Umpolung of a covalent organic framework for high-performance cathodic sodium ion storage

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 increasing the potential for operation as a cathode material. Alongside increased specific capacity, an improved overall performance in sodium-ion batteries (SIBs) is achieved. Specifically, CityU-47 provides a high capacity of 286.31 mA h g⁻¹ at a current density of 0.1 A g⁻¹, and a cycle capacity of 210 mA h g⁻¹ at 2 A g⁻¹ over 1800 cycles is also achieved. This research offers fresh perspectives on enhancing battery performance, underscoring the importance of regulating electron structures at the atomic level. © 2025 The Author(s). Published by the Royal Society of Chemistry.