
330
tion kinetics in each region of the Li/SOC12 cell. The equations for the porous e l e c t r o d e region are p r e s e n t e d first,
followed by the e q u a t i o n s for the reservoir, separator, and
LiC1 film. The b o u n d a r y conditions and initial conditions
necessary to c o m p l e t e the e q u a t i o n set are p r e s e n t e d after
that. The overall e n e r g y balance u s e d to d e t e r m i n e the cell
t e m p e r a t u r e as it changes with t i m e is p r e s e n t e d last.
Porous electrode region.--In order to d e v e l o p a useful

and descriptive set of g o v e r n i n g e q u a t i o n s for t h e porous
electrode, its essential features m u s t be a c c o u n t e d for
w i t h o u t c o n s i d e r i n g its r a n d o m m i c r o s c o p i c geometry.
The m a c r o s c o p i c t h e o r y for porous electrodes r e v i e w e d by
N e w m a n and T i e d e m a n n (20), is u s e d for this purpose.
Essentially, t h e p o r o u s region is treated as a s u p e r p o s i t i o n
o f two continua, the ionically c o n d u c t i n g electrolyte (solution) phase and the electronically c o n d u c t i n g m a t r i x
(solid) phase. T h a t is, the porous electrode is p i c t u r e d as
one h o m o g e n e o u s region w h i c h can be d e s c r i b e d by various distributed quantities. T h e s e quantities are continuous in space and t i m e and are a v e r a g e d over a differential
v o l u m e of the porous region w h i c h is small relative to the
overall d i m e n s i o n s of the electrode yet large relative to the
p o r e structure. This v o l u m e averaging p r o c e d u r e has b e e n
u s e d to m o d e l other e l e c t r o c h e m i c a l systems (15, 25) and is
discussed_in detail by T r a i n h a m (21), Whitaker (26), and
D u n n i n g (27). E x a m p l e s of v o l u m e a v e r a g e d quantities are
t h e faradaic current in t h e solution phase and t h e electronic c u r r e n t in the m a t r i x phase of the porous electrode.
T h e c u r r e n t in the porous region m u s t be conserved. Ass u m i n g that the d o u b l e layer at the pore wall is e x t r e m e l y
t h i n relative to the pore dimensions, the electrolyte w i t h i n
t h e pores can be c o n s i d e r e d electrically neutral and gove r n e d by the electroneutrality condition w h i c h is
[5]
Y~ z~ci = 0
i
Also, c o n s e r v a t i o n of charge requires that the charge entering t h e solution phase, i2, m u s t be e q u a l to the charge
leaving the m a t r i x phase, i~, w h i c h in one d i m e n s i o n is exp r e s s e d as follows
SLk M ] zl ~
C o n c e n t r a t e d solution t h e o r y (22-24), in particular the

m u l t i c o m p o n e n t diffusion e q u a t i o n (MDE), is u s e d to dev e l o p t h e e q u a t i o n s describing the species transport. This
t h e o r y is u s e d b e c a u s e the solvent, SOC12, is i n v o l v e d in an
electrochemical reaction and is not p r e s e n t in e x c e s s
a m o u n t s relative to the solute, LiAIC14. The M D E for a
g i v e n species can be t h o u g h t of as a force balance w h i c h
d e s c r i b e s h o w the m o t i o n of that species is affected by the
m o t i o n of all the other species in the electrolyte. The
M D E s are i n v e r t e d (22-24) to obtain explicit e x p r e s s i o n s
for the species fluxes. The resulting flux e x p r e s s i o n s for a
b i n a r y electrolyte are
i2tiI
Ni = -DeffVci
' = 0
Ox
No = -Deff~Tco q- Cov l
Ox
(28)
v I = ~ NiVi = ~ ci~Zivi
i
Si k a
T UkF
[13]
a n d the effective diffusivity, D,ff, is defined

Deff= De ~1
[14]
w h e r e 41 is c h o s e n to be 1.5; this v a l u e is consistent with

earlier w o r k (7, 15). E q u a t i o n [14] relates t h e electrolyte diffusivity in the porous region, Deft, to that in the b u l k solution, D, by a c c o u n t i n g for the effects of porosity and tortuosity in the porous region (7, 15).
Solvent and electrolyte material balances.--Equations [9],

[11], [12], and [14] are i n t r o d u c e d into Eq. [8] to obtain the
following material balance e x p r e s s i o n s for t h e charged
species and for the solvent
a(eci)
(
-- - V .
-De~lVci
q-
i2t,"
z~F
)
4- ei v l
OiL=
Ox
[7]
(i=+,-,o)
[8]
~k
[9]
T h e subscripts +, - , and o refer to Li A1C14-, and SOC12,

respectively. In Eq. [8], 9 represents the fraction of the porous e l e c t r o d e v o l u m e w h i c h is v o i d of the m a t r i x phase
and filled w i t h electrolyte, ci is the c o n c e n t r a t i o n of species
i in t h e solution, Ni is the flux of species i a v e r a g e d over the
cross sectional area of the porous region, and R~ is the prod u c t i o n rate of species i per unit v o l u m e of electrode d u e
to c h e m i c a l or e l e c t r o c h e m i c a l reaction. Here, reaction [4]
is a s s u m e d to be the only reaction o c c u r r i n g w i t h i n the porous region. In Eq. [9], S~.kis the stoichiometric coefficient
of species i in e l e c t r o c h e m i c a l reaction k w h e n written in
the f o r m (24)
ik
(i =
nkF
o(eCo)
Ot
where
Ri =
(i = +, - , o)
__ S l , k a
w h e r e j is the local transfer current in a m p e r e s per cubic

c e n t i m e t e r s and ik is the rate of e l e c t r o c h e m i c a l reaction k
per unit area of active electrode surface area.
The material balance e q u a t i o n for each species i in t h e
solution phase is
0(eci)
--V.Ni+Ri
Ot
[12]
In Eq. [11] and [12] t h e v o l u m e average velocity is defined
- >: ~_
0i2.=
~x
[11]
[6]
The total current transferred from the m a t r i x phase to t h e

solution phase, -ai~.JOx or Oi~_JOx, is e q u a l to the n e t rate
of e l e c t r o c h e m i c a l reaction per unit v o l u m e of electrode
j = a ~ i~ -
(i = +, - )
q- c i v m
q- - -
ziF
Ot
' +
[10]
nke-
+, --)
- - V . (_De~IVc~ + CoVl) _ ~ So.ka ik

k nkF
[15]
[16]
E q u a t i o n [15] is for t h e two u n k n o w n s c+ and c_ and can be

r e d u c e d to one e q u a t i o n for one u n k n o w n by i n t r o d u c i n g
the following relationship
c-
C+
P+
C-
[17]
E q u a t i o n [17] e x p r e s s e s c o n s e r v a t i o n of mass for a completely dissociated salt, h e r e LiA1C14, w h e r e c is the concentration of the salt (or electrolyte). In Eq. [17], v+ and v_
are the n u m b e r of Li + and A1Ch- ions f o r m e d f r o m t h e
c o m p l e t e dissociation of one m o l e c u l e of LiA1C14, respectively. S u b s t i t u t i n g Eq. [17] into Eq. [15] yields t h e electrolyte material balance
O(ec)
(
-- - V " - D e ~
Ot
i2t
)
+ cv a
z+v+F
-~
S+.ka ik
[18]
-k n k v + F
N o t e that either relation in Eq. [17] can be substituted into

t h e c o r r e s p o n d i n g species balance, Eq. [15], to obtain the
s a m e result, Eq. [18]. T h e cation (i = +) material b a l a n c e
was c h o s e n h e r e to derive Eq. [18].
Solid phase material balance.--Equation [8] for t h e solid

phases, LiC1 here, is
C)E
Ohm' s law for the m a t r i x phase.--Ohm' s law for the m a t r i x
solid phases Si,kVi
Ot --
-aik
nkF
E, 2,
331
[19]
p h a s e is (15, 20)
it = -+effVcPl
[30]
Overall material balance.---The three material balance
O'eft = ~(1 - e~ ~1
[31]
e q u a t i o n s are: Eq. [16] for t h e solvent, Eq. [18] for the electrolyte, and Eq. [19] for t h e solid species. T h e s e e q u a t i o n s
c o n t a i n t h e four u n k n o w n s , c, co, e, and v ' . T h e u n k n o w n co
can be e l i m i n a t e d f r o m t h e s e e q u a t i o n s via the following
i n d e p e n d e n t t h e r m o d y n a m i c relationship
E q u a t i o n [31] is u s e d to a c c o u n t for the effect of the m a t r i x

p h a s e tortuosity on the c o n d u c t i v i t y of the solid material,
~r. T h e initial porosity, e~ is u s e d in Eq. [31] b e c a u s e t h e matrix c o n d u c t i v i t y is a s s u m e d to c h a n g e insignificantly as
LiC1 precipitates.
E q u a t i o n [6] can be used to eliminate il f r o m Eq. [30]. Integrating Eq. [6] w i t h respect to x and a p p l y i n g the boundary c o n d i t i o n s
E q u a t i o n [19] d e s c r i b e s the porosity c h a n g e of the porous

c a t h o d e as LiC1 precipitates in the pores.
1 = cVe + coVo
[20]
w h e r e t h e partial m o l a r v o l u m e of the electrolyte, V~, is defined as

V+ = v+V+ + v_~'_
[21]
E q u a t i o n [20] e x p r e s s e s c o n s e r v a t i o n of v o l u m e and can be

t h o u g h t of as a definition for t h e partial m o l a r v o l u m e s Vi
(29). W h e n Eq. [15] and [16] are p r e m u l t i p l i e d by V+, V_, and
Vo, respectively, and t h e three resulting e q u a t i o n s are substituted into Eq. [19] an overall material balance is obtained. This is true b e c a u s e the resulting e q u a t i o n is a linear c o m b i n a t i o n of all t h e species balances. E q u a t i o n [20]
is u s e d to simplify this balance to yield the following overall material balance e x p r e s s i o n
+v.
Si,k~Ti
aik
+ (~JoSo,k+ Q~t-ms+,k + vj+ms-,k) nkF
[22]
where
at
integration yields
VxII =
[ s~
1
-- _ _
S i r~Ti
"
n4F
'
- (PoSo,+ + Q+t_"s+,+ + P+t+"+_,+)/i==
[24]
is,= = 0
i,
[33]
Oqb1
in - i2.= = -(~eff
[34]
ax
Electrode kinetics.--The e l e c t r o c h e m i c a l reaction rates, ik,

in Eq. [18] and [19] d e p e n d u p o n the local c o n c e n t r a t i o n s of
the c h e m i c a l species, the potential driving force for reaction, and t e m p e r a t u r e . A n a l o g o u s to c h e m i c a l kinetics,
t h e s e d e p e n d e n c i e s are not d e s c r i b e d by f u n d a m e n t a l
laws. The B u t l e r - V o l m e r polarization e q u a t i o n (15, 30) is
used here
( ci Ip+'kexp(~
\ RT
Ci i qi,k
The potential driving force for e l e c t r o c h e m i c a l reaction k

i s tic)1 -- (I)2 -- Uk,ref w h e r e Uk.refis the e q u i l i b r i u m potential of
reaction k m e a s u r e d relative to the r e f e r e n c e electrode.
T h e electrokinetie p a r a m e t e r s io,k,ref,aa.k, and ac,k are the exc h a n g e c u r r e n t density, anodic transfer coefficient, and cat h o d i c transfer coefficient, respectively. The transfer coefficients for a given reaction s u m to the total n u m b e r of
electrons i n v o l v e d in that reaction
c~,k + c~c.k= nk
Ohm's law for the electrolyte.--The faradaic current density, i2, is a f u n c t i o n of the c h e m i c a l potential, i+~,and solution potential, +s (20, 24). This relationship, O h m ' s law for
t h e solution phase, for a binary electrolyte is (24)
is
--VcP2
Keff
vRT ( s+.4 + t+m
\n4v+
-- ~
z+v+
So,4Ct
--
Vl~
[32]
S u b s t i t u t i n g Eq. [33] into Eq. [30] yields
ik=i~
[23]
and
il,x = in
ilz + i2,x
Only reaction [4] is a s s u m e d to occur w i t h i n the positive

electrode, hence, Eq. [7] can be substituted into Eq. [22].
T h e resulting e q u a t i o n can be integrated to yield an explicit e x p r e s s i o n for v=m in t e r m s of i2.x. B a s e d o n t h e fact
t h a t t h e c u r r e n t is zero w h e n the v e l o c i t y is zero
Vx" = i2,x = 0
x = O,
results in the following relationship
[36]
T h e rate of reaction k per u n i t v o l u m e of porous elect r o d e is aik w h e r e a is t h e available active surface area p e r
unit v o l u m e of electrode. The variable a changes as the
LiC1 precipitates on the pore walls, a c c o r d i n g to reaction
[4], and can be d e s c r i b e d by (27, 31)
[25]
n4Co/
a = a O [ l _ ( e ~\ - - - ~ /
[37]
where
v=v+
[26]
+v-
and
I~e = v+l~+ + v-I~- = v R T l n (cfa ~
[27]
In Eq. [25], t h e stoichiometric coefficients of reaction [4] are

u s e d b e c a u s e this reaction is c h o s e h as t h e r e f e r e n c e elect r o d e reaction. Also, the effective electrolyte conductivity,
Keff, is defined a n a l o g o u s l y to the effective electrolyte diffusivity,
Deft
[28]
Keff = KE~1
E q u a t i o n s [20], [27], and [28] can be s u b s t i t u t e d into Eq. [25],

a s s u m i n g f and a s are constants, to yield t h e following
O h m ' s law e x p r e s s i o n for t h e electrolyte
+ t+.
is - -V@s
Ke ~1
w h e r e ~ is an e x p e r i m e n t a l l y d e t e r m i n e d p a r a m e t e r u s e d
to d e s c r i b e the m o r p h o l o g y of the precipitate. In writing
Eq. [37] it is a s s u m e d that all the LiC1 p r o d u c e d f r o m reaction [4] precipitates i n s t a n t a n e o u s l y and passivates the surface it covers. Large values of ~ indicate n e e d l e - s h a p e d deposits w h e r e a s small values r e p r e s e n t flat deposits (31).
S u b s t i t u t i n g Eq. [35] and [37] into Eq. [7] yields the foll o w i n g e q u a t i o n e x p r e s s i n g c o n s e r v a t i o n of current
-- - - 7
\n4v+
z+v+ n4(1 --
--
c~Te)/ c
[29]
Ox
\ +-~-/ J k
/ OCa+kF
--
-- Ukref))
|
exp
\Ci.~fl
'
( - ~+e'kF
(q~i -
Ci t qi,k
- [!\ei,,.o,]-<P2 - Uk .ref)) ]
[38]
332
Altogether, six e q u a t i o n s and six u n k n o w n s are u s e d to

d e s c r i b e the porous electrode region. The six e q u a t i o n s
are t h e electrolyte material balance, Eq. [18]; the solid species material balance, Eq. [19]; t h e overall material balance,
Eq. [24]; O h m ' s law for the electrolyte, Eq. [29]; O h m ' s law
for t h e m a t r i x phase, Eq. [34]; and c o n s e r v a t i o n of current
u s i n g the B u t l e r - V o l m e r equation, Eq. [38]. The six unk n o w n s are the electrolyte concentration, c; the porosity, e;
the v o l u m e average velocity, v=m;the faradaic c u r r e n t density, i2,=; the potential in t h e m a t r i x phase, (P,; and t h e potential in t h e solution phase, q~2. Simplified forms of Eq.
[18], [19], [24], [29], [34], and [38] are u s e d to d e s c r i b e t h e rem a i n i n g regions of the cell: the reservoir, the separator,
and the LiC1 film.
R e s e r v o i r . - - T h e reservoir, the space b e t w e e n t h e separator and the positive porous electrode, contains electrolyte
and serves to supply SOC12 to the positive e l e c t r o d e as it is
c o n s u m e d via reaction [4]. The solid m a t r i x phase does not
exist in this region, therefore t h e u n k n o w n s e, i~.=, and (P~
h a v e no m e a n i n g . T h e y are treated as d u m m y variables
and their values are arbitrarily set as follows
9= 1
[39]
(P~ = 0
[40]
i~.= = 0
[41]
4Li + 2SOC12 ~ 4LiC1 + SO2 + S
[48]
R e s e a r c h e r s (32-35) believe that the film passivates the Li

and inhibits the mass transport of SOC12 to the Li surface.
S o m e w o r k e r s (34, 35) h a v e d e s c r i b e d t h e LiC1 film as consisting of two parts: a relatively thin, n o n p o r o u s layer of
LiC1 f o r m e d on top of the Li anode surface called t h e solid
electrolyte i n t e r p h a s e (SEI) and a m u c h thicker, porous
layer of LiC1 f o r m e d on top of the S E I called the s e c o n d a r y
porous layer. T h e s e workers h a v e p r o p o s e d that it is the
S E I w h i c h passivates the Li surface b e c a u s e the s e c o n d a r y
layer has a coarse crystalline, porous structure (32) w h i c h
c a n n o t be a s s u m e d to h a v e t h e resistance properties necessary for c o m p l e t e passivation of the Li. P e l e d (35) v i e w s
t h e s e c o n d a r y porous layer as a m e m b r a n e w h i c h inhibits
t h e flow of ions to and f r o m the SEI. Here, the transition
b e t w e e n the S E I and s e c o n d a r y layer is a s s u m e d to be distinct, and t h e layers are treated separately. The S E I surface
is treated h e r e as the Li a n o d e surface h a v i n g modified
(passivation) kinetics and t h e s e c o n d a r y porous LiC1 layer
is treated here like a separator.
The g o v e r n i n g e q u a t i o n s for the secondary, porous LiC1
film are d e v e l o p e d in the s a m e m a n n e r as t h o s e for the separator. The e q u a t i o n s are: a c o n s t a n t porosity
9 = ef
[49]
the electrolyte balance
U s i n g Eq. [41] in Eq. [33] yields

~C
i2,x = in
E q u a t i o n s [18] and [29] for t h e p o r o u s electrode can be

simplified for t h e reservoir u s i n g Eq. [39] and [42]. The electrolyte balance b e c o m e s
O h m ' s law for the electrolyte
in
0C
DV2c - V - (cv m)
[43]
[50]
e f - = Def~3V2c - V 9 ( c v m)
Ot
[42]
v R T (s+,4 + t+" _
.
Ke[3 -- -Vr
- ~ - - - \n4v+
So4C~o
z+v+
~I vc [51]
n4(1 - c f / e ) /
Ot
and O h m ' s law for the electrolyte b e c o m e s

in
K
v R T [ S+,4
- -VdP2
-- F - -
\n4v+
So.4C(Zo \ Vc
J - - [44]
n4(1 - c~?~)/ c
t+ m
-~
z+v+
N o t e that effective properties are not u s e d in Eq. [43] and

[44] b e c a u s e no m a t r i x phase exists. E q u a t i o n [24] is u s e d
to calculate the v o l u m e average velocity. In s u m m a r y , the
six g o v e r n i n g e q u a t i o n s for this region are Eq. [24], [39],
[40], [42], [43], and [44].
Separator.--The
separator is an inert, porous layer (usually a glass m a t t i n g material) w h i c h p r e v e n t s the n e g a t i v e
and positive electrodes f r o m t o u c h i n g and t h u s s h o r t i n g
t h e cell. The separator porosity (e~) is constant, h e n c e
9= 9
[45]
The solid phase of the separator is a n o n c o n d u c t i n g material; gP~ does not exist and is set to zero as in Eq. [40]. All
c u r r e n t resides in the electrolyte, h e n c e Eq. [42] applies.
U s i n g Eq. [42] and [45] to simplify Eq. [18] and [29], the electrolyte balance for the separator is
ac
e ~ - = D9
Ot
[46]
- V . ( c v m)
and O h m ' s law for t h e electrolyte is

in
v R T ( s+.4 + t+ m
-
K9 ~2
s~176
-I Vc
VgP~
--
-- T
\n4v+
Z+v+
n4(1 - c~Z~)/
[47]
and Eq. [24], [40], [42]. The value of the e x p o n e n t ~3 is set to

1.5.
The s e c o n d a r y porous film grows as t i m e progresses but
its t h i c k n e s s is k e p t c o n s t a n t here. F i l m g r o w t h m a y o c c u r
by reaction [3] w h e r e the C1- ions are a p r o d u c t of t h e cathode reaction. Tsaur and Pollard (7) a s s u m e that t h e rate of
reaction [48] governs the film growth. H o w e v e r , reaction
[48] is the s u m of the two e l e c t r o c h e m i c a l half-reactions [ 1]
and [4] and does not occur on discharge b e c a u s e the lithi u m is anodically protected. The s e c o n d a r y porous layer is
not of u n i f o r m t h i c k n e s s o v e r the surface of the l i t h i u m
(33), its m o r p h o l o g y d e p e n d s strongly on t h e storage t e m p e r a t u r e (33), and m e c h a n i c a l r u p t u r e m a y occur d u r i n g
d i s c h a r g e (32). B e c a u s e of these complications, t h e film
t h i c k n e s s is k e p t c o n s t a n t and can be t h o u g h t of as an
average v a l u e of the t h i c k n e s s w h i c h varies in space and
time. The m o d e l will be u s e d to predict the effects of the
film t h i c k n e s s and porosity on the cell performance.
Boundary
conditions.--The
boundaries, from left to
right in Fig. 1, are the Li a n o d e surface (taken as the S E I
surface here), the LiC1 film/separator interface, the separator/reservoir interface, the reservoir/porous c a t h o d e interface, and the c a t h o d e current collector surface. The gove r n i n g e q u a t i o n s at each b o u n d a r y are g i v e n next.
SEI surface.--The
S E I is treated as the Li a n o d e surface
w i t h m o d i f i e d kinetics. The rate of reaction [1] is calculated
u s i n g Eq. [35] with kinetic p a r a m e t e r s r e p r e s e n t i n g the
passivation. L i t h i u m ions m u s t travel f r o m the S E I surface
at the s a m e rate at w h i c h t h e y are produced, thus the flux
of this species m u s t equal its reaction rate
N o t e that effective properties h a v e b e e n u s e d in Eq. [46]

and [47] to characterize the transport and c o n d u c t i v i t y in
t h e separator. The e x p o n e n t ~2 is analogous to ~1 and its
v a l u e is .set to 1.5. The overall material balance is Eq. [24].
In s u m m a r y , the six g o v e r n i n g e q u a t i o n s for the separator
are Eq. [24], [40], [42], [45], [46], and [47].
Lithium
chloride film.--The
stability of the lithium
a n o d e is attributed to the LiC1 film w h i c h forms from the
corrosion of the Li by the SOC12 on o p e n circuit (32-35)
N+ = -v+Def~3Vclf +
i2t+ u
+ v+cv m = -
z+F
s+,~ .
h
nlF
[52]
The solvent flux is zero at this b o u n d a r y

No = -Def~3Vcofr + CoVm = 0
[53]
U s i n g Eq. [20], Eq. [53] can be written

No = Def~3"
VeVClf ~- (1
cfde)v m = 0
[54]
333
I n Eq. [52]-[54], a n d in equations to follow, only the x comp o n e n t of the del operator is i n t e n d e d a n d the vertical bar
with a subscript, IJ, indicates that the q u a n t i t y is to be evalu a t e d at the interface of the region j. At the film interface,
all the c u r r e n t is transferred from the a n o d e surface to the
solution phase, h e n c e i~.~is zero a n d Eq. [42] applies. Equation [7] for a flat plate electrode is
that all of the c u r r e n t has b e e n transferred from the solution phase to the m a t r i x phase at the c u r r e n t collector,
thus
i2,x = 0
[66]
Also, the v o l u m e average velocity is a s s u m e d to be essentially zero at this b o u n d a r y

v=I = 0
in = Y~ ik
[55]
where Eq. [35] is used to calculate ik. The porosity is treated

as a d u m m y variable a n d it is arbitrarily set equal to the
LiC1 film porosity, Eq. [49]. At this b o u n d a r y dpl is arbitrarily set to zero, Eq. [40], to establish a reference point from
w h i c h to calculate all other potentials. The absolute values
of q), a n d q)~ have no significance; only the value of the difference 9 1 - r is meaningful. The value of r given Eq.
[40], is d e t e r m i n e d from Eq. [55]. In s u m m a r y , the b o u n d ary c o n d i t i o n s at the SEI b o u n d a r y are Eq. [40], [42], [49],
[52], [54], a n d [55].
L i C l f i l m ~ s e p a r a t o r i n t e r f a c e . - - A t this b o u n d a r y the flux
of each species i is c o n t i n u o u s
Nilf = N~I~
As at the SEI surface, the flux of each species m u s t equal

its reaction rate. The electrolyte flux is zero here
N+ = -v+De~'Vclp~ +-
9f~3Vcff = 9
[58]
[59]
As in the film a n d separator regions, Eq. [40] a n d [42] apply.

The porosity is arbitrarily set equal to 9 Eq. [45]. I n summary, the b o u n d a r y conditions at this b o u n d a r y are Eq.
[40], [42], [45], [57], [58], a n d [59].
Vr
e~2Vc]~ = Vc]~
[60]
I n i t i a l c o n d i t i o n s . - - T o complete the e q u a t i o n set, the

initial c o n d i t i o n s m u s t be specified for those variables that
d e p e n d explicitly on time, c a n d e. These initial conditions
are
c = cinit
9 = e~
(all x)
a n d Eq. [40], [42], a n d [45].

Reservoir~porous electrode i n t e r f a c e . - - T h e b o u n d a r y con-
ditions at this interface i n c l u d e c o n t i n u i t y of flux

VC[r = 9
du
dt
dq
-
dt
V~P21~= e~'vq~2]ne
[64]
a n d Eq. [42]. This b o u n d a r y i n c l u d e s the porous electrode

surface, h e n c e porosity will change as will the v o l u m e
average velocity as described by Eq. [19] a n d [24], respectively. E q u a t i o n [34] is applied at this b o u n d a r y as follows
VcP,lp~ = 0
[74]
dt
dT
C
dt
[75]
dt
The c h a n g e in the m e c h a n i c a l work, d w / d t , is zero; no mechanical work is done on or b y the cell w h e n the v o l u m e is
constant. The change in the heat c o n t e n t of cell, dq/dt, is
a t t r i b u t e d to three sources (sinks): heat transferred across
the cell b o u n d a r i e s (~t), heat generated by polarization @p),
a n d heat generated b y e n t r o p y effects (6) (36). The heat
transfer can be described b y
O~t = - h o ( T -
TA)
[76]
where ho is the heat transfer coefficient characterizing the

heat flow from the cell to the s u r r o u n d i n g s . Here, the temperature of the s u r r o u n d i n g s is a s s u m e d to r e m a i n constant at TA. The r e m a i n i n g two sources of heat are given b y
(36)
~+~=i
Eoc - E -
T dEoc~
d T / = in (Etn - E)
[77]
[65]
Li]SOC12
battery m a y be pictured in one d i m e n s i o n as a series of
cells s a n d w i c h e d together. The c u r r e n t collector of the porous cathode separates the cathodes of two consecutive
cells. With this configuration in mind, the o n e - d i m e n s i o n a l
d i s t r i b u t i o n of the faradaic c u r r e n t density will be essentially zero at the c u r r e n t collector. That is, it is a s s u m e d
P o r o u s electrode c u r r e n t collector s u r f a c e . - - A
dw
+ - -
where u is the i n t e r n a l energy of the cell. When c o n s t a n t

v o l u m e conditions are a s s u m e d
[63]
c o n t i n u i t y of faradaic c u r r e n t
[73]
Cell e n e r g y b a l a n c e . - - A n e n e r g y b a l a n c e is i n c l u d e d in
the m o d e l to d e t e r m i n e the cell t e m p e r a t u r e as it changes
with time. The e n e r g y balance follows from the first law of
thermodynamics
[61]
[62]
[72]
(porous electrode)
e~2V~p2[~= V~P2[r
[71]
=J
pe
du
c o n t i n u i t y of faradaic c u r r e n t
[70]
where j is calculated u s i n g Eq. [7], [35], a n d [37]. The porosity c h a n g e is calculated u s i n g Eq. [19].
c o n t i n u o u s velocity
Vx% = V~"pr
[69]
= 0
Oi2.=
S e p a r a t o r ~ r e s e r v o i r i n t e r f a c e . - - T h e b o u n d a r y conditions
here are analogous to those at the LiC1 film/separator

b o u n d a r y . These e q u a t i o n s are: c o n t i n u i t y of flux
[68]
The transfer c u r r e n t at this b o u n d a r y is given b y
E q u a t i o n [47] for the separator a n d Eq. [51] for the LiC1 film
are equated, a n d Eq. [58] is used, to yield the following
e q u a t i o n which expresses c o n t i n u i t y of faradaic c u r r e n t
9~VcP2]f = e~2Vq)2l~
+ v+cv u = 0
Similarly, Eq. [29] b e c o m e s
c]X
S u b s t i t u t i n g Eq. [11], [17], [20], a n d [57] into Eq. [56] yields

the following e q u a t i o n expressing c o n t i n u i t y of the electrolyte flux
z+F
VcIpe = 0
[56]
[57]
i2t+ u
U s i n g Eq. [66] a n d [67], Eq. [68] can be written
a n d the velocity is c o n t i n u o u s
Vx=[~ = v~=[~
[67]
Etn in Eq. [77], t e r m e d the t h e r m o n e u t r a l potential, is the

theoretical open-circuit potential of the cell at absolute
zero. S u b s t i t u t i n g Eq. [75], [76], a n d [77] into Eq. [74] yields
the overall energy b a l a n c e
dT
C - - = - h o ( T - TA) + in (Etn
dt
- -
E)
[78]
d. Electrochem. Soc., Vol. 136, No. 2, February 1989 9 The Electrochemical Society, Inc.
334
Table I. Parameter values used in model
Parameter
Physical properties
Ref.
Value
v
z+
t+"
V~ (cm3/mol)
~ZL,Cl(cm3/mo1)
D (cm2/s)
Etn (V)
C (J/cm2K)
1
1
0.5
77.97
20.5
~
-3.723
0.2
Parameter
v_
z
t "
~ro(cm3/mol)
(~(~-1 cm-b
K(~-1 em-l)
(7, 38)
(48)
(36)
(5, 7, 14)
dEoc/dT (V/K)
Value
Ref.
1
-1
0.5
72.63
45.5
t
2.28 x 1O-4
(45)
(49)
(36)
Kinetic parameters
Parameter
Li oxidation (reaction [1])

Value
s+,l
-1
q+.l
io,l,~a(A/em2)
5.0 x 10 4
Ul.~ef(V)
Et, + T dEoc/dT
~a,1
ar
nl
Ref.
Parameter
SOC12 reduction (reaction [4])

Value
s+.4
So.4
SLiC1,4
q+,4
qo,4
a~
(36)
0.25
0.75
1
(A/em3)
U4.~f(V)
~.4
~,4
n4
-2
-1
2
1
0.5
1.0
0.05
0.0
Ref.
(31)
1
2
tSee Appendix.
N o t e that each t e r m in Eq. [78] is based on the total active
surface area in the cell. The initial c o n d i t i o n for T h e r e is
T = TA
(all x)
[79]
Model Parameters
T h e p a r a m e t e r values i n p u t to t h e m o d e l are listed in
T a b l e I. The partial m o l a r v o l u m e s and t r a n s f e r e n c e n u m bers w e r e a s s u m e d to be c o n s t a n t t h r o u g h o u t t h e disc h a r g e at the values listed in Table I. The kinetic p a r a m e ters io,,,~f, aa,1, C~c,1, and a~
w e r e c h o s e n so that t h e
m o d e l predictions c o m p a r e d favorably w i t h e x p e r i m e n t a l
data (32, 37-41). A t e m p e r a t u r e d e p e n d e n t e x p r e s s i o n for
t h e diffusion coefficient and a t e m p e r a t u r e , c o n c e n t r a t i o n
d e p e n d e n t e x p r e s s i o n for the c o n d u c t i v i t y are g i v e n in the
Appendix.
The i n d e p e n d e n t adjustable p a r a m e t e r s in this m o d e l
d e v e l o p m e n t are the porous e l e c t r o d e t h i c k n e s s (Spe), t h e
initial porosity o f t h e porous electrode (e~ t h e t h i c k n e s s o f
t h e electrolyte reservoir (St), the t h i c k n e s s of t h e separator
(Ss), t h e porosity of the separator (es), t h e LiC1 film thickn e s s (Sf), t h e LiC1 film porosity (el), the initial electrolyte
c o n c e n t r a t i o n (c~it), the h e a t transfer coefficient (ho), the
c u r r e n t density (in), and the t e m p e r a t u r e of the surroundings (TA). One objective of this w o r k was to use the m o d e l
to d e t e r m i n e w h i c h o f t h e s e i n d e p e n d e n t adjustable par a m e t e r s affects cell p e r f o r m a n c e the most. Table II lists
typical values for t h e s e i n d e p e n d e n t adjustable parameters (5). U n l e s s o t h e r w i s e noted, t h e s e base case values are
u s e d t h r o u g h o u t t h e w o r k p r e s e n t e d here.
Method of Solution
T h e s y s t e m of coupled, nonlinear, ordinary differential
e q u a t i o n s d e s c r i b i n g the Li/SOC12 cell, s h o w n in Fig. i, is
s o l v e d n u m e r i c a l l y b e c a u s e an analytical solution is not
possible. The spatial derivatives are a p p r o x i m a t e d u s i n g
finite differences accurate to O(hx) 2 w h e r e h x is the largest
step size in the x direction. I m p l i c i t stepping, accurate to
O(ht), is u s e d for the t i m e derivatives. A N e w t o n - R a p h s o n
Table II. Base case values of the independent adjustable parameters
Parameter
Spe (cm)
Sr (cm)
Ss (cm)
Sf (cm)
c~nit(]14)
in (A/cm2)
Value
0.0335
0.01
0.0127
0.001
1.5
0.03
Parameter
Value
e~
0.85
e~
ef
ho (J/cm2Ks)
TA (K)
0.7
0.1
6.0 x 10-~
298.15
a l g o r i t h m using d e B o o r ' s b a n d e d m a t r i x solver (42-43) is

u s e d to solve the s y s t e m of finite difference equations. The
p r o c e d u r e is iterative and requires initial guesses of the
u n k n o w n s . S t e p sizes in b o t h space and t i m e w e r e r e d u c e d
until p r e d i c t e d cell voltages w e r e r e p r o d u c i b l e to three
significant digits.
Results and Discussion

F i g u r e 2 shows p r e d i c t e d electrolyte c o n c e n t r a t i o n profiles and h o w t h e y c h a n g e w i t h time. N o t e that the concentration profiles are relatively flat in t h e separator and reserv o i r regions indicating that diffusion, migration, and
c o n v e c t i o n of species are essentially u n i n h i b i t e d in t h e s e
regions. C o n v e c t i o n contributes least to t h e species transport; vx" is O(10 .5 cm/s) and the c o n v e c t i o n t e r m is an
o r d e r of m a g n i t u d e less t h a n the diffusion and m i g r a t i o n
t e r m s in Eq. [18], [43], [46], and [50]. The large c o n c e n t r a t i o n
gradients in t h e film region are due to the small porosity of
this region w h i c h r e d u c e s significantly the effective diffusivity. N e a r the b e g i n n i n g of discharge t r a n s p o r t in t h e porous electrode region is essentially uninhibited. As the discharge proceeds, LiC] begins to fill the pores of the
e l e c t r o d e and transport b e c o m e s m o r e difficult as evid e n c e d by the steeper c o n c e n t r a t i o n gradients at later
times. T h e electrolyte c o n c e n t r a t i o n increases t h r o u g h o u t
the cell as t i m e progresses and the solvent c o n c e n t r a t i o n
decreases a c c o r d i n g to Eq. [20]. T h e s e profiles s h o w that
t h r o u g h o u t m o s t of the d i s c h a r g e cell p e r f o r m a n c e is dictated by the rate of reaction [4] at the cathode. Tsaur and
Pollard (7) predict diffusion control as e v i d e n c e d by the
large c o n c e n t r a t i o n gradients in t h e separator of their simu l a t e d cell; t h e y a s s u m e a c o n s t a n t reservoir c o n c e n t r a t i o n
a priori. This difference, reaction control h e r e vs. diffusion
control (7), is due to the different g o v e r n i n g e q u a t i o n s and
b o u n d a r y conditions as well as the differing i n p u t parameters u s e d in their m o d e l and the p r e s e n t model. Specifically, Tsaur and Pollard use different electrokinetic par a m e t e r s and investigate h i g h e r discharge rates (e.g., 80
m A / c m 2) t h a n are used here. As m e n t i o n e d earlier, their
m a t h e m a t i c a l description of the film and r e s e r v o i r regions
are different f r o m those u s e d here; t h e y a s s u m e Li corrosion d u r i n g t h e discharge and treat the reservoir as a wellm i x e d ~egion. In addition, differing c o n d u c t i v i t y and diffusion coefficient expressions are used. T h e s e differences
all c o n t r i b u t e to the differences in t h e p r e d i c t e d quantities. F r o m Fig. 2 it can be seen that the c h a n g e in the concentration across the reservoir is a b o u t half w h a t it is in the
separator and, u n d e r conditions of diffusion control, this
c h a n g e could effect the results significantly. H i g h e r dis-
335
30.0
4.0
t = 2160 s
t = 1440 s
............
t =720s
___ t = O s
t = 2160 s
25.0
t = 1440 s
..............
t = 720 s
t=Os
:80.0
3.0
15.0
I0.0
2.0
\
\
5.0
Sep.
Res.
Porous
electrode
0.0
1.0
0.00
0.02
0.00
Fig. 2. Typical electrolyte concentration profiles

c h a r g e rates, l o w e r t e m p e r a t u r e s , f a s t e r p o r o u s e l e c t r o d e
r e a c t i o n k i n e t i c s (i.e., l a r g e r e x c h a n g e c u r r e n t d e n s i t i e s for
t h e t h i o n y l c h l o r i d e r e d u c t i o n o n t h e c a r b o n electrode),
l o w e r initial c o n c e n t r a t i o n s , a n d s m a l l e r p o r o s i t i e s all cont r i b u t e to c h a n g i n g t h e r e a c t i o n c o n t r o l l e d c o n d i t i o n s obs e r v e d h e r e to d i f f u s i o n c o n t r o l l e d c o n d i t i o n s .
F i g u r e s 3-5 i l l u s t r a t e tt~e s p a c e - t i m e b e h a v i o r of t h e por o u s e l e c t r o d e porosity, f a r a d a i c c u r r e n t d e n s i t y , a n d over-
0.01
0.02
0.03
- S f - S s - S r (cm)
Fig. 4. Typical profiles of the faradaic current density in the porous
electrode.
0.04
p o t e n t i a l , r e s p e c t i v e l y . T h e s e profiles s h o w t h a t t h e react i o n r a t e d i s t r i b u t i o n c h a n g e s v e r y little as t i m e

p r o g r e s s e s . T h e r e a c t i o n r a t e will b e g r e a t e s t at t h e f r o n t of
t h e p o r o u s e l e c t r o d e b e c a u s e t h e m a t r i x c o n d u c t i v i t y (or) is
m u c h l a r g e r t h a n t h e e l e c t r o l y t e c o n d u c t i v i t y (K) (7). T h a t
is, at t h e r e s e r v o i r / p o r o u s e l e c t r o d e i n t e r f a c e all c u r r e n t resides in the solution phase but upon entering the porous
e l e c t r o d e t h e c u r r e n t will b e t r a n s f e r r e d r a p i d l y to t h e m a t r i x p h a s e b e c a u s e t h e m a t r i x p h a s e offers less r e s i s t a n c e
to c u r r e n t flow. H o w e v e r as LiCI p r e c i p i t a t e s , fills t h e
p o r e s as s h o w n in Fig. 3, a n d d e c r e a s e s t h e a v a i l a b l e a c t i v e
s u r f a c e area, a c c o r d i n g to Eq. [37], t h e r e a c t i o n r a t e distrib u t i o n b e c o m e s m o r e u n i f o r m . T h i s c h a n g e c a n b e s e e n in
Fig. 4 w h e r e t h e i2.= d i s t r i b u t i o n flattens out; t h e r e a c t i o n
0.8
0.00
~
. /
0.6
. /
-0.05
0.4
_ _ _ _ _
..............
t=0s
t = 720 s
-0.10
,0,
I
. . . .
..............
t = 1440 s
~ --2160 s
0.2
t=Os
t = 720 s
t = 1440 s
$ = 2160 s
-0.15
0.0
0.00
0.02
0.01
0.03
-0.20
:c.-Sf-S
s-S
(em)
Fig. 3. Typical porosity changes in the porous electrode during discharge.
0.00
0.01
0.02:
O.OB
o ~ - S f - S s - S r (era)
Fig. 5. Typical overpotentiol profiles in the porous electrode
336
rate is the slope of the i2.= vs. x curve. F i g u r e 5 shows that

t h e overpotential, the driving force for e l e c t r o c h e m i c a l reaction, is highest at the front of the electrode as e x p e c t e d .
T h e overpotential increases w i t h t i m e indicating that the
e l e c t r o c h e m i c a l reaction m u s t p r o c e e d at a faster rate to
c o m p e n s a t e for decreasing available active surface area.
As the end of discharge is approached, the front portion
of the electrode b e c o m e s clogged w i t h LiC1 precipitate
(see Fig. 3). L i t h i u m ions are u n a b l e to cross this barrier
h e n c e the electrolyte c o n c e n t r a t i o n increases rapidly in
the film, separator, and reservoir as it is continually prod u c e d at t h e anode. At this p o i n t t h e electrolyte c o n t a i n e d
in the pores of the porous electrode supplies the l i t h i u m
ions c o n s u m e d in r e d u c t i o n reaction [4]. The electrolyte
c o n c e n t r a t i o n drops in the vicinity of the highest reaction
rate (the front of the electrode) and the electrolyte supply
c o n t a i n e d in t h e b a c k portion of the electrode m u s t diffuse
to this reaction plane. This b e h a v i o r can be seen from
Fig. 4 w h e r e t h e current density distribution at t = 2160s
falls b a c k f r o m t h e flatter profiles exhibit at earlier times.
Eventually, t h e front of t h e e l e c t r o d e b e c o m e s d e p l e t e d of
electrolyte and is u n a b l e to s u p p o r t further reaction, h e n c e
c u r r e n t flow, and the cell fails. This failure is indicated by
the m o d e l w h e n c o n v e r g e n c e c a n n o t be achieved.
The m o d e l can be used to d e m o n s t r a t e the effects of the
i n d e p e n d e n t design criteria on cell performance. T h e least
influential parameters, for the reaction controlled conditions here, w e r e found to be Sr and Ss. F o r e x a m p l e , decreasing either Sr or S~ by an order of m a g n i t u d e resulted
in changes in t h e discharge t i m e and cell voltage of less
t h a n 1%. T h e m o s t influential p a r a m e t e r s on cell performa n c e w e r e f o u n d to be Spe, e~ and ci,~t. The p a r a m e t e r s characterizing the LiC1 film, ef and Sf, s h o w small to m o d e r a t e
effects on cell performance.
As s h o w n in Fig. 6, b e y o n d a porous electrode t h i c k n e s s
of a p p r o x i m a t e l y 0.1 c m there is little gain in cell lifetime.
Apparently, for t h i c k n e s s e s b e y o n d 0.1 c m the advantages
of i n c r e a s e d active surface area and electrolyte storage are
d i m i n i s h e d by the increase in cell resistance and h e n c e decrease in cell lifetime. It is difficult to d e t e r m i n e the effect
of the p o r o u s electrode porosity on cell p e r f o r m a n c e because w h e n porosity is c h a n g e d the active surface area, a,
is also changed. K e e p i n g a c o n s t a n t here, t h e cell lifetime
is d e c r e a s e d by 49 and 86% for e~ decreased to 0.6 and 0.35,
respectively. This d e c r e a s e in lifetime occurs s i m p l y be-
1.0
0.9
cause there exists less v o i d v o l u m e for the precipitating

LiC1 to fill. Changes in Spe and e~ h a v e v e r y little effect on
t h e operating voltage and t e m p e r a t u r e ; the voltage and
t e m p e r a t u r e v a r i e d by less t h a n 1% for the cases studied
here.
F i g u r e 7 shows the p r e d i c t e d effect of initial electrolyte
c o n c e n t r a t i o n on cell lifetime. Caution is n e e d e d w h e n
c o m p a r i n g cell p e r f o r m a n c e for different c o n c e n t r a t i o n s
b e c a u s e the average operating voltage decreases as initial
electrolyte c o n c e n t r a t i o n decreases. F o r e x a m p l e , the
average operating voltage for cl~it = 0.25M was a b o u t 8%
l o w e r than that for the base case. This c o n c e n t r a t i o n c o u l d
not be i n c l u d e d in Fig. 7 b e c a u s e the p r e d i c t e d voltage
transient fell b e l o w the cutoff voltage (2.9V) c h o s e n to det e r m i n e cell lifetime. B e y o n d a c o n c e n t r a t i o n of approxim a t e l y 2M there is little increase in cell lifetime or average
cell voltage. At c o n c e n t r a t i o n s b e l o w 1M the o v e r p o t e n t i a l
r e q u i r e d to drive the e l e c t r o c h e m i c a l reaction at a fast
e n o u g h rate to s u p p o r t t h e current draw is necessarily
high, especially at the front of the porous electrode. This
acceleration of reaction rate causes the pores to fill up
q u i c k l y with LiC1, and the cell fails rapidly as s h o w n in
Fig. 7. Also, for initial c o n c e n t r a t i o n s of a b o u t 0.5M and
b e l o w the shape of the cell voltage transient changes; cell
voltage initially increases, reaches a m a x i m u m , and t h e n
decreases. This initial increase in voltage is attributed to
t h e rather large initial increase in c o n d u c t i v i t y as the concentration of lithium ions increases. L a t e r the voltage decreases due to the decreasing porosity in the porous elect r o d e and the resulting increase in resistivity.
The porosity of the LiC1 film w h i c h forms on the lithium
a n o d e has a m o d e r a t e effect on cell performance. P o r o s i t y
of this film varies d e p e n d i n g on storage t e m p e r a t u r e ;
h i g h e r storage t e m p e r a t u r e s t e n d to p r o d u c e larger LiC1
crystals and m o r e c o m p a c t films (33). Several observations
can be m a d e h e r e from the m o d e l predictions. F i l m porosities b e y o n d 0.1 s e e m to h a v e little to no effect on cell lifetime, voltage, or t e m p e r a t u r e . B e l o w a porosity of 0.1, cell
voltage begins to decrease due to the greater h i n d r a n c e of
species transport in the film. F o r e x a m p l e , for a porosity of
0.05, the average cell voltage and cell lifetime are r e d u c e d
by 3% as c o m p a r e d to the base case. W h e n porosity is ext r e m e l y low (e.g., 0.005) the m o d e l predicts that the cell will
n o t operate for the 30 m A / c m 2 drain c o n s i d e r e d here. F o r a
film porosity of 0.025, t h e m o d e l predicts h i g h e r cell t e m -
0.7
. . . .
. . . .
. . . .
. . . .
0,6
0.8
0.7
_
0.5
0.6
0.5
0.4
0.4
0.3
. . . .
0.00
0.05
0.10
Spe
0.15
0.20
(em)
Fig. 6. Dependence of cell lifetime on porous electrode thickness
0.3
n
0.0
1.0
2.0
]
3.0
4.0
Cinit (M)
Fig. 7. Dependence of cell lifetime on initial electrolyte concentration
3.0
i
2.5
i
1
i n = 15 mA/cm 2
2.0
i n = 30 mA/cm 2
i n = 60 mA/cm 2
1,5
'
0.0
20.0
40.0
60.0
80.0
(c/era2)
Fig. 8. Dependence of cell lifetime and capacity on discharge rate
p e r a t u r e s ( a b o u t 10~ h i g h e r o n t h e a v e r a g e ) a n d a n avera g e cell v o l t a g e a b o u t 11% l o w e r t h a n t h a t for t h e b a s e bec a u s e of t h e i n c r e a s e d cell r e s i s t a n c e . T h e s e r e s u l t s s h o w
t h a t it is a d v a n t a g e o u s to m a i n t a i n low t e m p e r a t u r e stora g e ( r o o m t e m p e r a t u r e ) so t h a t t h e film d o e s n o t b e c o m e
too compact.
T h e film t h i c k n e s s h a s little effect o n cell p e r f o r m a n c e
for t h e c o n d i t i o n s s t u d i e d here. C h a n g e s in cell l i f e t i m e o f
less t h a n 0.1% are p r e d i c t e d w h e n Sfis d e c r e a s e d to 0.5 ~ m
or i n c r e a s e d to 40 ~m. H o w e v e r , d e p e n d i n g o n t h e film porosity, t h e a v e r a g e cell v o l t a g e c a n b e d e c r e a s e d signific a n t l y w h e n t h e film is thick. F o r t h e 40 ~ m film t h i c k n e s s ,
337
t h e a v e r a g e cell v o l t a g e w a s d e c r e a s e d b y a b o u t 4% as
c o m p a r e d to t h e b a s e case.
T h e effect of d i s c h a r g e r a t e o n cell v o l t a g e is s h o w n i n
Fig. 8. As e x p e c t e d , cell voltage, lifetime, a n d c a p a c i t y are
i n c r e a s e d w h e n d i s c h a r g e r a t e is d e c r e a s e d . T h e s e c u r v e s
compare favorably with experimental voltage-time curves
(37, 38, 41). E x p e r i m e n t a l a n d p r e d i c t e d d i s c h a r g e c u r v e s
for a 15 m A / c m 2 d i s c h a r g e are s h o w n i n Fig. 9. A l t h o u g h
o p e r a t i n g v o l t a g e s a n d cell l i f e t i m e s differ, t h e g e n e r a l
s h a p e of e a c h c u r v e is similar; a r e l a t i v e l y c o n s t a n t cell pot e n t i a l t h r o u g h o u t m o s t of t h e d i s c h a r g e u n t i l t h e e n d o f
d i s c h a r g e is a p p r o a c h e d w h e r e a r a p i d d e t e r i o r a t i o n of t h e
cell v o l t a g e occurs. It is difficult to o b t a i n close a g r e e m e n t
b e t w e e n m o d e l p r e d i c t i o n s a n d e x p e r i m e n t a l d a t a rep o r t e d i n t h e l i t e r a t u r e d u e to t h e l a c k of cell s p e c i f i c a t i o n s
(e.g., p o r o u s e l e c t r o d e p o r o s i t y a n d t h i c k n e s s , a n d separat o r p o r o s i t y a n d t h i c k n e s s ) a n d d u e to t h e d i f f e r e n c e s in
t h e e x p e r i m e n t a l d a t a r e p o r t e d . F o r e x a m p l e , Fig. 3 of Ref.
(38) a n d Fig. 8 of Ref. (41) s h o w s u b s t a n t i a l l y d i f f e r e n t disc h a r g e c u r v e s for a d i s c h a r g e c u r r e n t d e n s i t y of 15 m A / c m 2
as s h o w n i n Fig. 9. T h e s e d i f f e r e n c e s c a n b e a t t r i b u t e d to
t h e d i f f e r e n t e l e c t r o d e m a t e r i a l s , initial e l e c t r o l y t e c o n c e n t r a t i o n s , a n d cell d i m e n s i o n s used. M o d e l p r e d i c t i o n s are
i n a g r e e m e n t w i t h t h i s o b s e r v a t i o n ; as s h o w n earlier, t h e
m o d e l p r e d i c t i o n s s h o w l a r g e s e n s i t i v i t y to s e v e r a l o f
t h e s e p h y s i c a l p a r a m e t e r s (electrolyte c o n c e n t r a t i o n , porous electrode thickness).
T h e t e m p e r a t u r e - t i m e c u r v e s for v a r i o u s d i s c h a r g e r a t e s
are s h o w n in Fig. 10. T h e initial rise i n t e m p e r a t u r e i s d u e
to t h e p o l a r i z a t i o n of t h e e l e c t r o d e s a n d e n t r o p y effects as
r e p r e s e n t e d b y t h e t e r m s ~/, a n d ~ i n Eq. [77]. As t h e t e m p e r a t u r e of t h e cell i n c r e a s e s t h e r a t e of h e a t t r a n s f e r to t h e
s u r r o u n d i n g s i n c r e a s e s u n t i l a n e q u i l i b r i u m is a l m o s t
r e a c h e d w h e r e t h e h e a t t r a n s f e r is a b o u t e q u a l to t h e h e a t
g e n e r a t i o n . T h e s e e q u i l i b r i a are r e p r e s e n t e d b y t h e plat e a u s i n t h e c u r v e s in Fig. 10. A t h i g h e r d i s c h a r g e r a t e s
t h e s e p l a t e a u s b e c o m e less d i s t i n c t b e c a u s e t h e h e a t t r a n s fer c a n n o t k e e p p a c e w i t h t h e g r e a t e r h e a t g e n e r a t i o n prod u c e d b y t h e m o r e s e v e r e e l e c t r o d e p o l a r i z a t i o n s at h i g h e r
d i s c h a r g e rates. A t t h e e n d of d i s c h a r g e localized r e a c t a n t
d e p l e t i o n c a u s e s s e v e r e p o l a r i z a t i o n a n d t h e cell t e m p e r a t u r e is d r i v e n u p w a r d at a f a s t e r r a t e as s h o w n b y t h e tail
e n d s o f t h e c u r v e s in Fig. 10. T h i s s u r g e in cell t e m p e r a t u r e
at t h e e n d o f d i s c h a r g e c o u l d lead to u n s a f e b e h a v i o r b y
r a p i d l y i n c r e a s i n g t h e i n t e r n a l p r e s s u r e or p o s s i b l y trigg e r i n g e x o t h e r m i c r u n a w a y r e a c t i o n s (11). To a v o i d t h i s
h a z a r d t h e cell c o u l d b e o p e r a t e d b e l o w c e r t a i n d i s c h a r g e
395.0
"-..,
3.0
2.5
i n = 15 mA/cm 2
i n = 30 m h / c m 2
i n = 60 mA/cm 2
375.0
L
i
i
i
i
i
i
i
i
1
355.0
335.0
theoretical
curve,
Cinit = 1.5 M
- from
r e f . 3 8 , Cinit - 1.5 M
9 .......
. from
r e f . 4 1 , e i a i t -- 1 . 8 M
315.0
i n = 15 mA/cm 2
1.5
'
0.0
I
2.0
1.0
l
3.0
t (hr)
Fig. 9. Comparison of predicted and experimental voltage transients
for a 15 mA/cm2 discharge.
295.0
0.0
0.4
0.8
1.2
1.6
(hr)
Fig. 10. Dependence of cell temperature on discharge rate
338
rates and a m b i e n t t e m p e r a t u r e limits or it could be u s e d

up to a limited t i m e well before r e a c h i n g t h e end of discharge. T h e s e t e m p e r a t u r e profiles e x h i b i t the s a m e general pattern of e x p e r i m e n t a l t e m p e r a t u r e - t i m e curves (39).
I m p r o v e d heat transfer paths could be investigated using
the m o d e l by c h a n g i n g t h e e n e r g y balance parameters, C
and ho, or m o d i f y i n g the e n e r g y balance, Eq. [78].
M o d e l predictions are only as good as the i n p u t to the
model. The results p r e s e n t e d here are in good a g r e e m e n t
w i t h e x p e r i m e n t a l data r e p o r t e d in the literature perhaps
b e c a u s e of t h e detailed theoretical d e v e l o p m e n t and the
trial and error p e r t u r b a t i o n of s o m e of the kinetic parameters m e n t i o n e d earlier. The kinetic p a r a m e t e r s and physical properties used in the p r e s e n t analysis m a y c h a n g e significantly for different applications which, in turn, could
significantly effect m o d e l predictions. The versatility to
c h a n g e m o d e l inputs to simulate different applications is
an i m p o r t a n t aspect of this model.
T h e kinetic parameters, io.,,~ef, a~
~.,, ~o,~, ~,4, ~,4,
and t h e m o r p h o l o g y p a r a m e t e r ~ w h i c h is u s e d to calculate a, are t h e least k n o w n b e c a u s e t h e s e p a r a m e t e r s cannot be d e t e r m i n e d easily by e x p e r i m e n t . Also t h e s e par a m e t e r s are not constant values; the kinetic p a r a m e t e r s
for t h e SOC12 r e d u c t i o n are specific to the t y p e of carbons
u s e d for t h e porous electrode, for example. The m o r p h o l ogy p a r a m e t e r will c h a n g e d e p e n d i n g on the discharge
rate and cell temperature. E x p e r i m e n t a l data along w i t h
c o m p l e t e cell specifications (including porosities) and
p h y s i c a l p r o p e r t y data (such as diffusivity and c o n d u c t i v ity) c o u l d be u s e d in c o n j u n c t i o n with a p a r a m e t e r estimation t e c h n i q u e to estimate t h e s e kinetic parameters. A detailed sensitivity analysis of the m o d e l predictions to
changes in t h e s e kinetic p a r a m e t e r s is b e y o n d t h e scope of
this w o r k t h o u g h a few i t e m s are of note. T h e o x i d a t i o n exc h a n g e c u r r e n t density, io,~,ref, can significantly effect cell
voltage and lifetime w h e r e a s the r e d u c t i o n e x c h a n g e current density, a~
seems to influence cell lifetime m o r e
t h a n cell voltage. F o r e x a m p l e , increasing a~
by an
o r d e r of m a g n i t u d e results in a 15% r e d u c t i o n in cell life
and a less t h a n 1% increase in cell voltage.
S o m e of the physical properties used h e r e w e r e estim a t e d f r o m t h e available data in the literature (6, 7, 37,
44-46). A n a p p r o x i m a t e e x p r e s s i o n for diffusivity, as des c r i b e d in the A p p e n d i x , was u s e d and c o n s t a n t transf e r e n c e n u m b e r s w e r e assumed. The sensitivity of m o d e l
p r e d i c t i o n s to small changes in these properties was
briefly investigated. If D is halved, cell lifetime decreases
by only 6%. If t+" is d e c r e a s e d to 0.25 t h e r e is an 18% decrease in cell lifetime due to t h e resulting d e c r e a s e in species transport, Eq. [11], and the increase in IR drop across
t h e cell as indicated by O h m ' s law for the electrolyte.
C h a n g e s in D and t+" h a v e negligible effect on cell voltage
and t e m p e r a t u r e . Similarly, changes in c o n d u c t i v i t y will
directly effect the I R drop across the cell as dictated by the
O h m ' s law e x p r e s s i o n for the electrolyte. D e c r e a s i n g cond u c t i v i t y will increase the IR drop and d e c r e a s e cell voltage and lifetime.
Conclusionsand Recommendations
A o n e - d i m e n s i o n a l m o d e l of a c o m p l e t e Li/SOC12 cell
has b e e n d e v e l o p e d and used to d e m o n s t r a t e b o t h design
and operational changes that can be m a d e to increase cell
c a p a c i t y and life. A large n u m b e r of cases could be studied
u s i n g t h e m o d e l to d e t e r m i n e optimal and safe designs for
various cell specifications and discharge rates. This ability
to investigate different designs s i m p l y by c h a n g i n g m o d e l
inputs is w h e r e the v a l u e of the m o d e l lies. In addition, the
m o d e l can be u s e d along with a p a r a m e t e r e s t i m a t i o n techn i q u e to e s t i m a t e kinetic p a r a m e t e r s for various c a r b o n
materials and electrolyte chemistry.
I m p r o v e m e n t s in the m o d e l w o u l d i n c l u d e a c c o u n t i n g
for the g r o w t h of the LiC1 film as the cell discharges, t h e
a d d i t i o n of the Cl-, SO2, and S species to d e t e r m i n e their
effects on cell performance, c h a n g i n g the e n e r g y balance
to a c c o u n t for m o r e c o m p l e x heat transfer paths, and the
m o d e l i n g of a stack of cells r e p r e s e n t i n g the cross section
of an entire Li/SOC12 battery. Also porous electrode
swelling has b e e n s h o w n to be an i m p o r t a n t aspect of cell
p e r f o r m a n c e during high rate dischaTge (47) and should be

a d d e d to the model.
Acknowledgments
This w o r k was f u n d e d by the National A e r o n a u t i c s and
S p a c e A d m i n i s t r a t i o n u n d e r Grant No. N A G 9-177.
M a n u s c r i p t s u b m i t t e d Sept. 9, 1987; revised m a n u s c r i p t
r e c e i v e d March 2, 1988.
Texas A & M University assisted in meeting the publication costs of this article.
APPENDIX
Physical Properties
T h e c o n d u c t i v i t y of the electrolyte, K, is a f u n c t i o n of
c o n c e n t r a t i o n and temperature. Szpak and V e n k a t a s e t t y
(2) suggest that this functionality should be i n c l u d e d in the
battery m o d e l i n g b e c a u s e of the large changes in t h e cond u c t i v i t y as the battery discharges. A n e m p i r i c a l expression, similar in f o r m to o t h e r c o n d u c t i v i t y e x p r e s i o n s (7,
15, 16), describing this functionality has b e e n d e v e l o p e d
from the available data (6, 37, 44-46)
K=
{~1c exp (B2c + ~3c2) e x p (B4/T) (c < 1.SM)

~5 e x p (~4/T
(c -> 1.SM)
[80]
w h e r e ~1 = 135.45 ~-1 c m 1, ~2 = 399.09 cm3/mol, ~3 =

-2.5055 10 -~ cm6/mol 2, ~4 = -711.69 K, and ~5 = 0.22244
~-~ c m -~. The data for LiA1C14 m i x t u r e s ( e q u i m o l a r mixtures of LiC1 and A1C13) are for one t e m p e r a t u r e only,
298.15 K (37, 44). The c o n c e n t r a t i o n range of this data is
0.000313-2.0M. The d e p e n d e n c e of c o n d u c t i v i t y on temp e r a t u r e and c o n c e n t r a t i o n for c o n c e n t r a t i o n s a b o v e 2.0M
was e s t i m a t e d f r o m c o n d u c t i v i t y data for a similar electrolyte, SOC12 c o n t a i n i n g S Q , S, and e q u i m o l a r a m o u n t s of
LiC1 and A1C13 (45-46). E q u a t i o n [80] can be u s e d to continu o u s c o n d u c t i v i t i e s and derivatives (with respect to concentration and temperature) unlike a c o n d u c t i v i t y expression p r e s e n t e d earlier (7).
No data exist to p e r f o r m a similar analysis for the diffusion coefficient. The diffusivity was a s s u m e d to be a function of t e m p e r a t u r e and i n d e p e n d e n t of concentration.
T h e d e p e n d e n c e of diffusivity on t e m p e r a t u r e was ass u m e d to be identical to the d e p e n d e n c e of c o n d u c t i v i t y
on t e m p e r a t u r e as was d o n e in p r e v i o u s w o r k (7). T h e exp r e s s i o n used here is
D = 1~6e x p (~4/T)
[81]
w h e r e ~6 = 1.0 10 4 cm~/s.
LIST OF SYMBOLS
specific active surface area of t h e p o r o u s material,
cm-1
a~
initial v a l u e of a, c m -1
a~
p r o p e r t y e x p r e s s i n g s e c o n d a r y reference state of
electrolyte, cm3/mol
c
c o n c e n t r a t i o n of t h e electrolyte, m o Y c m ~
cl
c o n c e n t r a t i o n of species i, m o l / c m 3
cl,ref r e f e r e n c e c o n c e n t r a t i o n of species i, m o l / c m 3
C
h e a t capacity of the cell, J / c m 2 K
D
diffusion coefficient of the binary electrolyte, cm2/s
Deff effective diffusion coefficient of electrolyte, cm2/s
E
cell voltage, V
Eoc open-circuit voltage of the cell, V
Etn t h e r m o n e u t r a l potential of the cell, V
f
m e a n activity coefficient of electrolyte
F
F a r a d a y ' s constant, 96,487 C/tool of electrons
ho
h e a t transfer coefficient, W/cm 2 K
ik
reaction rate of e l e c t r o c h e m i c a l reaction k, A / c m 2
in
total cell c u r r e n t density, A / c m 2
io,k,re~ e x c h a n g e current density of reaction k at Cref,A / c m 2
i,
superficial current density in the m a t r i x phase,
A/cm 2
i2
superficial current density in t h e solution phase,
A/cm2
j
current transferred b e t w e e n phases, A / c m 3
K,,1 friction coefficient for interaction b e t w e e n species i
and 1, J s / c m ~
nk
n u m b e r of electrons transferred in the e l e c t r o c h e m i cal reaction k
Ni
superficial flux of species i, moYcm 2 s
Pl,k anodic reaction order of species i in reaction k
qi,k cathodic reaction order of species i in reaction k
q
net heat in cell, J / c m 3
C/ht
energy change due to heat transfer between cell and

surroundings, W/cm 3
q:p heat generated due to cell polarization, W/cm2
heat generated due to entropy effects, W/cm 2
R
universal gas constant, 8.3143 J/tool K
Ri
production rate of species i due to reaction, mol/cm 3
s
thickness of region l, cm
Sl
S],k
stoichiometric coefficient of species i in reaction k
t
time, s
cell lifetime, h
tcell
ti N
transference n u m b e r of species i relative to v"
T
cell temperature, K
TA ambient temperature, K
U
internal energy of the cell, J/cm 3
Yk,ref potential of reaction k relative to the reference electrode, V
superficial velocity of species i, cm/s
Vi
Vm
superficial volume average velocity, cm/s
V,
partial molar volume of species i, cm3/mol
W
net work done by or on the cell, J/cm 3
X
normal direction from SEI surface to porous electrode, cm
Zl
charge n u m b e r of species i
Greek Symbols
(~a.k transfer coefficient in the anodic direction of reaction k
ac.k transfer coefficient in the cathodic direction of reaction k
e
porosity or void volume fraction of the porous electrode
e~
initial porosity of the porous electrode
K
conductivity of the solution, ~-1 cm-1
Keff effective electrolyte conductivity, ~-1 cm-1
~i
chemical potential of species i, J/mol
v
n u m b e r of cations produce by dissociation of electrolyte
v_
n u m b e r of anions produce by dissociation of electrolyte
v
total n u m b e r of ions into which one molecule of the
salt dissociates
conductivity of the solid, ~/cm
~eff effective conductivity of the matrix phase, ~/cm
(Pl
potential in the matrix phase, V
(I)~ potential in the electrolyte, V
morphology parameter
E1
exponential for calculating effective properties in
the porous electrode region
~2
exponent for calculating effective properties in the
separator
~3
exponent for calculating effective properties in the
LiC1 film
Subscripts
e
electrolyte
f
LiC1 film
i
species i
init initial value
k
reaction k
o
solvent
pe
porous electrode
r
reservoir
s
separator
+
cation
anion
1
solid matrix phase
2
electrolyte phase
-
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University of South Carolina

Chemical Engineering, Department of

A Mathematical Model of a Lithium/Thionyl

Follow this and additional works at: http://scholarcommons.sc.edu/eche_facpub

Table A-I. Concentration,density,and mole fraction of LiAICI4-SOCI2

aCalculated by iteration as explained in the text.

Ib H e n r i k s e n s F o n d are t h a n k e d for p r o v i d i n g the financial basis of this work.

Manuscript submitted Nov. 30, 1987; revised manuscript

(p +_ 0.0001) = (0.594484 0.000934). XLjAlCI4

A Mathematical Model of a Lithium/Thionyl Chloride

of toxic gases and explosion. A m a t h e m a t i c a l m o d e l of this

Description of a Li/SOClz Cell

t h e r e d u c t i o n of SOC12 at the cathode

and the f o r m a t i o n of the LiC1 film on the a n o d e and the

F o u r species are i n c l u d e d in the model: Li +, A1CI(, SOC12,

Models of the Li/SOCI2 Cell

Collectors - ""- ~ - - - ~ "

iiii IIii ill *llji

d e t e r m i n e the c o n c e n t r a t i o n and reaction rate profiles in

The g o v e r n i n g e q u a t i o n s p r e s e n t e d n e x t d e s c r i b e conservation of mass and current, species transport, and reac-

Porous electrode region.--In order to d e v e l o p a useful

C o n c e n t r a t e d solution t h e o r y (22-24), in particular the

a n d the effective diffusivity, D,ff, is defined

w h e r e 41 is c h o s e n to be 1.5; this v a l u e is consistent with

Solvent and electrolyte material balances.--Equations [9],

T h e subscripts +, - , and o refer to Li A1C14-, and SOC12,

w h e r e j is the local transfer current in a m p e r e s per cubic

In Eq. [11] and [12] t h e v o l u m e average velocity is defined

The total current transferred from the m a t r i x phase to t h e

- - V . (_De~IVc~ + CoVl) _ ~ So.ka ik

E q u a t i o n [15] is for t h e two u n k n o w n s c+ and c_ and can be

N o t e that either relation in Eq. [17] can be substituted into

Solid phase material balance.--Equation [8] for t h e solid

Ohm' s law for the m a t r i x phase.--Ohm' s law for the m a t r i x

solid phases Si,kVi

Overall material balance.---The three material balance

E q u a t i o n [31] is u s e d to a c c o u n t for the effect of the m a t r i x

E q u a t i o n [19] d e s c r i b e s the porosity c h a n g e of the porous

w h e r e t h e partial m o l a r v o l u m e of the electrolyte, V~, is defined as

E q u a t i o n [20] e x p r e s s e s c o n s e r v a t i o n of v o l u m e and can be

+ (~JoSo,k+ Q~t-ms+,k + vj+ms-,k) nkF

- (PoSo,+ + Q+t_"s+,+ + P+t+"+_,+)/i==

Electrode kinetics.--The e l e c t r o c h e m i c a l reaction rates, ik,

The potential driving force for e l e c t r o c h e m i c a l reaction k

vRT ( s+.4 + t+m

S u b s t i t u t i n g Eq. [33] into Eq. [30] yields

Only reaction [4] is a s s u m e d to occur w i t h i n the positive

results in the following relationship

In Eq. [25], t h e stoichiometric coefficients of reaction [4] are

E q u a t i o n s [20], [27], and [28] can be s u b s t i t u t e d into Eq. [25],

Altogether, six e q u a t i o n s and six u n k n o w n s are u s e d to

4Li + 2SOC12 ~ 4LiC1 + SO2 + S

R e s e a r c h e r s (32-35) believe that the film passivates the Li

the electrolyte balance

U s i n g Eq. [41] in Eq. [33] yields

E q u a t i o n s [18] and [29] for t h e p o r o u s electrode can be

O h m ' s law for the electrolyte

and O h m ' s law for the electrolyte b e c o m e s

N o t e that effective properties are not u s e d in Eq. [43] and

and O h m ' s law for t h e electrolyte is

and Eq. [24], [40], [42]. The value of the e x p o n e n t ~3 is set to

N o t e that effective properties h a v e b e e n u s e d in Eq. [46]

The solvent flux is zero at this b o u n d a r y

U s i n g Eq. [20], Eq. [53] can be written