Electrochemical Stability of ZnMn₂O₄: Understanding Zn-Ion Rechargeable Battery Capacity and Degradation

Abstract

We present a refined Mn–Zn–H2O Pourbaix diagram with the emphasis on parameters relevant for the Zn/MnO2 rechargeable cells. It maps out boundaries of electrochemical stability for MnO2, ZnMn2O4, ZnMn3O7, and MnOOH. The diagram helps to rationalize experimental observation on processes and phases occurring during charge/discharge, including the position of charge/discharge redox peaks and capacity fade observed in rechargeable aqueous Zn-ion batteries for stationary storage. The proposed Pourbaix diagram is validated by observing the pH-dependent transformation of electrolytic manganese dioxide to hetaerolite and chalcophanite during discharge and charge, respectively. Our results can guide the selection of operating conditions (the potential range and pH) for existing aqueous Zn/MnO2 rechargeable cells to maximise their longevity. In addition, the relation between electrochemical stability boundaries and operating conditions can be used as an additional design criterion in exploration of future cathode materials for aqueous rechargeable batteries.