Targeted Docking of Localized Hydrogen Bond for Efficient and Reversible Zinc‐Ion Batteries

Abstract Hydrogen bond (HB) chemistry, a pivotal feature of aqueous zinc‐ion batteries, modulates electrochemical processes through weak electrostatic interactions among water molecules. However, significant challenges persist, including sluggish desolvation kinetics and inescapable parasitic reactions at the electrolyte‐electrode interface, associated with high water activity and strong Zn 2+ ‐solvent coordination. Herein, a targeted localized HB docking mechanism is activated by the polyhydroxy hexitol‐based electrolyte, optimizing Zn 2+ solvation structures via dipole interaction and reconstructing interfacial HB networks through preferential parallel adsorption. By combining in situ spectroscopic characterizations with theoretical calculations, we elucidate the dynamic evolution of localized HB networks, which enhance Zn 2+ deposition kinetics and homogeneity, suppress water‐induced side reactions, and mitigate vanadium framework collapse. Our findings support that the targeted HB docking strategy facilitates fast interfacial ion transport kinetics and enables high reversibility, with a substantially prolonged symmetric cell lifespan exceeding 5000 h. This work markedly advances the efficient and reversible zinc‐based batteries.