H+‐Insertion Boosted α‐MnO2 for an Aqueous Zn‐Ion Battery

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 ZnMn2 O4 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.