Interfacial Zn2+-solvation regulator towards reversible and stable Zn anode

Abstract

Aqueous zinc-ion batteries (AZIBs) are fundamentally challenged by the instability of the electrode/electrolyte interface, predominantly due to irreversible zinc (Zn) deposition and hydrogen evolution. Particularly, the intricate mechanisms behind the electrochemical discrepancies induced by interfacial Zn²⁺-solvation and deposition behavior demand comprehensive investigation. Organic molecules endowed with special functional groups (such as hydroxyl, carboxyl, etc.) have the potential to significantly optimize the solvation structure of Zn²⁺ and regulate the interfacial electric double layer (EDL). By increasing nucleation overpotential and decreasing interfacial free energy, these functional groups facilitate a lower critical nucleation radius, thereby forming an asymptotic nucleation model to promote uniform Zn deposition. Herein, this study presents a pioneering approach by introducing trace amounts of n-butanol as solvation regulators to engineer the homogenized Zn (H-Zn) anode with a uniform and dense structure. The interfacial reaction and structure evolution are explored by in/ex-situ experimental techniques, indicating that the H-Zn anode exhibits dendrite-free growth, no by-products, and weak hydrogen evolution, in sharp contrast to the bare Zn. Consequently, the H-Zn anode achieves a remarkable Zn utilization rate of approximately 20% and simultaneously sustains a prolonged cycle life exceeding 500 h. Moreover, the H-Zn//NH₄V₄O₁₀ (NVO) full battery showcases exceptional cycle stability, retaining 95.04% capacity retention after 400 cycles at a large current density of 5 A g⁻¹. This study enlightens solvation-regulated additives to develop Zn anode with superior utilization efficiency and extended operational lifespan.