Enhancing Two-Electron Reaction Contribution in MnO2 Cathode Material by Structural Engineering for Stable Cycling in Aqueous Zn Batteries

MnO2 is a promising cathode for aqueous Zn batteries. However, the cycling stability is seriously hindered by active material dissolution, and the pre-addition of Mn2+ salts in electrolytes is widely required. Herein, we propose a structural engineering strategy for MnO2 to enhance the capacity contribution from the reversible two-electron transfer reaction of MnO2/Mn2+ and realize stable cycling in Mn2+-free electrolytes. By compositing with MoO3, MnO2 exhibits weakened Mn–O bonds, more oxygen vacancies, spontaneous generation of structural water, and thus a lowered energy barrier for Mn release during discharge. Meanwhile, the composite material presents stronger electrostatic attractions for dissolved Mn2+, which ensures highly reversible re-deposition during charge. As a result, the mass ratios between materials undergoing reversible two-electron and one-electron transfer reactions increase from 0.85 in MnO2 to 1.68 in the MnO2/MoO3 composite material. In the ZnSO4 electrolyte, the MnO2/MoO3 cathode achieves 92.6% capacity retention after 300 cycles at 0.1 A g–1 (>1900 h), superior to 62.7% for MnO2. MnO2/MoO3 also retains 80.1% capacity after 16 000 cycles at 1 A g–1 (>3200 h). This work presents an effective path to realize stable cycling of MnO2 in Zn batteries.