The development of high-energy cathode for rechargeable aqueous zinc-ion batteries (ZIBs) is highly attractive. However, the disproportionation effect of Mn²⁺ seriously affects the capacity retention of ZIBs during cycling. Defect engineering provides efficient methods to enhance conductivity and structural stability of active materials. Here, a novel in situ generated bulk oxygen deficient Mn₃O₄ nanoframes cathode for rechargeable aqueous ZIBs is reported, with high capacity and good electrochemical stability. The oxygen-deficient Mn₃O₄ spheres display an excellent gravimetric capacity of 325.4 mAh g⁻¹ and a high energy density of 423 Wh kg⁻¹ at a power density of 2257.2 W kg⁻¹. Ex situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterization demonstrate the initial Mn₃O₄ is converted to ramsdellite MnO₂ for insertion and extraction of H⁺ and Zn²⁺. Theoretical modeling reveal that numerous edge sites and oxygen vacancies act as preferential intercalation sites for the zinc ions, leading to a much greater capacity than that of defect-free Mn₃O₄. These results highlight the potentials of defect engineering as a strategy of improving the electrochemical performance of Mn₃O₄ in aqueous rechargeable batteries.

用于可充电水性锌离子电池（ZIB）的高能正极的开发极具吸引力。然而，Mn ²⁺的歧化效应严重影响了ZIBs在循环过程中的容量保持率。缺陷工程为提高活性材料的导电性和结构稳定性提供了有效的方法。在这里，报道了一种用于可充电水性 ZIBs的新型原位生成的块状缺氧 Mn ₃ O ₄纳米框架阴极，具有高容量和良好的电化学稳定性。缺氧的 Mn ₃ O ₄球体显示出 325.4 mAh g ^-1的优异重量容量和 423 Wh kg ^-1的高能量密度功率密度为 2257.2 W kg ^-1。异位X 射线衍射 (XRD) 和 X 射线光电子能谱 (XPS) 表征证明初始 Mn ₃ O ₄转化为斜方锰矿 MnO ₂以插入和提取 H ⁺和 Zn ²⁺。理论模型表明，许多边缘位点和氧空位作为锌离子的优先嵌入位点，导致比无缺陷 Mn ₃ O _{4 的}容量大得多的容量。这些结果突出了缺陷工程作为提高 Mn ₃ O ₄电化学性能策略的潜力 在水性可充电电池中。