Compact Electrodeposition Enabled by Synchronized Charge Transfer for Stable Aqueous Zn Metal Anodes

Abstract Randomly oriented hexagonal zinc (Zn) electrodeposits severely compromise the stability and reversibility of Zn‐metal electrodes. These deposits originate from localized interfacial high current densities and the preferential growth of (002) planes extending into the electrolyte. The electroconvection in the bulk electrolyte can amplify interfacial ion depletion and further exacerbate the uneven interfacial electrochemical reactions. Here, it is demonstrated that benzyl alcohol acts as a blocking agent on the metal substrate, enabling synchronized charge transfer across the electrode‐electrolyte interface. This synchronized charge transfer process facilitates the incorporation of newly formed Zn atoms into step edges of the substrate lattice via a screw dislocation growth mechanism. Such a strategy promotes effective layer‐by‐layer growth, yielding uniform and compact Zn deposits. As a result, Zn||Zn cells exhibit exceptional plating/stripping stability for over 2800 h and maintain resilience at an 80% depth of discharge of Zn (DOD Zn ). Under a limited Zn supply (50% DOD Zn ), Zn||Ti cells achieve an average Coulombic efficiency of 92.8%, highlighting the high reversibility of Zn‐metal electrodes. Additionally, Zn||VS 2 full cells with a 10 µm‐thin Zn‐metal foil show significantly enhanced electrochemical reversibility and capacity retention. This work establishes a universal framework for stabilizing metal electrodes, prioritizing electrodeposition step synchronization over isolated process optimization.