Abstract: | Rechargeable Zn/MnO2 batteries using mild aqueous electrolytes are attracting extensive attention due to their low cost, high safety, and environmental friendliness. However, the charge‐storage mechanism involved remains a topic of controversy so far. Also, the practical energy density and cycling stability are still major issues for their applications. Herein, a free‐standing α‐MnO2 cathode for aqueous zinc‐ion batteries (ZIBs) is directly constructed with ultralong nanowires, leading to a rather high energy density of 384 mWh g?1 for the entire electrode. Greatly, the H+/Zn2+ coinsertion mechanism of α‐MnO2 cathode for aqueous ZIBs is confirmed by a combined analysis of in situ X‐ray diffractometry, ex situ transmission electron microscopy, and electrochemical methods. More interestingly, the Zn2+‐insertion is found to be less reversible than H+‐insertion in view of the dramatic capacity fading occurring in the Zn2+‐insertion step, which is further evidenced by the discovery of an irreversible ZnMn2O4 layer at the surface of α‐MnO2. Hence, the H+‐insertion process actually plays a crucial role in maintaining the cycling performance of the aqueous Zn/α‐MnO2 battery. This work is believed to provide an insight into the charge‐storage mechanism of α‐MnO2 in aqueous systems and paves the way for designing aqueous ZIBs with high energy density and long‐term cycling ability. |