Sulfonate‐Mediated Cation‐Switching in Hydrogel Electrolytes to Unlock Fast Ion Transport for Low‐Temperature Zinc Batteries

ABSTRACT Hydrogel electrolytes (HEs) are promising for zinc batteries owing to their high safety and intrinsic flexibility. However, limited carrier transfer kinetics from bulk phase to the interface of HEs hinder their practical applications at low temperatures. Here, we proposed a sulfonate‐mediated cation‐switching strategy to design antifreezing HEs with rapid ion transport for Zn batteries. The introduced Li + replaces Zn 2+ from oxygen coordination sites via strong sulfonate (−SO 3 − ) binding within the polymer matrix. The Li + ‐O bonds contract the polymer network, which in turn squeezes and rearranges the water molecules and ions in the pores into a highly interconnected state. This shifts the ion transport from a hopping‐dominated transport to a diffusion‐controlled, enhancing both ionic conductivity (7.75 mS cm −1 ) and Zn 2+ transference number (0.32) at −40°C. The liberated Zn 2+ further coordinates free water, lowering the glass transition temperature to −53.5°C. Moreover, the sacrificial process of polymer and salts results in the gradient interphase with a ZnS/ZnCO 3 ‐rich surface and a Li 2 S/Li 2 CO 3 ‐rich bottom, which reduced the Zn 2+ ‐diffused activation energy by nearly 50%. The Zn||VO 2 ‐V 2 O 5 /NC full cell with optimized HEs cell exhibits 83.7% capacity retention (5 000 cycles, −40°C) and 92% retention at 180° bending.