Interface Engineering of All‐Solid‐State Batteries Based on Inorganic Solid Electrolytes

Abstract All‐solid‐state batteries (ASSBs) based on inorganic solid electrolytes (SEs) are one of the most promising strategies for next‐generation energy storage systems and electronic devices due to the higher energy density and intrinsic safety. However, the poor solid‐solid contact and restricted chemical/electrochemical stability of inorganic SEs both in cathode and anode SE interfaces cause contact failure and the degeneration of SEs during prolonged charge‐discharge processes. As a result, the increasing interface resistance significantly affects the coulombic efficiency and cycling performance of ASSBs. Herein, we present a fundamental understanding of physical contact and chemical/electrochemical features of ASSB interfaces based on mainstream inorganic SEs and summarize the recent work on interface modification. SE doping, optimizing morphology, introducing interlayer/coating layer, and utilizing compatible electrode materials are the key methods to prevent side reactions, which are discussed separately in cathode/anode‐SE interface. We also highlight the constant extra stack pressure applied during ASSB cycling, which is important to the electrochemical performance. Finally, our perspectives on interface modification for practical high‐performance ASSBs are put forward.