Elecwochinrica Acta, Vol. 39. No. 4. pp. 511-526, 1994 copyright 1994 Elsevie .kience Ltd.

Q Printed in Great Britaia All ii&s rcsed 0013~4666/9456.00 + 0.00

THERMAL ANALYSIS OF LITHIUM POLYMER ELECTROLYTE BATTERIES BY A TWO DIMENSIONAL MODEL-THERMAL BEHAVIOUR AND DESIGN OPTIMIZATION
YUFEI C.&EN* and JAMESW. EVANS?
Materials Science Division, Lawrence Berkeley Laboratory/Department of Materials Science and Mineral Engineering, University of California, Berkeley, CA 94720, U.S.A. (Received 15 July 1993; in revisedform 27 September 1993) Ahstrati-Thermal analysis of lithium polymer electrolyte batteries is carried out to examine the relationship between battery thermal behaviour and design parameters. By studying the effect of stack size and cooling/insulating conditions on battery temperature under diRerent discharge rates, information is obtained as to how to maintain operating temperature by designing proper cell stacks and choosing proper cooling/insulating systems. Moreover, temperature distributions within cell stacks for different cell designs, including different thickness of cell components and different current collector materials, are calculated so as to carry out cell structure optimization from a heat transfer point of view. Finally, thermal characteristics of lithium polymer electrolyte batteries based on different positive electrodes (es V,O,, , TiS, and redox polymer) are discussed. Key words: mathematical model, heat transfer, polymer electrolyte, lithium batteries, design optimization.

NOMENCLATURE

average specific heat of battery/J kg- K- specific heat of layer i/J kg- K- E OC open-circuit voltage of one cell/V cut-off voltage of one cell/V p convective heat transfer coefficient/ Wme2K- superficial current density/Arm- a~ermag;Kthermal conductivity of battery/ f,

CP CPi

Ax AY
%
UY

cell voltage/V step length in X coordinate step length in Y coordinate

= kJpC, average thermal diffusivity direction/m? s - = k,/pC, average thermal diffusivity direction/m s- average density of battery, kgmw3 density of layer i/kg m- 3

Greek symbols

in X in Y

P Pi

k, kin k, k,

thermal conductivity of layer i/W m - K - t thermal conductivity of insulating material/ Wm-K- aWerma_gf;h_e:mal conductivity in X direction/

INTRODUCTION

average thermal conductivity in Y direction/ Wm-K- heat conduction distance/cm L thickness of insulating material/cm Li thickness of one cell/cm LX thickness of layer i/cm LXi thickness of cell stack/cm LX height of cell stack/cm LY width of cell stack/cm LZ N Cdl cell number in a stack rate of heat generation per unit volume/ 4 Wmm3 temperature of battery/K T temperature of cell/K T,, TOCO initial temperature of cell/K ambient temperature/K TV time/s t
l Visiting scholar. t Author to whom correspondence should be addressed.

Development of advanced rechargeable batteries for electric propulsion applications has been the subject of intensive study worldwide due to the beneficial impact[l] of battery-powered electric vehicles on atmospheric air quality. However, the main problems associated with battery-powered electric vehicles, eg the limited vehicle range and speed, would lead such vehicles to be less competitive as compared with those with internal combustion engines. Lithium batteries, which may have high specific energy and specific power, because of the lightness and high electropositivity of lithium, may provide solutions to the limitations of the current battery technology. In addition, polymer electrolyte based, all solid state lithium batteries have a number of other attractive features[2] which may also make this kind of battery suitable for electric vehicle applications. Accordingly, the lithium/polymer electrolyte battery has been considered to be one of the most promising long-term advanced battery technologies by the U.S. Advanced Battery Consortium[3].
517

518

Y. CHEN

and J. W. EVANS
Mathematical Model

To date, polymeric electrolyte based lithium batteries with either intercalation compound (eg V,O,, or TiS,)[4, 51 or redox polymer[6] as the active material of the positive electrode have been shown to exhibit attractive performance at a laboratory scale. Also, battery prototypes containing cells scaled-up by a factor of 1000 have been tested[7-91 and no evidence of degradation has been observed. It seems that lithium/polymer electrolyte batteries for electric vehicle applications may be close to reality in a few years. However, much work still remains to be done for large scale applications, among which is battery thermal management. This is because the low ionic conductivity of the polymer electrolyte has limited the application of the battery to elevated temperature (eg 80-14OC), and the operating temperature range should be maintained so as to achieve optimum performance. Mathematical simulation of heat transport within large batteries is an effective tool to obtain knowledge about whether excessive heat generated during the battery discharge/ recharge process can be removed, and how operating temperature can be controlled. Previous examples have been given by Choi and Yao[ 10, 1l] for leadacid batteries, Lee et aI.[12] for lead-acid and nickel/iron batteries, Parnell and Szpak[ 131 for Li/SOCl, batteries, and White and coworkers[14163 for Li/SOCl, cells and nickel-hydrogen batteries. In the previous paper by the present authors, basic heat transfer phenomena in lithium/polymer electrolyte batteries for electric vehicle applications have been presented[17]. In the present work, further studies of the effect of battery design parameters on battery thermal behaviour have been conducted by a modified model, with emphasis on the effect of insulation, thicknesses of cell components, and different current collector materials on temperature distribution, so as to obtain fundamantal ideas concerning the optimization of cell structure from the viewpoint of heat transfer. Furthermore, the heat transport phenomena in lithium/polymer electrolyte batteries with different positive electrodes are compared.
Cell
stack

As shown in Fig. 1, a battery is composed of one or more multi-cell stacks, and a cell stack is composed of many series-connected bipolar units connected in parallel[18]. The cell number in a stack is determined by the desired battery capacity and voltage. This design is considered to be suitable for traction battery applications and is expected to exhibit high specific energy. Because a thin-film cell design is adopted, the greatly differing thermal properties of different layers may have significant influence on heat transfer behaviour within a battery. In our previous work[17], heat transfer equations in cell stacks with heterogeneous thermal-physical properties of different layers were solved and the results indicated that the temperature within one cell is invariant across its thickness, and is close to that computed using the thermal properties of the polymer. Nevertheless, it appeared to be impractical, because of the long computation time, to calculate temperature profiles in a cell stack with practical thickness by the mathematical model for stacks with heterogeneous thermal properties. Therefore, thermal behaviour was conservatively predicted by treating the battery as consisting of a homogeneous isotropic medium with the thermal properties of the polymer (which had the poorest thermal transport properties in this system). This treatment is a sutlicient approximation for analysis when the maximum temperature in the battery is of concern. However, it may be argued that thermal conductivity is relatively large along the height (Y) direction. To take this feature into consideration, in the present paper, a modified two dimensional model in which the cell stack is assumed to be of orthotropic thermal properties, that is, the thermal conductivity in thickness (X) direction is different from that in height (Y) direction, is applied to further investigate the thermal performance of the batteries. More importantly, this improved model can be applied to analyze the effect of different cell component thicknesses and of using different

Extents1 rurhx

lnsuhtion

Coolinn
channel ,

Cell
suck /

----t
Current

collector Ncgh%
electrode

f
-t-

Polymer -I-electrolyte & 4 Positive electrode Bipolar connr.ctor

Fig. 1. Two-dimensional

model of bipolar

connected

cell stack.

Two dimensional analysis of lithium polymer batteries materials for the positive electrode and for the current collector. Because there is a significant shortage of experimental data for the thermal-physical properties of cell components in the literature, quantitative results cannot be obtained even by a three dimensional model. Therefore, for simplicity, only heat transfer in the X and Y direction is considered at this stage of modeling (see discussion in the following section). Under the above assumption, the following two-dimensional transient heat transport equation is obtained: cooling law is applied to obtain boundary tions : at x = 0 or LX, any y: -k_ El X aty=OorLY,anyx: =

519 condi-

MTx=oor~x T,) -

(6)

-k,E

pC,~==k,~+k,~+q w

ayy=oorr,r = h(Ty=oorLr

T,)-

(7)

(1)

where the thermal conductivities in X direction k, and in Y direction k, are estimated in a similar way to determining the equivalent electric resistances in an electric circuit consisting of series- or parallelconnected electric resistances, respectively, that is

(2)
and

If the battery temperature drops below its operational temperature during a low rate discharge, it might be expected that the cooling systems would be turned off and insulation material used to maintain battery temperature. In that case, heat will be conducted through the insulation material and then dissipated to the surroundings by natural air flow. Supposing that the temperature increase in insulation material is negligible (ie that the insulation is at a thermal quasi-steady state), and that the insulation material is treated as the boundary of the cell stack (as in Lees two-region model[12]), the following boundary conditions are obtained

The average volumetric heat capacity PC, is given by and The average thermal diffusivity in X direction (a3 or in Y direction (a,,) is the ratio of the corresponding average thermal conductivity (k, or k,) to average heat capacity. The average thermal diffusivities thus obtained are independent of the arrangement of cell components. However, preliminary calculations indicate that a good approximation to the temperature profiles calculated from the model for stacks with heterogeneous properties of different layers[17] has been achieved for the investigated multi-layer, thin-film configured stack design. q in equation (1) is the heat generation rate which is assumed to be uniform throughout the battery. In terms of the general expression of heat generation for battery systems derived by Bernardi et aI.[19], under the assumption that no phase change is involved and only electrochemical/intercalation reactions exist for the solid state lithium cells of the present investigation, q can be written as
N

(8)

where the term on the right hand side is obtained by equating the heat fluxes at the inside and outside surfaces of the insulation material. The battery is initially heated to operational temperature T,, , thus the initial condition is T=T,,,att=O,anyxandanyy. (10)

4= where temperature T is supposed to be the average battery temperature which will change during the battery discharge process. It is further assumed that forced convection is applied to the external surfaces (Y = 0 and Y = LY) and the cooling channels (X = 0, and X = LX), and that the air temperature and heat transfer coefficient are uniform around the stack surface. Newtons

The implicit alternating-direction technique[20] is applied to cast equation (1) associated with the boundary conditions, into finite difference forms which are then solved by the Gaussian elimination method. The solutions are unconditionally stable, and converge on the solutions of the original partial differential equation as At + 0, Ay + 0 and Ax + 0. Table 1 lists the parameters used in the present calculations. Most of the thermal-physical parameters for positive electrodes (V,O,, , TiS, and redox polymer) are not available in the literature. In order to conduct the mathematical simulation, certain assumptions for choosing the values of model parameters are needed. The density and specilic heat for V,0,3 are assumed to be approximated by those of V,O,[21], while its thermal conductivity value is chosen from within the parameter value range of metals and their oxides[21]. The specific heat and thermal conductivity of titanium oxi& are used for TiS,. Thermal parameters adopted for polymer are those of redox polymer and metallixed plastic current collector. The effective average density and

520

Y. CHEN and J. W. EVANS Table 1. Parameter values for model calculation Thermal-physical properties

Parameter
P

Li [21] 534.0 3514.6 81.8

Polymer 1200.0 [22] 2050.0 [23] 0.16 [23]

composite electrode

VJA,

TiS, composite electrode

Redox polymer composite electrode 1540.05 1916.2 2.03

Ni [21] 8900.0 471.0 82.7

Al [21] 2700.0 908.0 200.8

Wgme3)

C, (JKgK-) K (Wm-K-l)

2208.0* 2490.07 2285.03 1148.5 1054.62 884.6 5.77 7.18 5.71 Inout and initial data

System

Open-circuit voltage of one cell E, (V) Cut-off voltage of one cell E,,, (V) Temperature coefficient of E,, , dE,/dT (V K-l)
Current density i (mA cm -) Initial cell temperature qeO (K) Ambient temperature T, (K) Thickness of cell components LX, (pm)

f-i/v@,B

3.2 1.75
2.20 x lo-4 0.10-5.0 373

Li/TiS, 3.0 1.40 2.20 x lo-4 0.5-2.0 373 298 50-100 6.0 0.03

Li/Xl 11

3.0 1.0 2.20 x lo-4 0.5-4.0 357

Convention coefficient h (W m-K-l) Insulating material ki, (w m - 1K - )

* composition[4]: 45% v/o V6013; 5% v/o carbon; 50% v/o PEO-LiX. t composition[25] : 75.4% w/o V,O, 3; 5% w/o carbon; 19.6% w/o PEO-LiX. $composition[S]: 50% v/o TiS,; 10% v/o acetylene black; 40% v/o PEO-LiX. Ejcompositionr241: 45% w/o Xl ; 10% w/o carbon; 45% w/o PEO-LiX. 11 : himerca$todithiazole polymer. Xl specific heat for composite positive electrode are calculated as linear combinations of those (within the battery operation temperature range) of its consistent components. Calculated results indicate that the thermal behaviour of lithium/solid polymer electrolyte battery is mainly determined by the low thermal conductivity of the polymer. Therefore, it is considered that no significant error will be caused by choosing these values for model parameters. Discharge curves of lithium polymer electrolyte cells

with V,O,,, TiS, and redox polymer as composite positive electrodes reported by Hooper and coworkers[2, 43, by Gauthier et aI.[S] and by Liu et aI.[6], respectively, are used in the present calculations. For most battery systems, the temperature coefficients of open-circuit voltage are the values of a magnitude of 10e4V K- . In this paper, 2.2 x 10 -4 V K- is arbitrarily chosen, and preliminary calculations suggest that any likely discrepancy from the real value will not result in remarkable differences in temperature distribution. It seems that most experimental cells are of a thickness of about 4OOpm, though optimum cell thickness may be expected to be typically in the range from 150 to 2OOpm[26]. Except where otherwise indicated, results presented in this paper are for cell stacks consisting of cells with a thickness of
4OOpm (the difference in the thermal between 400 and 2OOym cells is discussed lowing section). behaviour in the fol-

which results in a cell stack thickness of about 6cm. It is necessary to study the influence of various design parameters and operating conditions on battery thermal behaviour so as to demonstrate whether battery prototypes can be successfully scaled-up. Munshi and Owens[25] assessed the optimum cell area to be between 400 and 2500cm2 from the point of view of achieving high specific energy and specific power. Therefore, LY = 20cm can be reasonably chosen as the height of a cell so as to study the effect of stack thickness (LX) on thermal behaviour. Figures 2 and 3 show temperature profiles in the center of a 10cm thick cell in the X direction (at y = LY/2) and in the Y direction (at x = Z,X/2), respectively (unless otherwise stated, results are for the Li/V,013 system). The flat temperature distributions in Y direction indicate that it is relatively easy to conduct heat in the Y direction
400 r __ c/o.3

hY

360 t

340 _c----t 320 i 0 /2 4 6

Cl8 --w 8 10

RESULTS

AND DISCUSSION

Temperature profiles in cell stacks

In order to design a battery with desired capacity and voltage, many cells are stacked together. For

example, in the Harwell prototype, 30 bipolarconnected-20-cell units are connected in parallel[7],

X/cm distributions in X direction (y = LY/ 2) in a 1Ocm thick cell stack at the end of discharge for rate C/O.3 and C/8. Fig. 2. Temperature

Two 400 -

dimensional analysis of lithium polymer batteries

c/o.3 390 r

521

___ , i 0.8cm
340

x
I I
2.0

10 Y/cm

15

20

I 0.5

II
1.0

I
2.5

1.5

L&m Fig. 5. Effect of thickness of insulation material on temperature in cell stack at the end of discharge of rate C/4 K,, = (LX = 10.0~~1, LY = 2O.Ocm, T,, = 373K, 0.03 Wm-K-l). materials are needed. Figure 5 shows the variation of the temperature in a cell stack at the end of discharge with the thickness of insulation under the assumption that the thermal conductivity of the material is 0.03 W m-l K-i (the thermal conductivity for typical insulating materials is from 0.03 to O.l7Wm-K-[27]). It is predicted that a 0.8cm thick layer of such an insulating material will be suitable to maintain the temperature around the initial temperature of the cell. This is probably one advantage of lithium polymer electrolyte batteries for electric vehicle applications because conventional insulation materials with a suitable thickness will be sufficient to maintain the temperature within the operating range. From Fig. 4, it can also be seen that if a stack thickness is larger than a certain value, the temperature will increase under high discharge rate (eg C/0.3). Figure 6 illustrates the effect of the convective heat transfer coefficient on temperature profile in a 5cm thick stack. Obviously, the improvement in cooling conditions is not an effective means of reducing the temperature increase in the center of a large stack. Instead, it may cause steep temperature profiles. In order to prevent the battery temperature
400

Fig. 3. Temperature distributions in Y direction (x = LX/ 2) in a 10cm thick cell stack at the end of discharge for rate C/O.3and C/g.

as compared with that in X direction. It can be seen that under low discharge rate, the temperature in the stack will decrease. However, under high discharge rate, temperature in the cell stack will increase significantly. This is because, on the one hand, the low thermal conductivity of the polymer will limit heat conduction in the X direction, and on the other hand, the relatively large dimension of the stack height will result in a long relaxation time for heat conduction @/a), even in the Y direction. Because steep temperature distributions exist in the X direction, the following results are intended to examine the effect of stack thickness and insulation on thermal behaviour.
Effect of stack size and insulation on maximum temperature

Figure 4 depicts the effect of stack thickness on maximum temperature in cell stacks for different discharge rates. The results are in good agreement with the observation that the major thermal management problem at low discharge rates is more likely to be the maintenance of operating temperature[2]. Because battery temperature will decrease during the process of low rate discharge, insulating

T 3::

1
-/ / -.-. h-25 W III-~ K- K- h-15 W ,-2 \ \

360 -

h-6 W m-2 K-

3505 0 0 2 4 6 8 10

2 X/cm

. LX/cm Fig. 4. Effect of stack size on maximum temperature in cell stacks for different discharge rate.

Fig. 6. Effect of heat transfer coetE&nt on temperature profile in thickness direction (Y = LY/2) at the end of discharge (LX = KOcm, LY = 20.0 cm, C/0.3).

Y. CHEN and J. W. EVANS 10

380 S iwy 370 F 360 t 350 1 0 I 1 I 2 X/cm I 3 I 4 I 5 20 40 60 LX+m 80 100 120 -*-LY=SOcm LY-2Ocm LY=IOcm

Fig. 7. Effect of stack height on temperature profile in X

direction (Y = LY/2) at the end of discharge of rate C/O.3 (LX = 5.0cn-1, l&O = 373 K).

Fig. 9. Effect of thickness of different layer on average thermal diffusivity of cell stack in X direction (basic cell: Li
(114pm),PEO(20prn),VO,(1OOpm),Al(15~m)).

from increasing significantly under a high discharge rate, a suitable stack thickness should be designed. For example, from Fig. 4, it can be seen that under the discharge rate of C/0.3, operational temperature can be approximately maintained if a stack is of a small thickness (around l.Ocm). In Figs 7 and 8, the effect of stack height (or plane area in three dimensions) on temperature profile and on maximum temperature in cell stacks, respectively, is shown. It is demonstrated that the increase in stack height within the range from 10 to 50cm will not significantly influence the temperature distributions in cell stacks. Therefore, it is considered that battery thermal behaviour will not be remarkably affected if the cell area is of a value within such a range from 400 to 2500cmz[25].
Effect of thickness of cell components on thermal behaviour

Optimum design of cell structure is important in order to obtain high specific power and specific

energy. Munshi and Owens[ZS, 281 discussed the dependence of specific energy and specific power on cell design. Based on their cell configuration (ie Li: 3 x cath. capacity; electrolyte: 0.2 x thickness of cathode; Ni: 25 pm as current collector; Al: 15 pm as bipolar connector), the effect of thicknesses of cell components on temperature profiles in cell stacks is investigated in the present work. Figures 9 and 10 show the effect of the thickness of lithium negative electrode, polymer electrolyte film and vanadium oxide composite positive electrode on average stack thermal diffusivity. It can be seen that thermal diffusivity increases with lithium thickness, and decreases with increasing thickness of the polymer electrolyte if the thicknesses of other components are kept constant. Also, the thermal diffusivity in the X direction has a very small value because the contribution to average thermal diffusivity in X direction mainly comes from that of polymer electrolyte, while the average thermal diffusivity in Y direction, is of the order of the magnitude

400

c/o.3

380

g ? ha

360

340
C/8

320

10 20 LYlcm 30 40 50
0

300 _ U

I 20

I 40

I 60 LX&m

I 80

I 100

I
120

Fig 8. Effect of stack height on maximum temperature at the end of discharge of rate C/O.3and C/8 (LX = S.Ocm,
qeo = 373 K).

Fig. 10. Effect of thickness of different layer on average thermal diffusivity of cell stack in Y direction (basic cell: Li (114pm), PEO (2Opm), VO, (lOOpm), Al (15pm)).

Two

dimensional analysis of lithium polymer batteries

523

1. Li(2Spm). PEO@pm), WJ5orSn). Ni(lpm) 2. LW 14j1m).PEO(2O(un), VO,(lOOW. Al(lSW

h-

380

3. Li(l14pm). PEO(4Opm), JO,(l~W, Al(lSW 4. Li(57pm). PEO(2Opm). VO,(lOOW. Al(lSpm)

thermal conductivity. However, it is considered, from a heat transport point of view, that there exist some better designs, for which temperature gradient within a cell stack may be minimized. Also, for different designs, the large temperature gradients in the X direction may again suggest that the low thermal conductivity in X direction will limit heat removal rate, and therefore, the heat transport behaviour in the battery through the thickness direction is mainly characterized by the low thermal conductivity of the polymer. E$iect of bipolar connector material on temperature
profile

370 I 0

2 X/cm

Fig. 11. Effect of thickness of different cell component on temperature profile in a cell stack (Y = LY/2) (LX = 5.0cm, LY = 20.0011, xeo = 373K, C/0.3).

of those of its metal components (Li: 4.36 x 10-sm2s-1 andNi: 1.97 x 10-sm2s-1). The effect of different design on the temperature profile is shown in Fig. 11, which is obtained under the assumption that the heat generation rate is the same within stacks with same thickness (this assumption is adopted so as to study the effect of thermal diffusivity on heat conduction). Contrary to what might be expected, an increase in lithium thickness does not cause a decrease in temperature, instead it results in a small increase in battery temperature. This is because, if stacks have close values of thermal diffusivities (lines 2 and 4 in Fig. 11, corresponding to 114 and 57 pm thick lithium negative electrode, respectively), the temperature increase in stacks with larger heat capacity will be lower (see Fig. 12, where it is shown that heat capacity decreases with increasing lithium electrode thickness). In Fig. 11, it appears that there is no dramatic difference in temperature distributions in the stack center for different cell design. This is probably because the variation of the thickness of different cell components, within a certain range, will not cause significant change in
2.5 -

In order to reduce the cost and weight associated with the nickel current collector, and thus to increase the specific energy and specific power of a battery, a low density metal (eg aluminum) and metallized plastic current collector (eg 1000 A Ni on each side of a plastic sheet[25]) have been suggested for use in lithium/polymer electrolyte batteries. It is interesting to calculate what kind of current collector is preferable. Figure 13 shows the effect of different bipolar connector materials on temperature profiles in a cell stack. The results indicate clearly that no marked difference in temperature profile will result from choosing different current collectors. Therefore, a metallized plastic current collector, the thermal conductivity of which is lower than those of Al and Ni, can be applied in the battery from a heat transfer point of view.
Temperature profiles in lithium polymer electrolyte batteries with redox polymer or TiSZ as positive electrode

In addition to vanadium oxide positive electrode based lithium polymer electrolyte batteries, significant advances have been achieved in the study of batteries with redox polymer[6] and TiS,[S] as positive electrodes. In relation to heat generation and heat transport in batteries, the most important characteristics distinguishing lithium/solid polymer electrolyte batteries from other batteries are the low

; ti : E 2 9 ; rp =

2.4 -

2.3 -

390

2.2 -

. 90,
380

i. Al(lS~)
2. MeUized phrtic (15~ plastic + 2xl000ANi) 3. Ni(lSpm)

2.12.0
I I I I I I

20

40

60

80

100

120

370 I-0

2 X/cm

LX/pm Fig. 12. Effect of thickness of &&rent layers on average heat capacity of cell stack (basic cell: Li (114&, PEO W/WI VO, (toorunh Al W/J&).

Fig. 13. Effect of bipolar current collector material on temperature profile in a cell stack (Y = LY/Z) (C/0.3,
Lx = 5.Ocm. LY = 2O.Ocm, T, = 373 K) (ceil component:

Li (114&, PEO(20~),

VO, (KJOkm))).

524
370 r
ia2.OmA

Y. CHENand J. W. EVANS

cm-z

340 t 330 w
0 1

3'

X/cm Fig. 14. Temperature profiles in a cell stack (Y = LY/2) under different discharge current density (Li/PEO-LiX/Xl, theoretical cell capacity: OS83mAhcn-*[6]) (LX = S.Ocm, LY = 2O.Ocm,Lx, = 0.04, T,, = 357K).

current density of the cell, and the low thermal conductivity of the polymer. Therefore, it would be expected that these two effects might cancel and that similar thermal behaviour will be exhibited in lithium polymer electrolyte batteries with different materials for positive electrodes. This can be seen from Figs 14 and 15, which show the calculated temperature profiles in the redox polymer (Xl: dimercapto dithiazole polymer) and in TiS, based batteries, respectively. It is found that thermal characteristics similar to those in V,O,, system exist in

to increase current density (if the path length between the electrodes is lOO/lm, a limiting current density is estimated to be 4mAcm-[29]). Finally, it is considered that there is a large excess of lithium with 1OOpm thick lithium metal foil and efforts must be made to reduce lithium thickness to 30-40 pm per cell[26]. Hence, thin-film configured cells, eg with a thickness around 2OOpm, should be adopted. If total heat generation in one cell is assumed to be the same in the 4OOpm thick experimental cell as that in the 2OOpm cell (this assumption is a good approximation if the contribution to the electrode polarization mainly comes from charge transfer), the maximum temperatures within a stack of the same thickness consisting of 400 and 2OOpm cells, respectively, are estimated as a function of current density and are shown in Fig. 16. As would be expected, the maximum temperature in 2OOpm cell stack is higher than that in 4OOcm cell stack. However, even in the 200/1m cell stack, it appears that the temperature increase under high discharge rate will not result in a thermal runaway problem, for instance, the maximum temperature in the cell stack is expected to be lower than the melting point of lithium. Effect of heat transport in width direction on results from two dimensional model In most batteries with a rectangular geometry, gradients are predominantly in the cell thickness direction, such as the temperature gradients in the X direction encountered in the present analysis. This is because there are usually substantial differences between material properties encountered in that direction and, as in the present case, heat transport in that direction is typically governed by one material of low conductivity. Consequently, in two dimensional modeling of batteries, the usual choice of the two dimensions is one in the thickness direction and one of the two orthogonal directions. It is thought that practical thin lilm lithium polymer electrolyte batteries for electric vehicles are likely to consist of cells of from 400 to 2500 cm2 area. The corresponding height and width would be from 20 to 50cm. Comparing the thermal diffusivities in Figs 9 and 10, the diffusivities in the X direction are
400 r / _--Mm.

TiS, and the redox polymer systems, that is, under low discharge rate, insulating materials are needed to maintain battery operational temperature, while temperature will rise in large stacks during high rate discharge. In most experimental cells, the cell thickness is about 4OOpm. However, this kind of design is not an optimum design. To obtain high specific power, a thin positive electrode film is needed[28]. Also, the thickness of the polymer electrolyte must be reduced
390 i=Z.OmA cm-

a----: hY

z
h I

380

370 One cell thickness 0.04cm 0.02cm

350 1 0

360 1 2 X/cm 3 4 5 350 d 0 0.5

1.0

1.5

2.0

Fig. 15. Temperature distributions in a cell stack (Y = LY/ 2) at the end of discharge under different discharge current density (Li/PEO-LiX/TiS, , theoretical cell capacity: 0.868mAhcm-2[5]) (LX = 5.0cm, = 2O.Ocm, LX, = LY O.O4cm, q=,, = 373 K).

ilmA cm- Fig. 16. Effect of discharge current density on maximum in a cell stack (Li/PE&LiX/TiS, , temperature LX = KOcm, = 2O.Ocm, Te,, = 373 K). LY

Two dimensional analysis of lithium polymer batteries

525

380

Kz;,
0 10 20
LZlcm Fig. 17. Effect of stack width (LZ) on maximum temperature in cell stacks for discharge rate C/O.3 (LY = 20.0cm, qeO = 373 K) *T,,,ur,iw: maximum temperature if cell stacks are insulated.

30

40

50

results indicate that the change in thicknesses of cell components within a certain range, and the adoption of different current collector materials may not result in significant differences in battery thermal performance from the viewpoint of heat transfer, though there may exist some better designs for which temperature gradients along the thickness direction may be minimized. The thermal characteristics of the batteries with different positive electrodes, including V,O,s , TiSl and redox polymer, have been compared, and this comparison suggests that this kind of battery has similar thermal behaviour because of the low thermal conductivity of the polymer and the small current density of the cell.
Acknowledgements--We would like to thank Professor L. C. De Jonghe of University of California at Berkeley for providing us experimental data. Our thanks also go to Dr Frank R. MacLamon, Lawrence Berkeley Laboratory for helpful comments on this work. The Li Foundation Inc., NY, is acknowledged for awarding Y. Chen a postdoctoral fellowship at Berkeley. Finally, we appreciate the comments from the reviewers of this paper.

two orders of magnitude less than those in the Y direction. For LX greater than, say, 5 cm, heat transport in the X direction becomes less than that in the Y and 2 directions. For such thick stacks, it is then plausible to use a second two-dimensional model where the chosen dimensions are the Y and Z directions. In that case, k, replaces k, in the equations above and, because k, equals k,, the model becomes a homogeneous one. Figure 17 shows the effect of the width of the battery on the maximum temperature in the battery. It can be seen that if the width is much larger than the battery height, the maximum temperature, in the stack will be very close to that when the stack is insulated. This implies that the two dimensional (X-Y) model, which has been used to generate the results of prior figures in this paper, will be satisfactory except for batteries where the height and width are comparable. For this last case, the alternative model described in this paragraph should be used, in the case of thick stacks, or, in the case of
thin stacks, a full three-dimensional model (which the authors hope to present in a future publication) should be employed.

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CONCLUSIONS Thermal analysis of lithium solid polymer electrolyte batteries has been conducted to obtain information about how to maintain operating temperature by designing a proper battery structure and choosing a suitable cooling/insulating scheme. It is demonstrated that under high discharge rate, in order to prevent battery temperature from increasing significantly and to minimize temperature gradients across the battery, cell stack8 with small thickness may be preferable. However, under low discharge rate, the thermal management problem is how to maintain battery operational temperature, which can be realized by choosing conventional insulating materials. The effect of thickness of cell components on the temperature profile has been investigated. Also, the effect of different bipolar connector materials on temperature distribution has been examined. The

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