In Situ Spontaneous Construction of Zinc Phosphate Coating Layer Toward Highly Reversible Zinc Metal Anodes

Aqueous zinc ion batteries have received widespread attention due to their merits of high safety, high theoretical specific capacity, low cost, and environmental benignity. Nevertheless, the irreversible issues of Zn anode deriving from side reactions and dendrite growth have hindered its commercialization in large‐scale energy storage systems. Herein, a zinc phosphate tetrahydrate (Zn3(PO4)2·4H2O, ZnPO) coating layer is in situ formed on the bare Zn by spontaneous redox reactions at room temperature to tackle the above issues. Particularly, the dense and brick‐like ZnPO layer can effectively separate the anode surface from the aqueous electrolyte, thus suppressing the serious side reactions. Moreover, the ZnPO layer with high ionic conductivity, high Zn2+ transference number, and low nucleation barrier permits rapid Zn2+ transport and enables uniform Zn deposition, ensuring dendrite‐free Zn deposition. As a result, the ZnPO@Zn symmetric battery achieves a high Coulombic efficiency of 99.8% and displays ultrahigh cycle stability over 6000 h (> 8 months), far surpassing its counterparts. Furthermore, the ZnPO@Zn||MnO2 full battery exhibits excellent electrochemical performances. Therefore, this work provides a new reference for simple and large‐scale preparation of highly reversible Zn metal anodes, and has great potential for practical applications. Zinc phosphate tetrahydrate (Zn3(PO4)2·4H2O, ZnPO) coating layer is in situ formed on the bare Zn by spontaneous redox reactions. The dense and brick‐like ZnPO with high crystallinity can effectively suppress side reactions and dendrite growth, which endows ZnPO@Zn with long‐term stability.