Although alkaline zinc-manganese dioxide batteries have dominated the primary battery applications, it is challenging to make them rechargeable. Here we report a high-performance rechargeable zinc-manganese dioxide system with an aqueous mild-acidic zinc triflate electrolyte. We demonstrate that the tunnel structured manganese dioxide polymorphs undergo a phase transition to layered zinc-buserite on first discharging, thus allowing subsequent intercalation of zinc cations in the latter structure. Based on this electrode mechanism, we formulate an aqueous zinc/manganese triflate electrolyte that enables the formation of a protective porous manganese oxide layer. The cathode exhibits a high reversible capacity of 225 mAh g⁻¹ and long-term cyclability with 94% capacity retention over 2000 cycles. Remarkably, the pouch zinc-manganese dioxide battery delivers a total energy density of 75.2 Wh kg⁻¹. As a result of the superior battery performance, the high safety of aqueous electrolyte, the facile cell assembly and the cost benefit of the source materials, this zinc-manganese dioxide system is believed to be promising for large-scale energy storage applications.

Involvement of dimethyl carbonate and trifluoromethanesulfonate anions in a hybrid aqueous electrolyte enables the formation of a new Zn ²⁺ -solvation structure and a ZnF ₂ –ZnCO ₃ -rich interphase that stabilizes the Zn battery chemistry.