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Electrochemical Modeling and Simulation

of Lithium Ion Batteries

C. Hellwig* and W. G. Bessler
German Aerospace Center (DLR), Institute of Technical Thermodynamics,
Thermodynamics, Stuttgart, Germany

Motivation Research group

Lithium-Ion batteries are recieving increased attention and Elementary kinetics Electrochemical simulation

importance for portable and mobile applications Multi-

Multi-scale approach

Fundamental processes on cell and electrode level are still not

Simulation software
sufficiently understood Modeling Simulation

Goal: Scientific understanding and model-based optimization of Research Group:

SOFC/GT hybrid plant Modeling in DENIS/MATLAB
electrochemical and transport processes in lithium-ion batteries Electrochemical
for supporting technological development Energy Technology
Head: Wolfgang G. Bessler Solid oxide fuel cells
Modeling framework [1] based on microscopic description of w/DLR-
Helmholtz Young Investigator
PEFC hybrid vehicle 6 PhD, 1 postdoc
thermodynamics, kinetics, transport and structure to predict
Macroscopic electrochemical observables (discharge / charge Optimization Interpretation
behavior, capacity, SOC) w/DLR-
w/DLR-FK Polymer electrolyte fuel
Direct-flame SOFC Lithium batteries cells
Ageing processes (SOH) and durability
Heat transport and hot spot formation
Uni Duisburg, Shinko

Modelling and simulation approach Results and discussion

Multi-scale approach to understand macroscopic electrochemical
Multi- 1D model: Simulated discharge characteristics
behavior (capacity,
capacity, power, SOC) and lifetime (SOH) from
microscopic physicochemistry
4.2 4.2
Overpotentials at 1C
LiC6 / LiCoO2 4.0

Cell voltage [V]

Cell voltage [V]

3.8 3.6
3.2 Eta Electrolyte
3.4 C/5 3.0 Eta Cathode
C/2 2.8
3.2 Eta Anode
3.0 2.4
0 1 2 3 4 5 0 1 2 3 4
2 2
Capacity [mAh/cm ] Capacity [mAh/cm ]

Charge neutrality condition c z

i i 0
Simulation shows typical voltage behavior at low discharge rates
c i zF
Nernst-Planck equation of ion transport Di c i i c i Di Pos. El. Separator Neg. El.
t RT 1.0 3.5
Stoichiometry x in LixC6 / LixCoO2

Concentration Li [mol / l]

E act
Arrhenius behavior of diffusion coefficients D D 0 exp 0.7 2.5
RT 0.6 x in LixCoO2

0.5 F act 0.5 F act
0.4 1.5
Butler-Volmer equation i i 0 exp exp
0.3 1.0
RT RT c(Li )
0.2 x in LixC6
LiMC LiM CoO 0.0 0.0
Stoichiometry of anode (x) and cathode (y) x 6
y 2
0 50 100 150 200 250 300
C MLi 6
CoO MLi 2 Distance through cell [m]

Amount of intercalation of Li in electrodes depends on location of

Half-cell potential of anode and cathode from empirical polynomials
each particle and differs inside one electrode [3]
Concentration of Li+ in electrolyte shows good aggreement with
Parameters [2,3,4]: D0 = 1.0710-11 m2/s, T = 298 K, i0 (Anode) =
other studies [4]
3.6105 A/m3, i0 (Cathode) = 3.6105 A/m3, C6 = 1050 kg/m3, CoO2
= 3225 kg/m3

Conclusions Outlook
Demonstrated multi-scale modeling and electrochemical Half-cell potentials based on physical thermodynamic data in
simulation for physically-based prediction of cell behavior order to reduce empiricism
1D simulations show typical discharge behavior. Distribution of Elementary kinetic models of side reactions such as SEI
loss processes can be quantified. formation leading to ageing of cells
Quantification of spatially resolved Li concentration in Heat production and heat transport as well as its feedback on
intercalation electrode and electrolyte electrochemical behavior (e.g., hot spot formation)

[1] W. G. Bessler, S. Gewies,

Gewies, and M. Vogler, Electrochim.
Electrochim. Acta 53, 1782-
1782-1800 (2007). [3] K. A. Smith, C. D. Rahn, C.-
C.-Y. Wang, Energy Conversion and Management 48, 2565-
2565-2578 (2007)
[2] G. Sikha,
Sikha, R. E. White, B. N. Popov,
Popov, Journal of The Electrochemical Society 152, A1682-
A1682-A1693 (2005) [4] D. Danilov,
Danilov, P. H. L. Notten,
Notten, Electrochim.
Electrochim. Acta 53, 5569-
5569-5578 (2008)