A lithium-ion battery cell’s electrochemical performance can be obtained through a series of standardized experiments, and the optimal operation and monitoring is performed when a model of the Li-ions is generated and adopted. With discrete-time parameter identification processes, the electrical circuit models (ECM) of the cells are derived. Over their wide range, the dual-polarization (DP) ECM is proposed to characterize two prismatic cells with different anode electrodes. In most of the studies on battery modeling, attention is paid to the accuracy comparison of the various ECMs, usually for a certain Li-ion, whereas the parameter identification methods of the ECMs are rarely compared. Hence in this work, three different approaches are performed for a certain temperature throughout the whole SoC range of the cells for two different load profiles, suitable for light- and heavy-duty electromotive applications. Analytical equations, least-square-based methods, and heuristic algorithms used for model parameterization are compared in terms of voltage accuracy, robustness, and computational time. The influence of the ECMs’ parameter variation on the voltage root mean square error (RMSE) is assessed as well with impedance spectroscopy in terms of Ohmic, internal, and total resistance comparisons. Li-ion cells are thoroughly electrically characterized and the following conclusions are drawn: (1) All methods are suitable for the modeling, giving a good agreement with the experimental data with less than 3% max voltage relative error and 30 mV RMSE in most cases. (2) Particle swarm optimization (PSO) method is the best trade-off in terms of computational time, accuracy, and robustness. (3) Genetic algorithm (GA) lack of computational time compared to PSO and LS (4) The internal resistance behavior, investigated for the PSO, showed a positive correlation to the voltage error, depending on the chemistry and loading profile.
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