Phase Field Modeling of Coupled Phase Separation and Diffusion-Induced Stress in Lithium Iron Phosphate Particles Reconstructed From Synchrotron Nano X-ray Tomography

In this study, the phase separation phenomenon and diffusion-induced stresses in lithium iron phosphate (LiFePO₄) particles under a potentiostatic discharging process have been simulated using the phase field method. The realistic particles reconstructed from synchrotron nano X-ray tomography along with idealized spherical and ellipsoid shaped particles were studied. The results show that stress and diffusion process in particles are strongly influenced by particle shapes, especially at the initial lithiation stage. Stresses in the realistic particles are higher than that in the idealized spherical ones by at least 30%. The diffusion-induced hydrostatic stress has a strong relationship with lithium ion concentration. The hydrostatic stresses and first principal stresses tend to shift from lower values to higher values as the particle takes in more lithium ions. Additionally, the diffusion-induced stresses are related to the maximum concentration difference in the particle. High concentration difference will cause high stresses. In ellipsoid particles, the stress levels increase with the aspect ratios. The model provides a design tool to optimize the performance of cathode materials with phase separation phenomena.