Architecture Dependence on the Dynamics of Nano-LiFePO₄ Electrodes

Elucidating the role of interparticle Li transport and multi-particle (de)lithiation kinetics in nanoparticulate two-phase electrode materials such as LiFePO₄ is a challenging task because of the small temporal and spatial scale associated with the process. Often, the relevant processes that determine the kinetics of (dis)charging an electrode are assumed to be exclusively those associated with Li transport to and from the counter-electrode, without a consideration of interactions between particles. However, the redistribution of Li between nanoparticles can have a strong influence on the overall cell rate performance. Using a continuum model to simulate the lithiation kinetics of a porous aggregate of LiFePO₄ nanoparticles, we demonstrate the impact of cell architecture (in terms of ionic and electronic connectivities between active particles) and cycling rate on the multi-particle (de)lithiation kinetics. Specifically, the connectivity between particles is shown to have a strong effect on "interparticle phase separation," a process by which active particles undergo additional cycling (charge during the overall discharge) and amplified reaction rates. We show that interparticle phase separation can be reduced or eliminated by improving ("homogenizing") the connectivity between particles. Extensive comparisons to experimental literature and insights toward improving the performance of nanoparticulate electrodes are also provided