Investigation of Microstructural Evolution in All-Solid-State Micro-Batteries through in situ Electrochemical TEM

Abstract: All-solid-state batteries hold great promise for electric vehicle applications due to their enhanced safety and higher energy density. However, further performance optimization requires a deeper understanding of their degradation mechanisms, particularly at the nanoscale. This study investigates the real-time degradation processes of an oxide-based all-solid-state micro-battery, using focused ion beam lamellae composed of LAGP as the solid electrolyte, LiFePO4 (LFP) composite as the positive electrode, and LiVPO4 (LVP) composite as the negative electrode. In situ electrochemical transmission electron microscopy (TEM) revealed critical degradation phenomena, including the formation of cracks along grain boundaries in the solid electrolyte due to lithium diffusion and mechanical stress. Additionally, the shrinkage of solid electrolyte particles and the formation of amorphous phases were observed. These findings highlight the importance of grain boundary dynamics and amorphization in the performance of solid electrolytes and provide insights into degradation mechanisms that can inform the design of more durable all-solid-state batteries.