Stress Evolution on the Phase Boundary in LiFePO4 Particles

Abstract

It is commonly thought that diffusion-induced stress is one of the main factors causing loss of capacity in electrode materials. To understand stress evolution on the phase boundary during the lithiation process, we develop a finite element model adopting lithium ion concentration-dependent anisotropic material properties and volume misfits. Increased mechanical stresses on the phase boundaries are observed during the lithiation process. When the particle is more fully lithiated, larger stresses occur on the free surfaces and these may be related to the cracks on the ac-plane. The C-rate dependent strain energy evolution is also studied. The result shows that with the same amount of lithiation, particles experience different strain energies due to varied C-rate discharging. The high elastic energy from the high C-rate model suggests that the system becomes unstable, and a homogeneous phase transformation path is more plausible for the system. The current study provides a connection between diffusion-induces stresses on the phase boundary and the cracking propensity on free surfaces. Thus, the study could be used to better understand the mechanisms that cause particle fracture and capacity loss.