Zimiao Lu

Aqueous zinc-ion batteries (AZIBs) are promising for grid-scale storage due to their safety, low cost, and environmental benignity. However, water-dipole enrichment in the inner Helmholtz plane (IHP) of Zn anodes triggers hydrogen evolution, corrosion, and dendrites, limiting cycle life. We report a trace “ionic liquid–polar solvent coupling” strategy: adding only 0.01 M EMIMBF₄ and 0.03 M DMSO to 2 M ZnSO₄ electrolyte. Hydrophobic EMIM⁺ adsorbs on the IHP to expel interfacial water, while BF₄⁻ enters the primary solvation shell and DMSO penetrates both first and second shells of Zn²⁺, forming a water-deficient coordination environment. This interfacial–solvation synergy suppresses parasitic reactions and directs preferentially oriented Zn deposition exclusively along the (101) facet, enabling dense vertical plating and in situ formation of a compact, inorganic-rich SEI (ZnCO₃–ZnSO₃–Zn(OH)₂). Consequently, Zn||Zn cells cycle stably for >5362 h at 1 mA cm⁻²/1 mAh cm⁻²; Zn||Cu cells achieve 1300 cycles with 99.8% average Coulombic efficiency; and Zn||V₂O₅ full cells retain 326.4 mAh g⁻¹ after 500 cycles. This work shows that minimal additive loading can simultaneously engineer the electrode–electrolyte interface and crystallographic deposition pathway, offering a simple yet robust design for ultra-stable AZIBs.