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LBL-32769
UC-331
Preprint
October 1992
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Prepared for the U.S. Department of Energy under Contract Number DE-AC0376SF00098
DISCLAIMER
This document was prepared as an account of work sponsored by the United States
Government. While this document is believed to contain correct information, neither the
United States Government nor any agency thereof, nor the Regents of the University of
California, nor any of their employees, makes any warranty, express or implied, or
assumes any legal responsibility for the accuracy, completeness, or usefulness of any
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United States Government or any agency thereof, or the Regents of the University of
California. The views and opinions of authors expressed herein do not necessarily state or
reflect those of the United States Government or any agency thereof or the Regents of the
University of California.
LBL-32769
UC-331
and
October 1992
This work was supported in part by the Assistant Secretary for Conserva-
tion and Renewable Energy, Office of Transportation Technologies, Elec-
tric and Hybrid Propulsion Division of the U. S. Department of Energy
under Contract No. DE-AC03-76SF00098.
Modeling of Galvanostatic Charge and Discharge
of the Lithium/Polymer/Insertion Cell
'i
Abstract
material.
..
'
2
Introduction
'" the amount of lithium inserted were used to relate the surface concen-
lytes have concluded that ion pairing and ion association are impor-
9
tanto Thus, the more complete concentrated solution theory is
appropriate.
theory in accounting for volume changes and polymer flow. One may also
wish to keep the model general so that the kinetics of the cathode can
4
Model Development
transport from the lithium anode through the polymer separator into the
the solvent for a lithium salt. Several polymer and salt combinations
11
with widely varying properties have been considered in the 1iterature.
lithium ion, and the diffusion coefficient of the lithium salt charac-
5
polymer
electrolyte
x=o
: .. '
12
In concentrated solution theory (see Newrnan ), the driving force
1. If we use the polymer as the reference species and take its velocity
(2)
and
itO
N (3)
v D"ilc + z F
t"
~es
to' and '"~.13
D' +
7
A material balance on the salt in' the separator is then given by:
Be (4)
Bt
al. ,14 the reaction at the anode is assumed to take the form:
Li + 9
p -
--+ Li+-e
p
+ e
I =
[ [a 1]
i 01 exp
lF1J
aRTs - exp -
[a lF1J
c RT S
1]] (6)
(7)
'151
aa a a
(8)
iol = F(k ) al (k ) cl (c _ c) al (c) cl
al cl max.
mer systems.
at this boundary (x=O). The other boundary conditions include the flux
; at x = O. (9)
The flux and .concentration of each species and the potential in the
solution phase are taken to be continuous between the separator and the
(10)
where is the volume fraction of the polymer in the cathode. The extra
the interface, which is averaged over the interfacial area between the
1.5
K-eff K-
and
0.5
D.
The boundary conditions rn the solution 'phase are that the flux of
N.
.1
o at x (12)
Be s
(13)
Bt
Be s
o at r=O. (14)
Br
Be s
D (15)
s Br at r=R s .
RT[
+y ln [C
T-C
s
C s] + {3c s + 1
r . (16)
8
This is similar to the expression proposed by West et al. The only
corrections and are taken to be constants that can be fit from experi-
tion:
Li+-e
p
+ 8
s
+ e - Li-8
s
+ e
p
U (18)
12
8
Using the parameters given by West et al. based on experimental data*
U ,= 2.17 + RT(-
~ 0.000558c
s
+ 8.10) . (20)
the TiS interface has not been reported, we set the parameter. k2 in
2
equation 17 equal to a value corresponding to a nearly reversible situa-
is:
o at x=ol' (21) -
(22)
0, (23)
I (24)
Thus, the current flows through either the' polymer/salt phase or the
insertion phase.
Table 1.
-13 2
D 5.0x10 m /s 16 T 100C
s
4
a 1. Ox10 S/m - (\ 50 /.tm
2
i 12.6 A/m 14,* 100 /.tm
0,1 2
a 0.5 R 1.0 /.tm
a,c s
11 1
*- c
0
1000 mol/m
3
+ ,-
3
c
T
29,000 mol/m - 0.3
~10 4
k2 1.0x10 m /mols - -
*
Quantities on the left are inherent properties of a specific system and
assuming one lithium atom per molecule of titanium disulfide and using
tion is
C
s,avg (25)
U =
c
T
b een 0b serve d
~n
.
exper~menta
1 d~sch arge curves. 3,17 A typical cutoff
voltage is about 1.7 volts; beyond this value the cell is severely
polarized.
first, and then the concentration profiles are nearly constant over most
the cathode is low. At the front of the cathode, x=0.33, the concentra-
tion dips for short times. This effect is easier to see in figure 4,
3.0------------~-----------r-----------T----------~~--------~
Charge
2.5
-
- I=10
2
I=20 Aim
Discharge I=13
I=10
0.5
O.O~--------~--------~--------~--------~--------~
0.0 0.2 0.4 0.6 0.8 1.0
u, utilization
1500
composite
cathode
E = 0.3
1000~------~~~~-----0 s--~-----=========~
50
----_________ 200------~
separator
500 ---400------'::=:J
600---~
12,600
o~------~------~~--------~--------~------~
0.0 0.2 0.4 0.6 0.8 1.0
x
Figure 3. Concentration profiles at long times.
2
I = 10 Aim. Dashed line divides the separator and
3
composite cathode. Initial concentration is 1000 mollm .
17
1200r--------r----~~r_------_r------~r_------~
1150
separator composite
1100
cathode
=0.3
1050
...
o
1000
950
900~------~----~~~--------~--------~------~
0.0 0.2 0.4 0.6 0.8 1.0
battery performance, cine should like the cell potential to fall below
its cutoff value only after nearly all of the active material is con-
tion distributions.
dimensionless parameter 5;
(26)
and is the ratio of diffusion time to discharge time. For 51, diffu-
at the surfac~ and the average concentration in the solid are nearly
Note that the radius of the particles would have to be on the same order
important.
(27)
For 1=10 A/m2, we find that 5=0.15. At high current densities, the low
19
the sharp drop in cell voltage at less than complete utilization of the
Figure 5 shows the local transfer current density across the compo-
12.
site cathode at various times during discharge. Newrnan gl. ves four
are
(28)
v 2 (a a +ac ]FaiOS;(l
=
RT
lJ
-+-
a ~ .
(29)
we expect that the ohmic drop will dominate the current distribution in
the porous electrode. The exchange current density in the cathode can
20
0.0
U)
I
N
E -0.2
"0 ,.......j
E
-0.4
\D
I
0
.-i
~ -0.6
n
...
+J -0.8
s::Q)
H
H
~
u -1.0
H
Q)
lH
(f)
s:: -1.2
cO
H
+J
-1.4
0.4 0.5 0.6 0.7 0.8 0.9 1.0
Q
(c ) a"2 (30)
s
be at their initial values. ,In our case, we find that 0=1.95 and /.1=68,
and we expect the ohmic drop to dominate at short times. This is under-
cathode "fills up," and the reaction shifts towards the center of the
phase it tapers off at long times. Figure 3 shows that the concentra-
tion in the electrolyte phase rapidly decreases at the back face. The
tration. Not only will the depletion of the electrolyte cause concen-
dix A), approaching zero in the depleted region near the back face of
the cathode while holding its theoretical capacity constant. This could
electrolyte phase are minimized. The use of this method for the current
2
system led to the conclusion that, for a current density of 10 A/m and
higher than the 84% that was obtained previously with a porosity of
0.30.
1.0~--~--~--~------~------~----~------~------~
.,
0.8 14,400s
~
0
-rl
+J
cO
N
-rl 0.6
rl
rl
+J
~
8040s
rl
cO 0.4
0
0
rl
...
::s
3240s
0.2
40s
O.O~==~==~~====~====~=========~====~
0.4 0.5
I
0.6 0.7 0.8 0.9 1.0
exist. This does not consider the disadvantages that may be associated
of the system, and cost of components; these issues will not be dis-
cussed here.
by calculating the average and peak power for a given discharge rate
. 2
predicted by the model. Using a three-hour discharge rate (12.1 A/m ),
The power and cell potential are plotted in figure 7 at different depths
estimate of the mass of material and size of the system. Basing calcu-
lations only on the mass of active cathode material used, the present
the ratio of peak power to average specific energy, which is lower than
Summary
the insertion cathode, the most important being the consideration of the
full cell sandwich. One can first analyze the validity of their assump-
200~------~------~--------~------~--------' 3.0
,
, 2.5
,1%
.- .-
150
2.0 ---.
N
E
>
"-'"
.......... , ro
8: .-
100 , ,, 1.5.
+-'
c
, , , Q)
, ...
,,
~
.- ... +-'
, , ... .- .- .- ... 80%
Q)
.- 0
~
0 /'
, a.
P-I , , ,
, , , .- , .- Q)
, ,
, , , , , ,, , , , '1.0 U
, , ,
50 , , , ,, ,
, ,,,,,,.-",
, , ,."
,,' 0.5
/~~
" ,
,~
,~
,#
,"
0 0.0
0 20 -40 60 80 100
Current (A/m2)
26
concentration varies by about 15% from its initial value for the present
lation using the same parameters as in the West model,8 including con-
trode, this does not occur in the current simulation. The final
material utilization predicted for the system has been increased from
separator/cathode interface.
the differing local states of charge in the solid particles. This could
3.0~------~~------~--~----~------~--------~
2.5
.,.-1 2.0
--- ---- ---
--- --- - - --
ro
.r-! o
.w
C 2
0) 1.5 I=50 Aim
.w
0
.P.t
,.-1
,.-1 1.0
0)
U
0.5
O.O~-------L--------~--------~-------L--------~
0.0 0.2 0.4 0.6 0.8 1.0
u, utilization
18
discharge, for example.
Acknowledgements
number were obtained from data available in the literature. The diffu-
b1e data were difficult to obtain. Activity coefficient data have not
been reported.
19
The conductivity of PEO-LiCF S0 was fit to a third order po1yno-
3 3
"1
m1a. Th e trans f erence number 20 was f"1t to t h e equat1on:
"
29
t~ 4
0.0107907 + 1.48837xlO- c
-12 2 20
The diffusion coefficient was taken to be 7.5x10 m /sec. The solu-
Appendix B Superposition
ac S t ac S ac S
(B-1)
-a-(R ,t)
r S f -at( Rs'~,.) ar (R s ' t-")
~ d"
~
o
ac s
-a-(R ,t)
n-2
L (c s,k+1-c)
s,k A + ( c s,n-c s,n-1) A (B-2)
r s k=O ~t n-k ~t 1 '
where
and
30
(B-4)
a( t)
a(r) (B-S)
a(r) = -r + 2; r~ [1 + 2
n=l
exp I [_~2] (B-6)
2
r is dimensionless time; r=tD
s
/R s . The values of a(r) and A _
n k
can be
List of Symbols
2 3
a specific interfacial area, m /m
3
c concentration of electrolyte, mol/m
'3
c. concentration of species i, mol/m
~
f activity coefficient
t time, s
0
t. transference number of species i
~
T temperature, K
lJ open-circuit potential, V
J
V cell pbtential, V
Ct
a'Ct c transfer coefficients
32
dimensionless current,density'
thickness of separator, m
porosity of electrode
,surface overpotential, V
r dimensionless time
electrical potential, V
Subscripts
r reference state
s solid phase
1 solid matrix
2 solution phase
Superscripts
References
135, 12 (1988).
(1981/82).
(199l) .
1480 (1982).
trodes with High Exchange Current Densities," Electrochim. Acta, 25, 315
(1980).
2231 (1988).
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