Revealing the Dominance of the Dissolution‐Deposition Mechanism in Aqueous Zn−MnO2 Batteries

Abstract Zn−MnO2 batteries have attracted extensive attention for grid‐scale energy storage applications, however, the energy storage chemistry of MnO2 in mild acidic aqueous electrolytes remains elusive and controversial. Using α‐MnO2 as a case study, we developed a methodology by coupling conventional coin batteries with customized beaker batteries to pinpoint the operating mechanism of Zn−MnO2 batteries. This approach visually simulates the operating state of batteries in different scenarios and allows for a comprehensive study of the operating mechanism of aqueous Zn−MnO2 batteries under mild acidic conditions. It is validated that the electrochemical performance can be modulated by controlling the addition of Mn2+ to the electrolyte. The method is utilized to systematically eliminate the possibility of Zn2+ and/or H+ intercalation/de‐intercalation reactions, thereby confirming the dominance of the MnO2/Mn2+ dissolution‐deposition mechanism. By combining a series of phase and spectroscopic characterizations, the compositional, morphological and structural evolution of electrodes and electrolytes during battery cycling is probed, elucidating the intrinsic battery chemistry of MnO2 in mild acid electrolytes. Such a methodology developed can be extended to other energy storage systems, providing a universal approach to accurately identify the reaction mechanism of aqueous aluminum‐ion batteries as well.