Achieving Unprecedent Cycling Life and Environmental Adaptability of Alkaline Zinc‐Based Batteries via Supramolecular Electrolyte Strategy

Abstract Zinc‐based batteries (ZBBs) in alkaline electrolytes with intrinsic safety and high power density have attracted extensive attention. However, their applications are significantly limited by the short cycling life, which originates from the water‐induced hydrogen evolution, corrosion, and dendrite formation at the Zn metal anode. Although various strategies, such as surface coatings and the introduction of specialized salts, have improved Zn anode stability, they often compromise electrochemical kinetics, especially under extreme working conditions (e.g., ultralow temperatures) due to the significantly influenced water activity. To overcome these challenges, an innovative dual‐crosslinked gel electrolyte (G‐PBA/PAAK), synthesized through esterification, non‐covalent self‐assembly, and polymerization, is developed. The rigid PAAK polymer framework provides superior mechanical strength, whereas the flexible G‐PBA supramolecular network enhances ion transport even at low temperatures. Moreover, abundant surface functional groups actively modulate interfacial electrochemical behavior of Zn anode. Benefiting from the triple advantages of the new electrolyte, ZBBs can operate at ultralow temperatures (−60 °C) and exhibit an exceptional cycle life of 30 000 cycles, which are the best of the reported alkaline ZBBs. Furthermore, with a practically high mass‐loading cathode (36.75 mg cm⁻²), stable cycling is sustained for over 60 days.