Breaking the Diffusion‐Limited Aggregation for Ordered Zn Deposition via Interfacial Structure‐Directing Engineering

ABSTRACT Uncontrolled dendrite growth during zinc plating/stripping hinders the practical application of aqueous zinc metal batteries in energy storage systems. In this study, the classical diffusion‐limited aggregation (DLA) theory was employed to understand the mechanisms of zinc dendritic growth fundamentally and then to guide the design of interfacial structure‐directing engineering. [EMIm]EtSO 4 ionic liquid as a structure‐directing agent was developed to successfully overcome the disordered Zn dendrite growth following the rules of “random motion” and “contact‐stick”. Comprehensive characterizations suggest that EMIm + cations guide the interfacial ordering process by building a buffer layer and a hydrophobic barrier on the Zn anode, while EtSO 4 − anions orchestrate the reconstruction of the Zn 2+ solvation structure. This synergistic regulation transforms zinc deposition morphology from stochastic fractal growth to highly ordered epitaxial growth. As a result, the zinc anode achieves 99.3% Coulombic efficiency at 1 mA cm −2 and stable cycling over 2000 h. It further endows the Zn||NVO battery with significantly improved stability and anti freezing performance (−40°C). This work demonstrates an interfacial engineering strategy that effectively suppresses DLA‐type dendritic growth, providing a new perspective for high‐performance aqueous zinc batteries.