Employing the Dynamics of the Electrochemical Interface in Aqueous Zinc‐Ion Battery Cathodes

Abstract Intrinsically stable materials are desirable for constructing energy storage devices, which aim to demonstrate durability under the harsh electrochemical conditions that are detrimental to their lifespan. However, it is demonstrated here that the intrinsic instability of an electrochemical interface can be converted from an obstacle into an advantage. In aqueous zinc‐ion batteries, manganese oxide (MnO 2 ) exhibits considerable dissolution even in electrolyte containing Mn 2+ salt. Balancing with redeposition alleviates the harmful impact of dissolution on performance and alters the trajectory of the active phase. Inclusion of Mn 2+ salt in the electrolyte induces MnO 2 deposition on all conductive surfaces, requiring that distracting side reactions be eliminated to isolate the dynamics of the active phase. Under conditions favoring dissolution, capacity decreases dramatically and a highly crystalline tetragonal ZnMn 2 O 4 phase forms, while redeposition helps maintain capacity and promotes a disordered cubic Zn‐rich phase. Ultimately, this work aims to illuminate a path forward to unlock the potential of batteries made with materials that are fundamentally unstable in their operating environment.