Synergistic Solvation‐Interface Regulation via a Zincophilic‐Hydrophobic Additive Enables Deep‐Cycling Zinc Metal Anodes

ABSTRACT Aqueous zinc‐ion batteries are regarded as a compelling candidate for large‐scale energy storage due to their inherent safety, low cost, and ease of production. However, their commercialization is impeded by critical issues of zinc anodes, including uncontrolled dendrite growth, hydrogen evolution, zinc corrosion, and by‐product accumulation. Herein, we report a synergistic solvation‐interface regulation strategy using sodium dodecyl diphenyl ether disulfonate (C 12 ‐MADS) as a multifunctional additive. Specifically, the sulfonate groups enter the Zn 2+ solvation sheath to displace coordinated water molecules, lowering the desolvation energy barrier. Concurrently, these sulfonate groups anchor onto the zinc surface via strong affinity, while the hydrophobic alkyl chains extend outward to create a water‐exclusive inner Helmholtz plane. This dual action homogenizes interfacial Zn 2+ flux, suppresses water‐induced side reactions, and promotes dense, dendrite‐free zinc deposition. Consequently, the C 12 ‐MADS modified electrolyte enables a Zn||Zn symmetric cell to stably cycle for 1600 h under rigorous conditions (10 mA cm −2 , 10 mAh cm −2 ), and a Zn||I 2 /CNT full cell delivers exceptional rate capability and extended cycling stability. This work provides molecular‐level insight into the synergistic solvation‐interface regulation mechanism and offers a rational design principle for durable aqueous Zn anodes.