Toward Hydrogen‐Free and Dendrite‐Free Aqueous Zinc Batteries: Formation of Zincophilic Protective Layer on Zn Anodes

Rechargeable aqueous Zn‐ion batteries (ZIBs) are regarded as one of the most promising devices for the next‐generation energy storage system. However, the uncontrolled dendrite growth on Zn metal anodes and the side hydrogen evolution reaction, which has not yet been well considered, hinder the practical application of these batteries. Herein, a uniform and robust metallic Sb protective layer is designed based on the theoretic calculation and decorated on Zn plate via in situ replacement reaction. Compared with the bare Zn plate, the as‐prepared Zn@Sb electrode provides abundant zincophilic sites for Zn nucleation, and homogenizes the electric field around the Zn anode surface, both of which promote the uniform Zn deposition to achieve a dendrite‐free morphology. Moreover, the Gibbs free energy (∆G (H)) calculation and in situ characterization demonstrate that hydrogen evolution reaction can be effectively suppressed by the Sb layer. Consequently, Sb‐modified Zn anodes exhibit an ultralow voltage hysteresis of 34 mV and achieve excellent cycling stability over 1000 h with hydrogen‐ and dendrite‐free behaviors. This work provides a facile and effective strategy to suppress both hydrogen evolution reaction and dendrite growth.