A Dynamically Stable Mixed Conducting Interphase for All‐Solid‐State Lithium Metal Batteries

Abstract All‐solid‐state lithium (Li) metal batteries (ASSLMBs) employing sulfide solid electrolytes have attracted increasing attention owing to superior safety and high energy density. However, the instability of sulfide electrolytes against Li metal induces the formation of two types of incompetent interphases, solid electrolyte interphase (SEI) and mixed conducting interphase (MCI), which significantly blocks rapid Li‐ion transport and induces uneven Li deposition and continuous interface degradation. In this contribution, a dynamically stable mixed conducting interphase (S‐MCI) is proposed by in situ stress self‐limiting reaction to achieve the compatibility of Li metal with composite sulfide electrolytes (Li₆PS₅Cl (LPSCl) and Li₁₀GeP₂S₁₂ (LGPS)). The rational design of composite electrolytes utilizes the expansion stress induced by the electrolyte decomposition to in turn constrain the further decomposition of LGPS. Consequently, the S‐MCI inherits the high dynamical stability of LPSCl‐derived SEI and the lithiophilic affinity of Li–Ge alloy in LGPS‐derived MCI. The Li||Li symmetric cells with the protection of S‐MCI can operate stably for 1500 h at 0.5 mA cm⁻² and 0.5 mAh cm⁻². The Li||NCM622 full cells present stable cycling for 100 cycles at 0.1 C with a high‐capacity retention of 93.7%. This work sheds fresh insight into constructing electrochemically stable interphase for high‐performance ASSLMBs.