Rechargeable zinc-ion batteries with manganese dioxide cathode: How critical is choice of manganese dioxide polymorphs in aqueous solutions?

In this work, different MnO2 polymorphs are applied as cathodes in zinc-ion batteries (ZIBs). All the polymorphs result in similar electrochemical behavior in weak acidic (1\M) ZnSO4 aqueous solutions at comparable specific capacity (200-225 mAh g(-1)), similar charge-discharge curves, and temporal stability owing to an irreversible modification of the pristine positive electrode during battery charge and discharge. This irreversibility stems from the dissolution and re-deposition of MnO2 and the formation of new manganese and zinc compounds (basic salt deposits such as ZnMn2O4, Mn2O3, and MnOOH). The additional (new) MnO2 phase is formed via two routes: disproportionation of Mn+3 ions formed during the discharge process and anodic oxidation of Mn2+ ions in a solution. According to X-ray diffraction and Raman spectroscopy analyses, the re-deposited MnO2 is in an amorphous state. The amorphous MnO2 covers the surface of the initial crystalline particles and affects the electrochemical behavior of the ZIBs. The strong pH dependence of the electrochemical response of the MnO2 electrodes is related to the H+ concentration effect on ionic equilibria in this system, such as the formation of basic zinc and manganese salts and hydroxides as well as the disproportionation of Mn+3 and anodic oxidation of Mn+2.