A Bio‐Inspired Methylation Approach to Salt‐Concentrated Hydrogel Electrolytes for Long‐Life Rechargeable Batteries

Abstract Hydrogel electrolytes hold great promise in developing flexible and safe batteries, but the presence of free solvent water makes battery chemistries constrained by H 2 evolution and electrode dissolution. Although maximizing salt concentration is recognized as an effective strategy to reduce water activity, the protic polymer matrices in classical hydrogels are occupied with hydrogen‐bonding and barely involved in the salt dissolution, which sets limitations on realizing stable salt‐concentrated environments before polymer‐salt phase separation occurs. Inspired by the role of protein methylation in regulating intracellular phase separation, here we transform the “inert” protic polymer skeletons into aprotic ones through methylation modification to weaken the hydrogen‐bonding, which releases free hydrogen bond acceptors as Lewis base sites to participate in cation solvation and thus assist salt dissolution. An unconventionally salt‐concentrated hydrogel electrolyte reaching a salt fraction up to 44 mol % while retaining a high Na + /H 2 O molar ratio of 1.0 is achieved without phase separation. Almost all water molecules are confined in the solvation shell of Na + with depressed activity and mobility, which addresses water‐induced parasitic reactions that limit the practical rechargeability of aqueous sodium‐ion batteries. The assembled Na 3 V 2 (PO 4 ) 3 //NaTi 2 (PO 4 ) 3 cell maintains 82.8 % capacity after 580 cycles, which is the longest cycle life reported to date.