Integrating Multiple Redox‐Active Units into Conductive Covalent Organic Frameworks for High‐Performance Sodium‐Ion Batteries

Abstract The rational design of porous covalent organic frameworks (COFs) with high conductivity and reversible redox activity is the key to improving their performance in sodium‐ion batteries (SIBs). Herein, we report a series of COFs (FPDC‐TPA‐COF, FPDC‐TPB‐COF, and FPDC‐TPT‐COF) based on an organosulfur linker, (trioxocyclohexane‐triylidene)tris(dithiole‐diylylidene))hexabenzaldehyde (FPDC). These COFs feature two‐dimensional crystalline structures, high porosity, good conductivity, and densely packed redox‐active sites, making them suitable for energy storage devices. Among them, FPDC‐TPT‐COF demonstrates a remarkably high specific capacity of 420 mAh g −1 (0.2 A g −1 ), excellent cycling stability (~87 % capacity retention after 3000 cycles, 1.0 A g −1 ) and high rate performance (339 mAh g −1 at 2.0 A g −1 ) as an anode for SIBs, surpassing most reported COF‐based electrodes. The superior performance is attributed to the dithiole moieties enhancing the conductivity and the presence of redox‐active carbonyl, imine, and triazine sites facilitating Na storage. Furthermore, the sodiation mechanism was elucidated through in situ experiments and density functional theory (DFT) calculations. This work highlights the advantages of integrating multiple functional groups into redox‐active COFs for the rational design of efficient and stable SIBs.