| Abstract: | All‐solid‐state batteries have attracted attention owing to the potential high energy density and safety; however, little success has been made on practical applications of solid‐state batteries, which is largely attributed to the solid–solid interface issues. A fundamental elucidation of electrode–electrolyte interface behaviors is of crucial significance but has proven difficult. The interfacial resistance and capacity fading issues in a solid‐state battery were probed, revealing a heterogeneous phase transition evolution at solid–solid interfaces. The strain‐induced interfacial change and the contact loss, as well as a dense metallic surface phase, deteriorate the electrochemical reaction in solid‐state batteries. Furthermore, the in situ growth of electrolytes on secondary particles is proposed to fabricate robust solid–solid interface. Our study enlightens new insights into the mechanism behind solid–solid interfacial reaction for optimizing advanced solid‐state batteries. |
