Equivalent circuit modelling for lithium-ion batteries

Marie-Therese von Srbik*1,2, Billy Wu2, Yannic Troxler1, Gregory J. Offer2 and Ricardo Martinez-Botas1
of Mechanical Engineering, Imperial College London, UK 2 Department of Earth Sciences and Engineering, Imperial College London, UK * E-mail of corresponding author: srbik@imperial.ac.uk
1 Department

1. Introduction
Batteries are becoming an increasingly important primary energy source for automotive applications. The simulation of battery behaviour in realistic operating conditions allows the prediction of voltage response, battery life and premature failure, all at reduced cost. Such predictions are crucial for developing optimised strategies for the vehicles Battery Management System (BMS). Robust, fast simulation with Electrical Equivalent Circuit Models (EEC) may be the answer. At lower complexity these models can fill in the gap between computationally-intensive high-fidelity models and purpose-built limited look-up tables. An example of this technique is given here. This project aims to arrive at a set of equivalent circuit models, in which the electrical elements represent electrochemical processes, including capacity and power fade.

2. Working principles

Liion batteries utilise lithium ions to reversibly convert from electrical to chemical energy. A battery cell consists of two electrodes, a cathode and an anode, with an ionically-conductive but electronically insulating separator in-between. The electrodes and the separator are soaked in the electrolyte. On either side of this unit, current collectors enable electrons to flow through the external circuit. Ideal discharge: Lithium ions diffuse from the anode to the cathode through the separator, via the electrolyte phase. Electric current must flow through the external circuit, to balance the charge exchanged during the chemical reactions taking place in the electrodes. During charge, the opposite process. In reality: Irreversibility of reactions + mechanical stresses effects compound over many cycles time-varying capacity and power fade

3. Equivalent circuit modelling

Electrical circuit elements with characteristic voltage response to a current load are chosen to mimic various electrochemical and physical phenomena in the cell. Various equivalent circuit architectures are used, depending on which phenomena must be captured. Electrochemical Impedance Spectroscopy (EIS) is a technique to measure the cell impedance at different excitation frequencies, by applying a small sinusoidal signal. The measured data is fitted to a pre-determined EEC, and parameter values for the circuit components are extracted. EIS is a non-invasive battery testing procedure, which can be performed during operation. Challenges: The temperature dependence of the electrochemical processes needs to be included in the electrical circuit elements Difficult to obtain battery parameters for the model (effective areas, particle sizes, lithium densities.) Difficult to identify circuitry parameters to fit cell phenomena, as effects from the two electrodes are usually not distinguishable in normal experiments Conclusions from experiment: Experimental EIS sweep of a 4.8 Ah Kokam lithium-polymer cell
60

Schematic of a Liion battery cell1

4. Stress Factors
Numerous stress factors can affect battery life, capacity and power fade. It is to be investigated how their effects can be taken into account by EEC modelling: Temperature How do high currents cause an increase in series and polarisation resistance? Depth of Discharge How significant is a small DoD operation window? Overcharge How damaging is overcharging? C-rate At what C-rates do various forms of damage start and when do they accelerate? Cycle number/history What is the effect of cycling on degradation?

50

-Imaginary impedance / m

40

30

Increasing cell voltage

Charge transfer resistance / m

2.8 V 3.0 V 3.2 V 3.4 V 3.6 V 3.8 V 4.0 V 4.2 V

C L RS RSEI

CPE
RCT

50

5. Temperature Dependency
Temperature strongly affects the parameters in a lithium-ion battery Parameters vary as a function of temperature as well as SOC Usually an Arrhenius rate law correlation
-80

40

30

20

10

20

3.0

10
-70

Charge transfer resistance / m

Imaginary impedance / m

-10 0 20 40 60 80

0 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4

-60 -50 -40 -30 -20 -10 0

Real impedance / m

Cell voltage / V

Decreasing temperature
-6 -4 -2 0 2 0 2 4 6 8 150 10 200

EIS Spectra of a 4.8 Ah Kokam lithium-polymer cell

Charge transfer resistance of a 4.8 Ah Kokam lithiumpolymer cell at different open circuit potentials

150

Charge transfer resistance Series resistance

2.0

100

Parameters vary non-linearly as a function of the State-Of-Charge (SOC) Charge transfer resistance increases at lower SOCs due to decreasing lithiation of anode It is more difficult to extract lithium when there is less of it Conclusions from simulation: Increasing number of electric circuitry elements fitted to result in the same impedance sweep as the real cell Simulated EIS curves
12
C1 CPE

50

1.5

0 1.0 -20 -10 0 10 20 30 40 50 60

50

100

Real impedance / m

Temperature / C

EIS spectra of a 4.8 Ah Kokam lithium-polymer cell at different temperature at 100 % SOC

Charge transfer resistance and series resistance as a function of temperature at 100 % SOC

3.5 3.0

C1 CPE W R1 R2 R3

Lithium-ion batteries perform better at higher temperatures (at the cost of lifetime) Charge transfer resistance increases exponentially at lower temperatures

10

R1 R2 R3

-Imaginary impedance / m

-Imginary impedance / m

2.5 2.0 1.5 1.0 0.5 0.0

6. Deliverables
T = 100 T = 200 T = 300 T = 400 T = 500
2 4 6 8 10 12 14 16

0 0 5 10 15 20 25 30 35 40

10 m 20 m 30 m 40 m 50 m
45 50

Real impedance / m

Real impedance / m

Simulated EIS spectra from equivalent circuits from a 0.01-10,000 Hz frequency range1 Constants used (unless otherwise varied): R1 = 2 m, R2 = 5 m, Cdl = 100 mF, R3 = 10 m and CPE = 10

Battery equivalent circuit model able to Predict voltage response to charge/discharge up to at least 20C Predict thermal response Predict causes and extents of types of damages within certain ranges of modes of operation Predict behaviour in realistic conditions, capacity and power fade Documentation of Model operating conditions and considerations to extend the operating envelope Suggestions for BMS strategies to reduce/limit damaging battery operating modes. The final equivalent circuit model can be a powerful complementary to an electrochemical model, and should be able to provide sufficient information to allow optimised battery operation within the vehicle energy system.

Electric circuit elements fitted to provide the same impedance spectrum as the measured one: The more elements, the more accurate the fit The more elements, the less obvious their physical meaning, and the more datasetspecific their prediction

References:
1 Dao,

T., Vyasarayani, C. P., & McPhee, J. (2012). Simplification and order reduction of lithium-ion battery model based on porous-electrode theory. Journal of Power Sources, 198, 329337. doi:10.1016/j.jpowsour.2011.09.034

For information on electrochemical battery modelling please refer to : Fault analysis and uneven heat generation in lithium-ion battery packs. Billy Wu, Vladimir Yufit, Monica Marinescu, David Howey, Gregory J. Offer, Ricardo Martinez-Botas and Nigel P. Brandon. VESI Conference. Warwick 2013.

Series resistance / m

-13 C -5 C 5 C 15 C 25 C 35 C 45 C 55 C

250
L RS

CPE
RSEI RCT

W
2.5

200