Jiangtao Tong, Yitong Wang, Yitong Wang, Yuhua Wang, Yuhua Wang, Haijun Zhang, J. X. Li, Denglei Zhu, Yao Guo, Xiaojing Bai, Chaojun Cui
ABSTRACT Aqueous zinc‐ion batteries (AZIBs) have garnered considerable attention due to their superior safety, affordability, and eco‐friendliness. However, the uncontrolled growth of zinc dendrites and the parasitic hydrogen evolution reaction (HER) severely limit their cycling stability and practical lifespan. In this study, sodium p ‐aminobenzenesulfonate (SABS) is introduced into ZnSO 4 ‐based electrolytes as a functional additive. SABS not only reconstructs the Zn 2+ solvation sheath but also forms stable complexes with Zn 2+ , facilitating the in‐situ formation of a robust three‐dimensional networked solid electrolyte interphase (SEI) on the zinc anode surface. As a result, Zn||Zn symmetric cells exhibit ultra‐stable cycling performance exceeding 2000 h at 1 mA cm −2 , while Zn||Cu asymmetric cells maintain over 2000 cycles at 5 mA cm −2 with high Coulombic efficiency. The underlying mechanism of interfacial stabilization and SEI‐like interphase formation is further elucidated by combining ex situ structural/chemical characterizations with density functional theory (DFT) calculations. Moreover, the Zn||I 2 @AC full cell containing SABS additives exhibits excellent specific capacity and long‐term cycling performance over a wide range of current densities. This work provides a promising electrolyte additive strategy to enhance the interfacial stability and electrochemical performance of AZIBs through coordinated solvation and interphase regulation.