ABSTRACT Aqueous Zn metal batteries (AZMBs) hold great promise for grid‐scale energy storage due to their inherent safety, low cost, and resource abundance. However, their practical deployment is hindered by issues such as unstable Zn deposition and persistent side reactions. Epitaxial electrodeposition, enabling the oriented growth of Zn via crystallographic inheritance from tailored substrates, has emerged as a fundamental strategy for achieving highly reversible Zn anodes. However, a systematic review dedicated to the mechanism of Zn epitaxy across different template architectures and electrochemical conditions remains absent. This review summarizes recent advances in Zn epitaxial deposition and outlines key design principles for achieving and sustaining epitaxial growth. We first clarify three prerequisites for epitaxial deposition: lattice matching, structural coherence, and interfacial kinetics. Related strategies are categorized into heteroepitaxy, induced by hexagonal layered materials, metal substrates, as well as homoepitaxy on single‐crystal Zn or textured polycrystalline Zn foils. Furthermore, failure mechanisms of epitaxial growth are unified into three interrelated types: nucleation mode deviation, structural strain degradation and interfacial chemical destabilization. Finally, building upon current limitations, this review outlines prospective directions, including pursuing practical epitaxy, guiding oriented stripping, controlling epitaxial facets, and generalizing metal epitaxy, aimed at guiding the design of high‐performance Zn anodes.
Zhong et al. (Fri,) studied this question.