Molecular Engineering Regulation Redox‐Active Sites and Nanostructures of Covalent Organic Framework for High‐Performance Lithium Sulfur Batteries

Abstract Research on the catalytic chemistry of lithium sulfur batteries (LSBs) primarily focuses on the development of catalytic active sites, with limited attention given to their structural stability. Furthermore, regulating the nanostructure of catalysts can enhance structural stability without compromising their intrinsic catalytic activity. This work presents a covalent organic framework (COF) with dual redox‐active sites (C═O and C═N) and large periodic π‐conjugated framework (denoted as CON‐COF). This framework is constructed through molecular engineering to mitigate the shuttling of lithium polysulfides (LiPSs), accelerate their conversion, regulate lithium ions (Li ⁺ ) dynamics, prevent dendrite formation, and maintain structural stability during cycling. Subsequently, CON‐COF is in situ grown on carbon nanotubes to enhances electrical conductivity and further improves structural stability. This combination significantly boosts the performance of LSBs, achieving a remarkable decay rate of 0.021% over 1000 cycles, along with an areal capacity of 8.3 mAh cm ⁻² under lean electrolyte conditions. Furthermore, pouch cells incorporating this configuration demonstrate exceptional long‐term stability, maintaining performance over 200 cycles. This strategy addresses the limitations of traditional catalyst design by effectively regulating both the redox‐active sites and nanostructures, paving the way for the future development of high‐performance LSBs.