Regulation Strategies and Mechanistic Understanding of Zinc Deposition Interfaces in Anode‐Free Aqueous Zinc Metal Batteries

ABSTRACT Anode‐free aqueous zinc metal batteries (AF‐AZMBs) eliminate Zn anodes and enable in situ Zn plating/stripping on inert current collectors to increase energy density with low cost and improved safety. Unlike conventional AZMBs, AF‐AZMBs lack a Zn reservoir, so that cathode‐derived Zn must be fully recovered through reversible plating, making zinc deposition chemistry fundamentally decisive for reversibility and failure evolution. Repeated deposition interface reconstruction induces heterogeneous nucleation, irreversible zinc loss, ion transport limitation, hydrogen evolution, and dead zinc formation, severely impairing plating‐stripping reversibility and practical application. Stable electrode‐electrolyte interface chemistry is pivotal for uniform zinc deposition, parasitic reaction suppression, and reversibility enhancement, making interfacial regulation targeting zinc deposition a research focus. This review summarizes recent advances in AF‐AZMBs, highlighting the core role of interfacial chemistry in optimizing zinc deposition dynamics and electrochemical performance. Three synergistic strategies, including electrolyte optimization, current collector modification, and separator interface engineering, are systematically analyzed in terms of their coordinated modulation of Zn 2 + transport behavior, nucleation thermodynamics, growth kinetics, and interfacial stability, thereby improving deposition uniformity and reversibility. By elucidating the interfacial mechanisms that govern zinc deposition stability in AF‐AZMBs, this review provides design principles for constructing high energy density, long lifespan systems via targeted interfacial chemistry.