A Zincophilic and Negatively‐Charged Self‐Reconstructed Stratified Interface for Regulating Zn ²⁺ Conduction and Nucleation Toward Conformal Dendrite‐Free Deposition

The practical deployment of aqueous Zn-ion batteries (ZIBs) is hindered by poor cycling stability, a consequence of dendrite growth and side reactions originating from irregular Zn nucleation and sluggish Zn²⁺ migration. Here, we construct a composite-phase NaMgF₃/Na₃InF₆ nanocube interphase (NMIF@Zn) that undergoes dynamic in situ reconstruction during plating into a stratified architecture. This transformation generates a zincophilic inner layer via preferential In³⁺ reduction, while the outer fluoride nanocubes retain a strong negative surface charge. The synergy between these reconstituted components and the nanocube matrix topology significantly enhances the interfacial electric double layer and creates unimpeded ion channels rich in zincophilic sites, collectively lowering the ion migration barrier and nucleation overpotential to enable conformal dendrite-free deposition. Consequently, the NMIF@Zn symmetric cell achieves superior cycling stability for 2000 h at 3 mA cm^-2/3 mAh cm^-2, along with stable operation at a high depth of discharge of 81.9%. When paired with a MnO₂ cathode, the interphase-optimized anode demonstrates excellent energy storage under high cathode loadings in both coin-type and pouch-cell configurations. This work establishes in situ interfacial conversion engineering as a powerful strategy to coordinately regulate ion flux and nucleation behavior, paving the way for durable Zn anodes in next-generation energy storage.