Hongbao Zheng, Xinyuan Zhang, Wenqiang Lu, Zhichao Hou, Zhixuan Wei, Nan Chen, Dong Zhang, Heng Jiang, Fei Du
The key challenge of implementing aqueous manganese (Mn) metal batteries is severe water-related parasitic reactions, including the hydrogen evolution reaction and Mn corrosion. These issues originate largely from the high reactivity of solvated water around manganese ions (Mn2+). Herein, we design a hydrogel electrolyte that reconstitutes the Mn2+ solvation structure and establishes a hydration-regulated ion-migration environment. The incorporated 18-crown-6 macrocycles on polymer chains bind strongly to Mn2+, reducing its hydration number from 5.51 to 1.39 and forming a water-repelling, polymer-guided conduction pathway. Dynamic measurements demonstrate uniform Mn deposition and suppressed detrimental gas evolution. Consequently, Mn plating/stripping in this hydrogel becomes highly reversible, achieving an average Coulombic efficiency of 95% over 350 cycles (Mn||Cu cells) and low polarization of ∼24 millivolts for over 1800 hours (Mn||Mn cells). Moreover, pouch cells paired with a silver vanadium oxide (AgVO) cathode (N/P ratio of 4.63) retain 95.3% of the initial capacities after 200 cycles. This work demonstrates an effective solvation-regulation strategy via hydrogel design for durable Mn anodes in aqueous batteries.