A Robust Molecular‐Bridged Hybrid Interphase for Dendrite‐Free and Durable Lithium Metal Batteries

ABSTRACT The practical implementation of lithium metal batteries (LMBs) requires overcoming the challenges posed by unstable interphase between Li metal and electrolyte, particularly under high areal capacities. Continuous chemical corrosion and non‐uniform plating/stripping degrade the solid electrolyte interphase (SEI), causing rapid capacity loss and safety risks. Herein, we propose a molecular bridged (MB) hybrid interphase integrated with dual silane coupling agents, enabling highly reversible Li anodes at high areal capacities in carbonate‐based electrolyte. The MB layer tightly anchors Li metal by chemical bonding, prevents delamination during high‐capacity Li deposition/dissolution, and decouples parasitic reaction from Li deposition by an anti‐corrosive coupling network. Consequently, the MB‐stabilized Li anode achieves an impressive cycling for 600 h at 1 mA cm −2 , and 8 mAh cm −2 , and sustains 474 cycles at 1 C with 80% capacity retention in Li||LiFePO 4 full cell. Furthermore, an Ah‐level pouch cell with high cathode loading (NCM811, ≈ 45.9 mg cm −2 ) maintains stable cycling at low N/P ratios (≈1.87). This strategy for constructing a molecular‐bridged interphase offers a new perspective for maintaining the artificial SEI integrity under harsh conditions, demonstrating the feasibility of durable, high‐performance LMBs with reduced Li loss.