Intermediate Layer‐Induced Hierarchical Organization of Synergistic Interface Protection Layer for High‐Performance and Dendrite‐Free Zn‐Ion Battery

Aqueous zinc‐ion batteries are promising candidates for next‐generation energy storage owing to their high safety and low cost. However, their practical application is severely hindered by parasitic reactions. Herein, we report a hierarchically synergistic interface protection strategy achieved by using an intermediate fluorine‐incorporated Au transitional layer formed on the Zn anode surface (Au–F@Zn). During Zn deposition, this Au–F intermediate transitional layer transforms into an hierarchically synergistic interface layer composed of ZnF 2 and Au interlayers. The ZnF 2 interlayer, possessing low electronic conductivity and weak H + adsorption strength, suppresses HER and corrosion reactions, enhances Zn 2+ transport, and effectively protects the deposited Zn from direct electrolyte exposure. Meanwhile, the Au interlayer, with strong Zn affinity, accelerates Zn nucleation kinetics and promotes uniform planar growth. Thanks to this synergistic interfacial regulation, Zn||Zn symmetric cells with the hierarchically synergistic interface layer exhibit exceptional cycling stability for over 4500 h at 1 mA cm −2 . Moreover, the Zn||Cu half‐cell with the hierarchically synergistic interface layer demonstrates excellent reversibility, achieving an average Coulombic efficiency of 99.5% over 2400 cycles. Importantly, MnO 2 ||HSI@Zn full cells retain approximately 77.69% of their initial capacity after 500 cycles, showcasing outstanding durability. This work presents that an hierarchically synergistic interface protection strategy paves the way for high‐performance and durable aqueous zinc‐ion batteries.