A silk fibroin hybrid hydrogel electrolyte enables highly robust aqueous zinc-ion batteries to operate from -60 to 60 °C.

Aqueous zinc-ion batteries (AZIBs) enable safe and sustainable grid-scale energy storage but are limited by dendrite growth, parasitic reactions, and poor temperature tolerance. Herein, we report a multifunctional silk fibroin/polyacrylamide hydrogel electrolyte (SF/PAM-HGE) enabling stable zinc electrochemistry from -60 to 60 °C. SF β-sheet-mediated network reconstruction enhances the mechanical properties of the hydrogel electrolyte, whereas SF's abundant polar groups disrupt water hydrogen bonds, granting the hydrogel wide-temperature adaptability. In addition, the ligand environment tailored by SF's zincophilic polar groups regulates the Zn2+ solvation structure, facilitates directional Zn2+ transport, and cooperates with preferential interfacial adsorption for guided uniform deposition, thereby suppressing dendrite growth and side reactions. Consequently, the SF/PAM-HGE endows symmetrical Zn cells with stable Zn plating/stripping across a broad temperature range. The Zn‖PANI cells achieve 18 000 cycles with nearly 100% capacity retention at -40 °C and operate stably from -60 to 60 °C. Furthermore, four-electron Zn‖I2 batteries deliver 391.6 mAh g-1 and cycle over 8000 times. Pouch cells also exhibit robust cycling with a high areal capacity of 3.96 mAh cm-2. This work provides a molecular-network design strategy for hydrogel electrolytes toward reliable all-climate AZIBs.