Li ₃ N‐Enriched Solid Electrolyte Interphase Derived From Interfacial Catalysis Toward High‐Performance Lithium Metal Batteries

ABSTRACT The commercialization of lithium metal batteries (LMBs) is fundamentally challenged by Li dendrite growth, which originates from an unstable solid electrolyte interphase (SEI). Engineering a Li 3 N‐enriched SEI is highly desirable for achieving high conductivity and mechanical strength, but the kinetic barrier of the LiNO 3 ‐to‐Li 3 N conversion remains a major obstacle. Here, we report a catalytic approach to engineer Li 3 N‐enriched SEI layers by accelerating LiNO 3 reduction using transition metal single‐atom catalysts supported on nitrogen‐doped carbon (M/NC, M = Cr, Mn, Fe, Co, Ni, Zn). Among them, Co/NC exhibits the highest catalytic activity, leading to an SEI with significantly enhanced mechanical robustness and ionic transport. Theoretical calculations reveal that the superior performance of Co/NC stems from the minimal energy difference between its frontier molecular orbitals and those of the key LiNO intermediate, facilitating the electron transfer process. Consequently, the symmetric battery using Co/NC catalyst achieves exceptional cyclability for over 2500 h (1 mA cm −2 , 1 mAh cm −2 ). When applied in full cells, the Co/NC‐modified current collector also yields a dramatically prolonged cycle life. This work underscores the profound role of interfacial catalysis in designing high‐performance SEI for practical LMBs.