Synergistic Stabilization of Zinc Anodes via Phenol Sulfonate Anion-Rich Electric Double Layer and Robust SEI

Electrolyte engineering extends Zinc anode cycling, yet how the solvation structure dynamically couples with electric double-layer (EDL) chemistry during electrochemical operation remains poorly understood. Herein, a zinc phenolsulfonate (Zn(PS)₂)-based hybrid electrolyte was constructed by introducing dimethyl sulfoxide (DMSO). In addition to reconstructing the electrolyte hydrogen-bond grids, DMSO promotes the establishment of a PS⁻-reinforced solvation environment. This tailored solvation structure drives the formation of a PS⁻-rich interfacial EDL, in which PS⁻ anions preferentially and uniformly adsorb on the Zn surface during dynamic electrochemical processes, thereby optimizing Zn²⁺ diffusion. Meanwhile, the PS⁻-rich stern layer, together with the preferential decomposition of anions, facilitates in situ construction of a robust SEI. The synergistic effects of the EDL and SEI enable regulation of zinc deposition morphology, ensuring the zinc anode durability even under harsh conditions. The Zn||Zn symmetric cells exhibit a long cycling life of 1650 h at a DOD of 57%, along with excellent cycling performance across a broad temperature range from −30°C to 60°C. Furthermore, the Zn||I₂@AC cells exhibit a capacity retention of 97.66% after 44 000 cycles at 10 A g⁻¹. The multidimensional insights into interfacial electrochemistry in this work provide rational design principles for tailoring next-generation aqueous batteries.