LAUSR

Hydrogel electrolyte is widely used in solid energy storage devices because of its high ionic conductivity, environmental friendliness, and non‐leakage property. However, hydrogel electrolyte is not resistant to freezing. Here, a high proton conductive zwitterionic hydrogel electrolyte with super conductivity of 1.51 mS cm–1 at −50 °C is fabricated by random copolymerization of acrylamide and zwitterionic monomer in the presence of 1 m H2SO4 and ethylene glycol (EG). The antifreezing performance and low temperature conductivity are ascribed to hydrogen bonds and ionic bonds between the components and water molecules in the system and can be tuned by changing the monomer ratio and EG contents. The proton hopping migration on the ionic group of the polymer chains and Grotthuss proton transport mechanism are responsible for the high proton conductivity while Grotthuss transport is dominated at the glassy state of the polymer chains. The electrolyte‐assembled supercapacitor (SC) offers high specific capacitance of 93.5 F g–1 at 25 °C and 62.0 F g–1 at −50 °C with a capacitance retention of 91.1% and 81.5% after 10 000 cycles, respectively. The SC can even work at −70 °C. The electrolyte outperforms most reported antifreezing hydrogel electrolytes and has high potential in low‐temperature devices.