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

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 etching process and followed by an in‐situ F substitution during the initial electrochemical cycling. The ZnBOF/Zn anode benefit preferential deposition of Zn2+ along the (002) plane without Zn dendrite, and the side reaction including by‐product and HER are dramatically suppressed. A combination of characterization methods, such as X‐ray absorption spectroscopy, show that the B‐containing passivation layer facilitates the transport of Zn2+ and mitigates water‐related side reactions, and the F atoms serve as zincophilic sites that enhance the transfer kinetics of Zn2+. 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||MnO2 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.