Achieving Reversible Zinc Electrodeposition through a Holistic Interfacial Energy Framework

Abstract

Aqueous zinc (Zn) metal batteries (ZMBs) are promising for grid-scale storage, yet their long-term stability is constrained by interfacial processes at the Zn anode, where dendritic growth and hydrogen evolution originate from coupled transport and reaction events. Although electrolyte and interphase strategies have mitigated individual failure modes, they rarely capture the continuous sequence through which Zn deposition proceeds. Zn growth is governed by an interfacial energy cascade that connects ion transport in the diffusion layer, desolvation, and competitive adsorption within the Helmholtz region, and the nucleation energetics that dictate crystallographic development. Recognizing these steps as energetically linked clarifies how changes in Zn 2+ flux, desolvation barriers, or nucleation landscapes propagate downstream to determine deposit morphology and stability. When these transitions are aligned, Zn evolves toward compact, coherent architectures, and parasitic reactions are substantially reduced. Building on this framework, this review highlights how Zn deposition emerges from a continuous energetic sequence in which diffusionlayer transport reshapes the Zn 2+ /H + arrival hierarchy, the Helmholtz layer governs desolvation and interfacial selectivity, and the nucleation landscape directs crystallographic evolution. Viewing these steps as a coupled cascade provides a unified mechanistic picture of Zn interfacial behavior. We further highlight operando characterization and multiscale modeling techniques that now make this coupling experimentally and computationally accessible, offering actionable principles for designing stable aqueous Zn anodes.