Direct Proof of the Reversible Dissolution/Deposition of Mn2+/Mn4+ for Mild-Acid Zn-MnO2 Batteries with Porous Carbon Interlayers

Mild-acid Zn-MnO2 batteries have been considered a promising alternative to Li-ion batteries for large scale energy storage systems because of their high safety. There have been remarkable improvements in the electrochemical performance of Zn-MnO2 batteries, although the reaction mechanism of the MnO2 cathode is not fully understood and still remains controversial. Herein, the reversible dissolution/deposition (Mn2+/Mn4+) mechanism of the MnO2 cathode through a 2e(-) reaction is directly evidenced using solution-based analyses, including electron spin resonance spectroscopy and the designed electrochemical experiments. Solid MnO2 (Mn4+) is reduced into Mn2+ (aq) dissolved in the electrolyte during discharge. Mn2+ ions are then deposited on the cathode surface in the form of the mixture of the poorly crystalline Zn-containing MnO2 compounds through two-step reactions during charge. Moreover, the failure mechanism of mild-acid Zn-MnO2 batteries is elucidated in terms of the loss of electrochemically active Mn2+. In this regard, a porous carbon interlayer is introduced to entrap the dissolved Mn2+ ions. The carbon interlayer suppresses the loss of Mn2+ during cycling, resulting in the excellent electrochemical performance of pouch-type Zn-MnO2 cells, such as negligible capacity fading over 100 cycles. These findings provide fundamental insights into strategies to improve the electrochemical performance of aqueous Zn-MnO2 batteries.