Tough Hydro‐Aerogels with Cation Specificity Enabled Ultra‐High Stability for Multifunctional Sensing and Quasi‐Solid‐State Electrolyte Applications

Abstract The anion‐specific effects of the salting‐in and salting‐out phenomena are extensively observed in hydrogels, whereas the cation specificity of hydrogels is rarely reported. Herein, a multi‐step strategy including borax pre‐gelation, saline soaking, freeze‐drying, and rehydrating is developed to fabricate polyvinyl alcohol gels with cation specificity, exhibiting the specific ordering of effects on the mechanical properties of gels as Ca²⁺ > Li⁺ > Mg²⁺ >> Fe³⁺ > Cu²⁺ >> Co²⁺ ≈ Ni²⁺ ≈ Zn²⁺. The multiple effects of the fabrication strategy, including the electrostatic repulsion among cations, skeleton support function of graphene oxide nanosheets, and water absorption and retention of ions, endow the gels with the dual characteristics of hydrogels and aerogels (i.e., hydro‐aerogels). The hydro‐aerogels prepared with the cationic salting‐out effect display attractive pressure sensing performance with excellent stability over 90 days and enable continuous monitoring of ambient humidity in real‐time and effective work in seawater to detect various parameters (e.g., depth, salinity, and temperature). The hydro‐aerogels prepared without borax pretreatment or using the cationic salting‐in effect can serve as quasi‐solid‐state electrolytes in supercapacitors, with 99.59% capacitance retention after 10 000 cycles. This study realizes cation specificity in hydrogels and designs multifunctional hydro‐aerogels for promising applications in various fields.