Adjusting Interface Dynamics: A New Insight into the Role of Electrolyte Additive in Facilitating Highly Reversible (002)‐Textured Zinc Anode at High Current and Areal Densities

Abstract Facilitating (002)‐textured zinc growth is crucial for achieving dendrite‐free zinc deposition in zinc‐ion batteries. Electrolyte engineering holds promise in directing zinc electrodeposition toward this desired orientation. However, despite the (002) plane's lower surface energy compared to other facets, it remains unclear why this plane does not dominate zinc crystal faces during electrodeposition under normal conditions. This knowledge gap underscores the need to better understand zinc electrodeposition behaviors and the influence of electrolyte compositions on its crystallographic texture. This study explores different tetraazamacrocycle derivatives as electrolyte additives. It reveals that achieving (002)‐textured zinc deposition is not solely dictated by thermodynamic equilibrium but also significantly influenced by interface dynamics. In typical ZnSO 4 electrolytes, imbalanced kinetics among reduction, ion diffusion, and adatom diffusion processes lead to electroconvection and disorderly zinc accumulation, hindering proper zinc growth. In contrast, introducing specific tetraazamacrocycle derivative in the electrolyte regulates reduction rate, enhances limiting current density, and expedites adatom diffusion, mitigating hydrodynamic instability and dendrite growth. This regulation restores the thermodynamically favorable flat (002)‐textured zinc deposition, extending the zinc anode's lifespan to 1800 h at 5 mA cm −2 and 5 mAh cm −2 , enabling the fabrication of a high‐performance zinc ion hybrid capacitor prototype capable of stable operation for 40 000 cycles.