Interfacial Double‐Coordination Effect Guiding Uniform Electrodeposition for Reversible Zinc Metal Anode

Abstract The long‐term reversible plating/stripping of Zn metal anode is a critical aspect within aqueous zinc‐ion batteries (ZIBs). However, it is limited by uncontrolled electrodeposition and side reactions occurring at the anode/electrolyte interface. Guided by the metal‐coordination chemistry, a novel additive, sodium diphenylamine sulfonate (DASS), is added into ZnSO 4 electrolyte to guide stably invertible zinc deposition. Theoretical calculations and experimental results reveal that the DASS can adsorbed on the Zn anode surface due to the strong double coordination effect between N, S sites and Zn (Zn─N, Zn─S), and this adsorbed DASS layer can not only prevent the intimate contact between H 2 O and anode to inhibit interfacial side reactions, but also guide the 3D Zn 2+ ion diffusion and uniform electrodeposition to inhibit zinc dendrites. Consequently, the DASS additive enables an ultra‐long stable cycling up to 2400 h at 1 mA cm −2 (1 mAh cm −2 ), even at an ultra‐high current density of 20 mA cm −2 , a stable cycling of 250 h is demonstrated, highlighting the reliable coordination effect at the anode/electrolyte interface. This study offers a new perspective on the interfacial double‐coordination effect for achieving highly reversible Zn metal anodes in aqueous rechargeable zinc‐ion batteries.