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The key challenges in aqueous zinc-manganese dioxide batteries (MnO2//Zn) are their poor electrochemical kinetics and stability, which are mainly due to low conductivity and the inevitable dissolution of MnO2. A synergistic combination of a Co-doped σ-MnO2electrode (Co-MnO2) and a Co(CH3COO)2•4H2O (CoAc) electrolyte additive is here developed to design a high-performance aqueous MnO2//Zn battery (denoted as a Co-MnO2//Zn battery with CoAc). The introduction of Co ions (Co3+/Co2+) into the σ-MnO2electrode is achieved via a facile one-step electrodeposition method. Benefitting from the synergistic coupling effect of the Co-MnO2electrode and the CoAc electrolyte additive, the fabricated Co-MnO2//Zn battery with CoAc shows a commendable discharge capacity of 313.8 mAh g−1at 0.5 A g−1, excellent rate performance, excellent durability over 1000 cycles (∼ 92% capacity retention at 1.0 A g−1) and admirable energy density (439.3 Wh kg−1), which is a significant improvement compared with an un-doped σ-MnO2//Zn battery.