Abstract
ABSTRACT
The instability of aqueous Zn batteries originates not only from the intrinsic reactivity of water, but also from the continuous hydrogen‐bonded network that enables cooperative interfacial degradation. In conventional aqueous electrolytes, this percolated water network supports proton relay, hydrogen evolution reaction (HER), local alkalization, by‐product precipitation, and Zn
2+
flux distortion, thereby forming a self‐amplifying failure loop at the Zn/electrolyte interface. Herein, we propose a molecular gating strategy to regulate this reactive water network using 4‐hydroxy‐2‐butanone (HBN) as a dual‐site hydrogen‐bond modulator. The carbonyl and hydroxyl groups of HBN competitively interact with water, fragmenting the continuous H
2
O–H
2
O hydrogen‐bond network into low‐cooperativity water domains and suppressing proton‐relay HER. Concurrently, HBN mildly reshapes the Zn
2+
solvation sheath environment toward a less water‐dominated configuration, moderating interfacial charge‑transfer while preserving essential Zn
2+
transport. This topology‐gated aqueous regime simultaneously suppresses water‐induced side reactions, prevents alkaline passivation‐driven Zn
2+
flux distortion, and enables compact Zn deposition. Consequently, the optimized electrolyte affords highly reversible Zn plating/stripping with an average Coulombic efficiency of 99.12% over 800 cycles and supports a 1.0 Ah‐level NVO||Zn pouch cell for 70 cycles with negligible capacity decay.