Reactive and Adaptive Interphase Engineering for Regulating Interfacial Li + Transport in Li 2 OHCl Antiperovskite Solid‐State Batteries

ABSTRACT Lithium‐rich antiperovskite solid electrolytes, exemplified by Li 2 OHCl, are promising for all‐solid‐state lithium metal batteries. However, their practical implementation is severely constrained by interfacial instability with lithium metal, where nonuniform Li + flux and mechanical degradation induce dendrite growth. Herein, we introduce a MoS 2 ‐enabled adaptive interlayer on Li 2 OHCl that stabilizes the Li/SSE interface by regulating interfacial Li + transport. MoS 2 establishes a dual‐regulated Li + transport mechanism, in which the intrinsically Li + migration barrier in the MoS 2 bulk acts as a current‐limiting regulator, while the substantially lower diffusion barrier along the MoS 2 surface enables rapid lateral Li + redistribution. This synergistic “current‐limiting and fast‐transfer” effect effectively homogenizes interfacial Li + flux and suppresses localized ion accumulation that initiates lithium dendrites. Meanwhile, electrochemical reactions between MoS 2 and lithium metal form a composite interphase composed of lithiophilic Li 2 S and conductive Mo, which collectively lower the lithium nucleation overpotential, accelerate interfacial charge transfer, and stabilize the deposition front. Consequently, lithium‐metal symmetric cells exhibit stable cycling for over 1000 h with prolonged short‐circuit time, and all‐solid‐state lithium‐metal full cells demonstrate markedly improved cycling stability. This work establishes interfacial ion‐transport regulation as a design principle for stabilizing lithium‐metal anodes and provides a strategy for interface engineering in antiperovskite solid‐state batteries.