Mathematical model for the representation of the electrical behaviour of a lithium cell

A CAPEL
Alcatel Space Toulouse-France

1. INTRODUCTION Lithium ion systems have recently merged as a promising technology for energy storage in space applications with a high energy density reaching up to 1SOWh/Kg associated with a better charge retention than conventional systems, mainly NiCd and NiH2. The drawback of this technology' concerns the electrical performances which remain hardly predictable as they depend strongly on the species associated to lithium in the positive electrode, the material of the negative electrode, the selected technology ruling the lithium ion transfers from one electrode to the other and finally the industrial assembly process. This sophisticated technology induces an additional constraining consequence which implies the charge process and more specifically the end of charge procedure as irreversible degradations take place in case of any overcharge. However the prediction of the electrical performances is a must in the design of a satellite power system as the environmental conditions (temperature, power profiles and life time) affect them strongly. The approach which has been considered consists to give priority to a modular model, representative of the lithium ion systems where a reduced number of parameters reflects the dependence with environmental conditions while being able to integrate ageing effects. The Zimmerman model has been presented in the seventies (1) for the representation of the NiCd technology. It has been shown to be very suitable for the modelling of the lithium systems by its ability to associate electrochemical and statistical representations of cell operations. Its definitive advantage is its feature to represent the cell by an electrical network where branch currents and node voltages describe the internal processes of the cell while remaining compatible with the electrical system of a spacecraft. This model has been set up in the case of the G4 cell from SAFT. It consists in representing the behavior of the cell in all conditions by an equivalent non linear electrical circuit submitted to the electrical stimuli of the spacecraft power system. The influence of the internal temperature is introduced by an another

electrical network representing the thermal model of the cell in its environment.

2.

.ELECTRICAL MODEL OF THE LITHIUM CELL

The model of the lithium cell which has been developed is represented on fig 1 and is composed of 4 electrical elements, 2 capacitances and 2 resistances. Both capacitances are non linear, one gaussian C(ul) representing the energy storage effect, the second having an error function profile D(u2) for the difhsion and the internal charge equilibrium processes, UI and u2 being the voltages across respective capacitance terminals, separated by a non linear resistance r. The ohmic losses of the cell are represented by the linear resistance RB.

U1

+- i2

iB

-0
Fig 1: Electrical circuit representing the lithium-ion cell The capacitance C(u,) results to be the contribution of 2 capacitances Cl(ul) and C2(u1)in parallel and is described as the sum of two gaussian functions. It follows the analytical form given in (2.1):

where AI,B ,UIand U M I and Az, B2 , and u M 2 are parameters dependent on the cell current and temperature. The capacitance D(uZ)has the following forms (2.2): D(u,)=$(l+erf(u,-u,))

for for

0524, 1 4 1
4,l I u , I u ,

Gu,) = Q ( % 4
1976

-242)

0-7803-7067-8/01/$10.00 02001 IEEE

where Do , is also a parameter dependent on the cell current and temperature. The parameters uE, and uMare dependent on the cell technology and impose the extreme limits of the safe operation of the cell. They are respectively equal to 2JV and 5,OV. As the principle of the charge conservation has to be fulfilled, the following condition is imposed, if Q is the total capacity of the cell:
4,1
4,1

current is. imposed by the external network during discharge and charge, by applying:

When the cell voltage reaches an imposed limit v3, in order to avoid an overcharge, a tapper condition takes place and the current is defined by:

Q = lC(u,)du,+ lG(uz)duz
2,7
2-7

(2.3) On fig 3 are detailed the voltage and current waveforms during an 100% discharge-charge cycle for the theoretical model outputs and the test data at room temperature.
4.2

The reason which has conducted to select these analytical forms for the non linear capacitances comes from the comparison between the measured cell capacitance and the theoretical cell capacitances. Their profiles are represented on fig2 versus terminal voltages.

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fig 2: Measured (a) and theoretical (b) capacitance profiles for a complete cycle (charge and discharge) The superimposition of 2 gaussian profiles appears clearly in the measured capacitance with their respective maxima at 3,85V and 3,55V in discharge moving to 3,9V and 3,6V in charge. The diffusion effect, represented by the error function, is the consequence of the important difference in capacitance value between both edges of the gaussian curves which normally drift to zero. This measured capacitance reaches 350000F at 4,lV and is reduced to 50000F at 3,2V. The cell voltage is then available when the cell

I -20 1

.......................................................................................

__

fig 3: Comparison of cell voltage and current for theoretical model and test data

3. CURRENT DEPENDENCE OF THE MODEL PARAMETERS The representation of the electrical performances of the lithium cell, whatever is its technology and manufacturer is possible by calling to an electrical network composed of only 4 elements. The evaluation of extensive test data has conducted to give non linear forms to the capacitances and the resistance r interconnecting them and a linear form to the cell input resistance RB. Therefore 9 parameters
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have been identified which are A,, B1, U M ~and A,, B2, u M 2 for the 2 gaussian capacitances in parallel, then Do for the error function capacitance and finally Re and r for the resistances. The investigation among the possible analytical forms which offer a good correlation between test data and theoretical results has conducted to give preference to relations describing electrochemical processes. The Tafel law has appeared perfectly adequate to satisfy this requirement and even introduce some coherence between the parameters which will call for further investigations. It has been established, if i(t) is the instantaneous cell current, positive in charge and negative in discharge, and io a current reference for the cell under investigation, the following laws defining the dependence of the gaussian parameters with the current For the first capacitance Cl(ul) it comes:

investigation of the dependence of the electrical model of the lithium cell with the current has finally resulted to increase the number of model parameters as now 16 coefficients, only temperature dependent, have been identified.

4. TEMPERATURE DEPENDENCE OF PARAMETERS The prediction of the internal cell temperature T(t) with time is essential to get a realistic representation of the electrical behavior of the cell as the 16 identified model parameters are only temperature sensitive. The coherence with the Zimmennan approach has conducted to give preference to a thermal representation of the cell by an equivalent electrical network describing the heat transfer in the cell elements and its exchange with the spacecraft environment. This equivalent electrical network is detailed on fig 4.

A, = U,, + a,,Log(l+-)

w
10

(3.1)

B, = 4 , +bl,Log(l+i(t))
10

(3.2)

For the second capacitance Cz(ur)it comes as well:

A, = U,,

+ u,,Log(l

i(t) +-)
10

(3.3)

4 = b,, + b,,Log(l

+-)

40
10

(3.4)

The coefficients all, aI2, aZ1, aZ2 and io are only depending with the temperature according linear laws which will be detailed in next chapter. The same dependence applies to the maximum voltages of the gaussian curves UMl and uM,. The Tafel law is also verified with the diffusion capacitance D(u2) which is defined by:

i(t) D = d, + d,Log(l +-)

20

(3.5)
fig4: Thermal model of the cell in space environment The prediction of the internal cell temperature requires the knowledge of the power PB(t) involved in the internal losses and in the electrochemical processes. If vo,-(t) is the open circuit voltage of the cell and v(t) the cell terminal voltage, it has been established that(4.1):

where coefficients dl, and dZ, are also dependent with the cell temperature T(t). The Tafel law is also extended to the non linear resistance r interconnecting the capacitances C(u,) and D(uz). with the same analytical form:
Y

( i t) = r, + r,Log(l+-)
10

(3 -6)

where coefficients rl, and rz are also depending only with the cell temperature T(t). The resistance RB appears not be affected by the cell current i(t). This approach puts in evidence a surprising coherence of the non linear parameters with the cell current according analytical forms derived from the Tafel law. A typical parameter has been identified which is present in all relationships. It appears to be typical of a given technology and cell capacity and is only affected by the temperature and, certainly with the capacity degradation of the cell with the life time. The

dvoc Ps(t) = R,i2 ( t ) + i(t>(v,,(t) - v ( t ) - T ( t ) ) dt

The comparison between measured and theoretical node temperatures of the cell and its environment are displayed on fig5 over the same complete cycle displayed on fig3 at room temperature. The plate temperature is at 19,5"C and the cell temperature varies from 20,2" up to 24,6"C reaching maxima at end of discharge and at end of charge with constant current. During the tapering phase, the temperature drifts down as the power losses are strongly reduced. It can be stated that power losses predominate
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in this technology, being influenced by the electrochemical power generation when the operating point moves in the minima between the gaussian curves. The results confirm the adequacy of the selected approach for modeling the electrical and the thermal behavior of the cell.

The new coefficients are constant in a given mode but are unfortunately different between charge and discharge. The other coefficients of the gaussian capacitance C2(ul) remain linear with temperature, same value in charge as in discharge. They are:
a 2 2

25

= a227(4 + a220

(4.13) (4.14) (4.15) (4.16)

and
24

b 2 1
b22

23

= b211T(t)+b*10 = b221W) + 4 2 0

and
22

UM2

= U,, 1 T(t> + *MO

21

19 0 tMM 2MM 3 m

Another parameter has required a non linear dependence with the temperature. It concerns the typical reference current io. The following analytical law has been experimented with success:
uyao
S M M

Mmo

7MM

io
fig 5Evolution of the node temperatures over 1 cycle The extensive investigation made on test data has shown that satisfying results are available with a linear dependence of most coefficients with the cell temperature. For the gaussian capacitance Cl(ul) it has been verified that:

= io,LogT(t)

+ io,

(4.17)

where all new coeflicients are constants for a given technology as well in charge or in discharge modes. The same results apply for the capacitance D(u2) and resistances r and Rg. It comes:

The coefficients ioland ioohave resulted to be identical in charge and in discharge. The equivalent electrical model of the lithium cell, with its dependence with the current and the temperature ,is finally described by 78 coefficients, 34 for the charge and 34 for the discharge mode. Furthermore, these coefficients reflect the behavior of a given technology at beginning of life. The aging effect, certainly, will modify some of them. This influence will be the objective of a further investigation and is just indicated here. This complexity of this model is fortunately easy to handle as most of the coefficients are identical in both modes and they remain related by physical laws, familiar to electrochemical and electrical engineers. On table 1 are indicated the values of these coefficients with their directory structure. It can be verified that 25 coefficients remain unchanged from discharge to charge modes which leads to the conclusion that the influence of the current and the temperature can be described by 43 parameters using the derived Zimmerman electrical model with its associated thermal-electrical representation.
5. VALIDATION OF THE ELECTRICAL MODEL The validation of the derived Zimmerman model associated with a representative thermal model of the lithium cell is the logical follow on of this study. An extensive number of test data have been processed where the cell current, the temperature and the depth of discharge have been successively selected as the varying parameter. An accurate validation of this mathematical model with test data requires the comparison of measured and predicted cell capacitance

it was not For the gaussian capacitance C~(UI) possible to adjust data and theoretical results without calling for a non linear dependence of coefficient aZl such as:

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Table I voltage is an indicator of the state of charge of the as well as the displays of the evolution of electrical cell. Then the charge takes place 15A for all tests and thermal parameters. These steps have of course been completed for every test but the demonstration with a tapering phase when a defined voltage is will be limited to the direct comparison of cell reached, here 4,1 V voltages for few examples as the authorized length of The direct comparison of test data and theoretical cell voltage evolutions are detailed on fig5,6 and 7. On this paper cannot afford such a detailed presentation. In the frame of this presentation, four examples have fig5 is detailed this sequence for a light discharge 4A been chosen as representative of the electrical model at 10C. The predicted discharge voltage is slightly developments. Complete discharges and charges at above the measured data, indicating an estimation of 1O"then 20" and 30C with identical charge current a higher Ah capacity. This deviation is logically confirmed by an end of discharge voltage 3,15V of 15A and an end of charge voltage detection at 4,lV will be described with respectively 4A, 10A and instead of the measured 2,75V. The open circuit voltage 3,35V has the same value for both model and 22A discharge currents. test and calls to the conclusion that an identical state +1 of charge is detected. This point is confirmed during the charge phase as the taper voltage is reached 3 . 9 simultaneouslyby the model and the test. On fig6 the discharge current is increased to 10A and 3 . 7 the cell temperature environment is 20C. The prediction seems perfect for the discharge but a lower 35 open circuit voltage indicates a slightly lower state of charge. 33 On fig7 the discharge current is still increased to 22A at 30C. The deviation between theoretical and test 3 , i data appear negligible for all phases. The validation between the model and reality 2.9 requires the comparison of cell voltages in quite different conditions. It is the case on fig8 where data 2.7 0 1 M m l D w o M w o 4 m w y x y x I 6 M M extracted from a regular cycling with a limited duty cycle of 30 % at room temperature has been selected fig5: Theoretical and measured cell voltage at 10C to verify the adequacy of the model with very different stimuli conditions. The discharge current is The full discharge tests have all an identical profile. 24A and the taper voltage is reduced to 3,8W with a When the discharge voltage reaches 2,7V the charge current of 10A. discharge current is discontinued and the cell in open circuit recovers with a profile which is representative of the internal diffusion process. The open circuit
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4.m

the charge voltages is present which seems to converge toward the measured values after several cycles. 6. CONCLUSION The objectives which have directed the modelling of the lithium cell for space applications (but the approach may be extended to other needs) were to achieve an equivalent electrical network of the cell capable to predict its electrical performances combined with its thermal features. The derivation of the Zimmerman approach to model a storage cell has resulted to give a very flexible representation as the beginning of life of the cell is perfectly described with 43 constants. This number may appear to be high. However each constant is closely related to physical, electrochemical features of the cell and the active material which enter in its manufacturing. As a consequence simplified relationships between these constants and the cell data sheet are possible. They have not been detailed in this paper for length constraints reasons. Furthermore these constants may be utilised to generate additional relationships in order to predict the ageing effect of the cell operating in a long term mission with variable stress conditions. This model extension has been already experimented for NiCd (2) and will be the scope of the next step of investigation

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fig6: Theoretical and measured cell voltage at 20C

References
(1) H.Zimmerman-R.Peterson:An electrochemical cell equivalent circuit for storage battery in power system applications by digital computer.IECE Proc. Las Vegas-Nevada 1970 Cassagne-A.Cape1-G.Picart-G.Gave(2) M.P P.Willmann-G.Dudley-B.Hende1-B .ChattelanW.Dunford. Comparison between ELAN test results and an improved Zimmerman model ESPC Proc. Poitiers-France 1995

fig7: Theoretical and measured cell voltage at 30C

An open voltage phase is regularly introduced in

order to get information on the state of charge of the cell. It can be observed a good correlation in the behavior as identical end of discharge voltages involve identical states of charge, and therefore identical open circuit voltages. A slight deviation in
3,900

3.850 3,800 3,750 3,700 3,650 3,600 3,550 3,500

Fig8: Theoretical and measured cell voltage at 20"Cfor 30% DOD cycling

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