The rational design of electrode materials to modify their intrinsic electronic states effectively enhances the performance of rechargeable batteries. Herein, an umpolung strategy is implemented in preparing a polyimide-linked COF (CityU-47) through a polar inversion of the typical p-type triphenylamine (TPA) with a multi-carbonyl-contained n-type azatriangulenetrione (ATTO). This strategy can substantially decrease the energy level of the lowest unoccupied molecular orbital (LUMO), thereby augmenting the operation potential as cathode material. Alongside increased specific capacity, an improved overall performance in sodium-ion batteries (SIBs) is achieved. Specially, CityU-47 provides a high capacity of 286.31 mAh g-1 at a current density of 0.1 A g-1, and a cycle capacity of 210 mAh g-1 at 2 A g -1 over 1800 cycles was also achieved. This research offers fresh perspectives on enhancing battery performance, underscoring the importance of regulating electron structures at the atomic level.
