Conjugated Molecular Interconversion Accelerates Interfacial Desolvation Kinetics for Aqueous Zn Metal Batteries

ABSTRACT The commercial viability of aqueous zinc metal batteries is bottlenecked by sluggish Zn 2 + desolvation kinetics and erratic interfacial charge transfer. Here, we report a catalytic strategy using 4‐dimethylaminopyridine (DMAP) as an interfacial molecular catalyst that undergoes structural interconversion between neutral phenolic and quinoid resonance forms. Unlike passive interfaces, this π ‐conjugated molecule orients at the metal‐electrolyte interface to function as a desolvation relay. Through electron delocalization and reversible lone‐pair coordination, the active interface transiently replaces water ligands, lowering the activation energy for Zn 2 + reduction. This catalytic interconversion facilitates the in situ formation of a vertically ordered, ion‐conductive interphase that homogenizes Zn 2 + flux and eliminates parasitic reactions. As a result, Zn||Zn symmetric cells operate stably for 1500 h at 1 mA cm − 2 and 300 h at 20 mA cm − 2 with 10 mAh cm − 2 , while Zn||Cu cells exhibit highly reversible plating/stripping for over 1800 cycles. Full Zn||Br 2 cells deliver 225 mAh g − 1 over 1500 cycles with Coulombic efficiency exceeding 99.25%. Our findings demonstrate that transitioning from passive to catalytic interface design is a transformative route for high‐rate, long‐life aqueous energy storage.