Molecular Engineering-Guided (100) Oriented Zinc Deposition of Anionic Surface-Active Additives for Ultrastable Zinc-Ion Batteries

Aqueous zinc-ion batteries (AZIBs) represent a promising technology for grid-scale energy storage due to their intrinsic safety, environmental sustainability, and low cost. However, their practical implementation is hindered by severe anode instability issues, including uncontrollable dendrite growth and water-induced parasitic reactions. Here, we introduce sodium hexadecyl diphenyl ether disulfonate (SHDD) as a cost-effective, multifunctional electrolyte additive. The amphiphilic structure of SHDD– anion enables comprehensive interfacial regulation: the sulfonate groups facilitate Zn2+ desolvation while reducing water activity, and the adsorbed anions form a hydrophobic barrier that effectively suppresses the hydrogen evolution reaction (HER) and byproduct formation. Additionally, SHDD– anion adsorption induces vertically aligned and highly compact Zn2+ deposition along the Zn(100) crystal plane. Benefiting from this synergistic mechanism, the assembled Zn||Zn symmetric cells achieve exceptional cycling stability over 4200 h, while Zn||Cu half-cells maintain a 99.66% Coulombic efficiency. Furthermore, full cells with an NH4V4O10 cathode deliver 233.40 mAh g–1 at 1 A g–1 and retain 83% capacity after 600 cycles. Therefore, this study highlights the potential of molecular design in modulating crystal orientation and interface engineering for high-performance next-generation AZIBs.