Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability

Highlights A fluorinated zincophilic covalent organic framework (COF-S-F) with sulfonic acid group (-SO 3 H) is prepared on the surface of Zn anode, which promotes the desolvation of hydrated Zn ions and inhibits the side reactions. The highly electronegative -F group in COF-S-F promotes fast and uniform transport of Zn ions along the interconnected channels, which contributes to the uniform electrodeposition process of Zn metal. Zn@COF-S-F symmetric cell achieves a superior stability of 1,000 h and Zn@COF-S-F|MnO 2 cell delivers high specific capacity of 206.8 mAh g −1 at current density of 1.2 A g −1 . Achieving a highly robust zinc (Zn) metal anode is extremely important for improving the performance of aqueous Zn-ion batteries (AZIBs) for advancing “carbon neutrality” society, which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction, corrosion, and passivation, etc. Herein, an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups (COF-S-F) is developed on Zn metal (Zn@COF-S-F) as the artificial solid electrolyte interface (SEI). Sulfonic acid group (− SO 3 H) in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions, and the three-dimensional channel with fluoride group (-F) can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects, endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions. Consequently, Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage (50.5 mV) at the current density of 1.5 mA cm −2 . Zn@COF-S-F|MnO 2 cell delivers the discharge specific capacity of 206.8 mAh g −1 at the current density of 1.2 A g −1 after 800 cycles with high-capacity retention (87.9%). Enlightening, building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.