Physically Cross-Linked Silk Fibroin-Based Tough Hydrogel Electrolyte with Exceptional Water Retention and Freezing Tolerance

Flexible ionic conductive hydrogel is attracting significant interest as it could be one of the crucial components for multifunctional ionotronic devices. However, their features of inevitably drying out without package and freezing at subzero temperatures may greatly limit the applications of conventional hydrogels in specific situations. Here, we present an ionic conductive hydrogel with water retention and freezing tolerance that consists of silk fibroin, ionic liquid, water, and inorganic salt. It is discovered that the ionic liquid serves multiple purposes to prevent water evaporation, decrease the freezing point, provide the essential conductivity of the hydrogel, etc. As a binary mixed solvent, the ionic liquid/water mixture enhances both water retention and freezing tolerance of the hydrogel electrolyte. Based on the silk fibroin (SF)/1-ethyl-3-methylimidazolium acetate (EMImAc)/H₂O/KCl hydrogel electrolyte, the flexible fiberlike supercapacitor could still function well at a temperature as low as -50 °C and after being stored in the open air for a long time. It is anticipated that this hydrogel will prove useful in developing new applications operating under harsh environments.