Electrical Double Layer and In Situ Polymerization SEI Enables High Reversible Zinc Metal Anode

Abstract Aqueous zinc‐ion batteries (AZIBs) stand out among new energy storage devices due to their excellent safety and environmental friendliness. However, the formation of dendrites and side reactions on the zinc metal anode during cycling have become the major obstacles to their commercialization. This study innovatively selected Sodium 4‐vinylbenzenesulfonate (VBS) as a multifunctional electrolyte additive to address the issues. The dissociated VBS‐ anions can not only significantly alter the hydrogen bond network structure of H 2 O in the electrolyte, but also preferentially adsorb on the surface of the zinc anode before H 2 O molecules, which will result in the development of organic anion‐rich interface and alterations to the electrical double layer (EDL) structure. Furthermore, the ─C═C─ structure in VBS leads to the formation of an in situ polymerized organic anion solid electrolyte interface (SEI) layer that adheres to the surface of the zinc anode. The mechanisms work together to significantly improve the performance of Zn//Zn symmetric batteries, achieving a cycle life of over 1800 h at 1 mA cm −2 and 1 mAh cm −2 . The introduction of VBS also enhances the cycling performance and capacity of Zn//δ‐MnO 2 full cells. This study provides a low‐cost solution for the development of AZIBs.