Synergistic solvation-interface engineering enables dendrite-free and long-life aqueous Zn-based energy storage

Aqueous zinc-ion batteries (AZIBs) face persistent challenges in reversibility, Coulombic efficiency (CE), and long-term cycling stability, primarily due to uncontrolled dendrite growth, parasitic hydrogen evolution reaction (HER), and sluggish desolvation kinetics of hydrated Zn2 + ions. Here, we introduce a zincophobic–hydrophobic synergistic strategy by incorporating a trace amount of tiron (TR) into a 2 M Zn(OTf)2 electrolyte. Contrary to conventional belief that zincophobicity impedes Zn deposition, TR simultaneously addresses all major failure modes. It preferentially adsorbs onto Zn surfaces, effectively blocking low nucleation overpotential sites and thereby guiding Zn2+ to deposit as uniform, petal-like nanostructures rather than dendrites. Concurrently, TR disrupts micelle-like [Zn(H₂O)ₙ]2+ solvation clusters via competitive coordination, forming a more labile solvation shell that lowers desolvation barriers and accelerates Zn2+ transport. In addition, the hydrophobic TR layer repels interfacial water, suppressing HER effectively. As a result, Zn||Zn symmetric cells exhibit an ultra-long cycling life of 1520 h (vs. 96 h control), Zn||Cu half-cells achieve a high CE of 98.8 %, and Zn||AC hybrid capacitors retain 95.1 % capacity over 5000 cycles. This work pioneers a generalizable solvation–interface co-engineering strategy that redefines the role of zincophobicity and hydrophobicity in Zn electrochemistry—offering a robust pathway toward high-performance, long-life aqueous zinc-based energy storage systems.