Mass-Charge Regulatory Microdomains Enable Coupled Structural and Interfacial Stabilization of Durable 3D Lithium Metal Anodes.

Three-dimensional (3D) architectures can stabilize lithium (Li) metal anodes (LMAs) by mitigating localized charge accumulation and volume fluctuation, but the enlarged anode/electrolyte interfaces aggravate parasitic reactions and unstable solid electrolyte interphase (SEI) evolution. In this study, we constructed a mass-charge regulatory microdomain-functionalized LMA (MCRM-Li) by mechanically integrating a hierarchically structured NiSx framework with Li foil to address this structure-interface dilemma. The embedded conductive matrix partitions bulk Li into ordered microdomains and establishes an interconnected electron transport network to dissipate localized current density. Simultaneously, the in situ formed Li2S-rich interphase suppresses solvent attack and induces Li2S/LiF-enriched SEI formation during cycling, thereby homogenizing Li+ flux and facilitating interfacial Li+ diffusion. Consequently, the symmetric cell based on MCRM-Li delivers an ultralong lifespan of over 5380 h with dendrite-free Li deposition. Moreover, LiFePO4 full cells retain 94.1% capacity after 1000 cycles at 2 C. This work provides a coupled structural-interfacial design paradigm for durable lithium metal batteries through regional control of electric-field distribution and interfacial mass transfer in operating 3D LMAs.