Resolving the Anti‐freezing/Self‐healing Trade‐off in Zn‐Ion Batteries with a Zn ²⁺ ‐Anchored Dynamic Quaternary Hydrogen‐Bond Network for Extreme‐Temperature Operation

ABSTRACT The commercialization of aqueous zinc‐ion batteries is hampered by a fundamental paradox: electrolytes with anti‐freezing properties typically lack self‐healing capability, and vice versa. Herein, we decouple this trade‐off through the ingenious design of a synergistic network within a eutectogel electrolyte. This network is governed by strong Zn 2+ coordination acting as rigid anchors, coupled with a dynamic quaternary hydrogen‐bond (HB) network involving glycerol, ClO 4 − , water, and polyacrylamide serving as flexible bridges. In this configuration, the strong Zn 2+ coordination and dense hydrogen bonds synergistically inhibit ice lattice formation to ensure anti‐freezing, while the reversible hydrogen bonds enable dynamic molecular reconfiguration for self‐healing. The resulting gel remains ice‐free at −75°C and self‐heals within 10 min even at −20°C. Concurrently, this unique structure reconstructs the Zn 2+ solvation sheath, significantly reducing the water coordination number from 3.65 to 2.62, which effectively suppresses water‐induced parasitic reactions. Coupled with robust in situ interfacial engineering, the assembled battery exhibits a high specific capacity and exceptional cycling stability (97.0% capacity retention after 1000 cycles at 5 A g −1 ) over a wide temperature range of 80°C (−20°C–60°C). This work not only provides a high‐performance electrolyte for practical zinc batteries but also establishes an innovative design paradigm for resolving property conflicts in advanced functional materials.