Entrapment and Reactivation of Polysulfides in Conductive Amphiphilic Covalent Organic Frameworks Enabling Superior Capacity and Stability of Lithium–Sulfur Batteries

Abstract Inhibiting the shuttle of polysulfides is of great significance for promoting the practical application of lithium–sulfur batteries (LSBs). Here, an imine‐linked covalent organic framework@carbon nanotube (COF@CNT) interlayer composed of triazine and boroxine rings is constructed between the sulfur cathode and the separator for polysulfides reception and reutilization. The introduction of CNT imparts the conductor characteristic to the interlayer attributed to electron tunneling in thin COF shell, and creates a hierarchical porous architecture for accommodating polysulfides. The uniform distribution of amphiphilic adsorption sites in COF microporous structure not only enables efficient entrapment of polysulfides while allowing the penetration of Li⁺ ions, but also provides a stable electrocatalytic channel for bidirectional conversion of active sulfur to achieve the substantially improved capacity and stability. The interlayer‐incorporated LSBs deliver an ultrahigh capacity of 1446 mA g⁻¹ at 0.1C and an ultralow capacity decay rate of 0.019% at 1C over 1500 cycles. Even at an electrolyte/sulfur ratio of 6 µL mg⁻¹, an outstanding capacity of 995 mAh g⁻¹ and capacity retention of 74.1% over 200 cycles at 0.2C are obtained. This work offers a compelling polysulfides entrapment and reactivation strategy for stimulating the study on ultra‐stable LSBs.