Full-Range Simulation of a Commercial LiFePO₄Electrode Accounting for Bulk and Surface Effects: A Comparative Analysis

The variable solid-state diffusivity (VSSD) and the resistive-reactant (RR) models that focus on different physical phenomena are used to investigate the solid-state transport (bulk effects) and electronic conductivity (surface effects) of LiFePO 4 (LFP). For the first time, the models are effectively validated against experimental galvanostatic discharge data over a full range of applied currents. To achieve a reasonable degree of accuracy, particle-level parameters are estimated by fitting to experimental data obtained under low-rate discharge conditions, whereas electrode-level properties are derived based on high-rate conditions. Particle size distribution turns out to play a pivotal role in determining the rate capability of the electrode determined by the VSSD and a revised version of the RR model. Based on the full-range comparative study, both the resistive-reactant effect and bulk-related rate limitations prove to contribute significantly to the electrode polarization, especially at high C-rate. The resistive-reactant effect is expected to increase in an electrode made of smaller LFP particles.