Boron‐Fluoride Dual‐atom Synergistic Regulated Interface Coating Enables Stable Zn‐Metal Anodes

Abstract Aqueous zinc‐based batteries provide promising opportunities for next‐generation rechargeable batteries. Nevertheless, Zn anode encounters severe challenges, such as Zn dendrite formation, surface corrosion, and hydrogen evolution reaction (HER). Here, we report a strategy to spontaneously construct a boron−fluoride dual‐atom regulated SEI (ZnBOF), which involves the formation of a B‐compound coating through an etching process followed by an in situ F substitution during the initial electrochemical cycling. The ZnBOF/Zn anode benefits preferential deposition of Zn 2+ along the (002) plane without Zn dendrite, and the side reactions including by‐product and HER are dramatically suppressed. A combination of characterization methods, such as X‐ray absorption spectroscopy, shows that the B‐containing passivation layer facilitates the transport of Zn 2+ and mitigates water‐related side reactions, and the F atoms serve as zincophilic sites that enhance the transfer kinetics of Zn 2+ . As expected, the well‐designed ZnBOF/Zn anode exhibits ultra‐stable Zn plating/stripping for 5000 h at 2 mA cm −2 . The assembled ZnBOF/Zn||MnO 2 batteries show impressive cycling stability, remaining 96.2% of the initial capacity (234.3 mAh g −1 ) after 1700 cycles at 1.0 A g −1 . Therefore, this work reveals a dual‐atom synergistic regulated strategy to fabricate a robust SEI for Zn anode, which contributes to the development of aqueous zinc‐based batteries.