(Invited) Using a Chemo-Mechanical Model to Investigate Electrolyte Infiltration and Surface Reconstruction within Cracked Cathode Material

Abstract

One of the main goals in modeling lithium-ion batteries is to improve/predict longevity and resilience of new chemistries. To that end, this talk investigates the formation of stress-induced fracture within polycrystalline cathode particles and the impact on capacity loss. The model captures anisotropic Li diffusion within a single polycrystalline particle comprised of hundreds to thousands of randomly oriented grains. Fracture is primarily due to non-ideal grain interactions with slight dependence on high-rate charge demands. Essentially, when neighboring grains are misaligned, they expand a different rates relative to one another leading to high stresses and ultimately the formation of intraparticle cracks. A previous study showed that small particle with large or single grain geometry tend to crack less and retain the most capacity.Cracks within the cathode particle that have access to the surface can potentially fill with electrolyte. When this happens, the cracks can be considered new active surface area where the lithium intercalation reaction can occur. Under sufficient conditions, this could lead to better performance because the grains of the cracked particle start to operate more like a network of single-grain particles. However, the newly open surface area is also subject to side reactions and surface reconstruction resulting in diminished transport properties and potentially trapped lithium. The goal of this talk is to investigate this balance between improved lithium transport pathways caused by lithium infiltration and the reduced diffusion due to surface reconstruction.