Engineering Electronic Delocalization Facilitates Interfacial Desolvation Kinetics for Dendrite‐Free Zinc‐Metal Batteries

Abstract Aqueous zinc‐ion batteries (AZIBs) have sparked widespread interest attributed to their excellent safety, low cost, and environmental friendliness. Nonetheless, the uncontrolled growth of dendrites, attributed to high desolvation energy of hydrated Zn ²⁺ and slow Zn ²⁺ transport kinetics, poses a significant obstacle to the utilization of AZIBs in energy storage systems. Herein, defect‐engineering is employed to modulate electron delocalization in metal sulfides for abundant active sites to regulate the desolvation and diffusion of zinc ions. Theoretical simulations and experimental results reveal that sulfur defects enhance electron delocalization, effectively reducing Zn ² ⁺ desolvation and diffusion barriers, facilitating the dissociation of Zn ²⁺ in the solvated structure and promote uniform zinc deposition. The Zn@VS _2‐x electrodes demonstrate exceptional electrochemical performance, delivering 1500 h at 3 mA cm ⁻² with an ultrahigh cumulative capacity of 2200 mAh cm ⁻² and maintaining a stable lifespan exceeding 5200 h at 0 °C. Coupled with NaV ₃ O ₈ , the full cell exhibits exceptional rate performance of 215.5 mAh g ⁻¹ at 8 A g ⁻¹ and a capacity retention of 85.8% after 1000 cycles at 5 A g ⁻¹ . This study not only validates the viability of employing interfacial catalysts to modulate zinc behaviors but also offers valuable insights into catalyst selection.