Hydrogen‐Bond‐Regulated and Rheologically Adaptive Interphase for Corrosion‐Suppressed Dense Zinc Deposition in Long‐Lasting 4 Ah Zinc Metal Batteries

The practical implementation of ampere‐hour‐scale aqueous zinc metal batteries is severely hindered by hydrogen evolution corrosion and dendritic growth under high‐current operation. Although regulating electrode–electrolyte interphase water via hydrogen bonding has been recognized as an effective strategy to suppress parasitic reactions, achieving dense, and uniform zinc deposition at high current densities remains a critical challenge due to interfacial instability and stress accumulation. Here, we construct a hydrogen‐bond‐network‐regulated ionic liquid layer coupled with a rheologically adaptive polydimethylsiloxane gel to establish a water‐poor and mechanically resilient interphase. The modified hydrogen‐bond network modulates the interfacial water environment, thereby contributing to suppressing corrosion. Simultaneously, the polydimethylsiloxane gel layer provides a hydrophobic barrier against water penetration and dynamically accommodates interfacial stress, enabling dense and uniform zinc deposition under high‐rate conditions. As a result, Zn||Zn symmetric cells exhibit exceptional cycling stability exceeding 1800 h at 50 and 25 mAh cm − 2 . More importantly, a 4 Ah pouch cell delivers stable cycling for 300 cycles with a cumulative capacity exceeding 1200 Ah. This work establishes a rational interphase engineering strategy for achieving durable, high‐capacity aqueous zinc metal batteries under practical high‐current conditions.