Metallosalen Covalent Organic Frameworks with Integrated Organic–Inorganic Active Sites for Enhanced Li Storage

Abstract Covalent organic frameworks (COFs) hold great promise as cathode materials for lithium‐ion batteries (LIBs), but their limited conductivity has hindered broader application. In this study, a novel metallosalen COF (Cu‐TH‐COF) is introduced, synthesized via a one‐pot method, incorporating redox‐active Cu ions into N 2 O 2 pockets and creating an extended π‐d conjugated structure. This design merges organic and inorganic active sites, enabling efficient multi‐electron transfer and improving the utilization of active sites in LIBs. The π‐d conjugation significantly enhances the electronic conductivity, resulting in improved rate performance. As a result, Cu‐TH‐COF delivers an impressive discharge capacity of 300 mAh g −1 at 50 mA g −1 and retains 174 mAh g −1 at 4000 mA g −1 , significantly outperforming its Cu‐free counterpart. This study demonstrates for the first time the potential of metallosalen COFs as high‐performance cathode materials and opens up a new strategy for next‐generation LIBs.