Doping Strategies for Improving Performance of Li‐Argyrodite Solid‐State Electrolyte

Li‐argyrodite solid‐state electrolyte (SSE) holds promise for all‐solid‐state lithium batteries (ASSLB) but faces limitations in room‐temperature ionic conductivity, electrode/electrolyte interface compatibility, and air stability. Doping strategies offer a viable approach to address these challenges. This article provides a comprehensive review of the structure–property relationships and recent doping strategies for Li‐argyrodite electrolytes. First, the crystal structural features are analyzed to elucidate the intrinsic relationship between the structure and key properties, including ionic conductivity and the electrochemical window. Second, the mechanisms by different dopants affecting the performance of Li‐argyrodite electrolytes are investigated, focusing on ionic conductivity, air stability, thermal stability, electrochemical performance, and interfacial stability. Finally, the current status and future development trends of Li‐argyrodite SSE are summarized, and targeted strategies are proposed to enhance the application in ASSLB.