Architecting Zincophilic‐Hydrophobic Domains Within Co‐Crosslinked Hydrogels for All‐Climate Aqueous Zinc‐Ion Batteries

Aqueous zinc‐ion batteries with hydrogel electrolytes have attracted considerable attention for wearable energy‐storage devices owing to their intrinsic safety and mechanical flexibility. However, conventional hydrogel electrolytes often exhibit limited rate capability and environmental adaptability, which are closely related to the decoupled regulation of ion transport and interfacial chemistry. To overcome these limitations, a spatially cooperative electrolyte‐engineering approach was developed through constructing a co‐crosslinked network ( p (AM‐ co ‐VIB)) through the copolymerization of acrylamide (AM) and 1‐vinyl‐3‐butylimidazolium bromide (VIB), while introducing 3‐(N,N‐dimethylmyristylammonio) propane sulfonate (ST) to construct a hydrogel electrolyte (PV‐S). The p (AM‐ co ‐VIB) network provides efficient ion‐transport pathways and structural robustness, while the ST‐derived zincophilic‐hydrophobic domains regulate the local Zn 2+ coordination environment, promoting homogeneous Zn 2+ distribution and confining interfacial water. Consequently, the PV‐S electrolyte delivers an average coulombic efficiency of 99.57%. Furthermore, the Zn||Zn symmetric cells sustain highly reversible Zn plating/stripping across a broad current‐density range of 1–40 mA cm −2 . Notably, stable operation can be maintained over a wide temperature window (−40°C to 80°C), with prolonged cycling exceeding 2800 h at −20°C. Additionally, the Zn||NVO full cell retains 82.4% capacity retention over 850 cycles. Remarkably, the Zn||NVO pouch cell with a limited N/P ratio (3.9) retains 92.1% capacity after 220 cycles.