Dynamic Amorphous Zn0.17MnO2−n·0.52H2O Electrochemical Crystal Transition for Highly Reversible Zinc‐Ion Batteries with Ultrahigh Capacity and Long Lifespan

Mn‐based oxides promise high energy density and low toxicity cathodes for aqueous zinc‐ion batteries (ZIBs) but suffer from complex irreversible phase transitions, accompanied by continuous disproportionation reactions and manganese dissolution. Tailor‐made reversible and robust crystal structure in Mn‐based material is crucial and challenging. Here a controllable electrochemical oxidation induced crystal transition strategy is developed for the transformation of cubic α‐Mn2O3 into amorphous Zn0.17MnO2−n·0.52H2O, which serves as the host of Zn2+, empowering more highly accessible built‐in zincophilic sites whilst alleviating the lattice repulsion of Zn2+ (de)intercalation. As confirmed by crystal structure evolution characterizations and theoretical simulations, the amorphous Zn0.17MnO2−n·0.52H2O with excellent electronic properties and low zinc‐ion migration barrier can be reversibly converted into ZnMn3O7·3H2O. This stabilized dynamic electrochemical crystal transition equilibrium contributes ultrahigh capacity (558 mAh g−1), high‐energy density (696 Wh kg−1@6 kW kg−1), and superior stability (5000 cycles). The approach can also extend to Mn3O4 and α‐MnO2, opening new insights into electrochemical oxidation induced crystal conversion to build highly reversible and durable ZIBs. An efficient electrochemical oxidation induced crystal transition from α‐Mn2O3 to amorphous Zn0.17MnO2−n·0.52H2O is developed, activating reversibly dynamic conversion to ZnMn3O7·3H2O upon Zn2+/H+ co‐(de)intercalation for highly reversible zinc‐ion batteries.