Synergistic d‐π Coupling and Interfacial Catalysis Enable Electron‐Ion Dual Kinetics in Ah‐Level Zinc‐Ion Batteries

ABSTRACT Aqueous zinc‐ion batteries (AZIBs) are constrained by mismatched electron and ion kinetics, where sluggish electronic transport in cathodes and high interfacial desolvation barriers of hydrated Zn 2+ jointly limit practical performance. Here, we report a molecular architectonic strategy that enables electron‐ion dual kinetics through synergistic d‐π coupling and interfacial catalysis. By in situ anchoring 1H‐imidazole‐4‐carboxylic acid (ICA) molecules onto tunnel‐structured VO 2 , an organic‐inorganic hybrid cathode (IVO 2 ) is constructed. The π ‐conjugated framework of ICA engages in strong d‐π orbital coupling with V 3d states, inducing p ‐type doping and enhancing electronic conductivity. Simultaneously, the abundant hydrogen‐bond donor/acceptor sites of ICA act as interfacial catalytic centers that lower the Zn 2+ desolvation energy barrier, thereby accelerating interfacial ion transfer. Benefiting from this coupled kinetic modulation, the optimized IVO 2 ‐1.5 cathode delivers a high specific capacity of 567.8 mAh g −1 and sustains over 10 000 cycles at ultrahigh rates. Importantly, this molecular‐scale kinetic advantage translates to practical devices, as an Ah‐level pouch cell with a mass loading of 21 mg cm −2 and a stringent N/P ratio of 9.1 achieves a discharge capacity of 1.01 Ah with over 100% capacity retention after 110 cycles. This work provides a viable strategy for bridging molecular‐scale kinetic engineering with practical aqueous batteries.