Rationally Designed Binder with Polysulfide‐Affinitive Moieties and Robust Network Structures for Improved Polysulfide Trapping and Structural Stability of Sulfur Cathode

Abstract Lithium–sulfur batteries (LSBs) have emerged as a promising next‐generation energy storage application owing to their high specific capacity and energy density. However, inherent insulating property of sulfur, along with its significant volume expansion during cycling, and shuttling behavior of lithium‐polysulfides (LiPSs), hinder their practical application. To overcome these issues, a crosslinked cationic waterborne polyurethane (CCWPU) is rationally designed as a binder for LSBs. The mechanical robustness of CCWPU enables it to withstand the high stress derived from volume expansion of sulfur, facilitating charge‐transferring through conserved charge‐transfer pathway and promoting interconversion of LiPSs. Additionally, polar urethane groups offer favorable interaction sites with LiPSs, mitigating shuttling behavior of LiPSs via polar‐polar interaction. Density functional theory investigations further elucidate that the incorporation of cationic moieties enhances LiPSs immobilization by confining S n x− (x = 1 or 2) in LiPSs, thereby improving sulfur utilization. Benefiting from these, the cell with CCWPU demonstrates reduced polarization, superior LiPSs conversion rates, and stable cycling performance. Moreover, water‐processable nature of CCWPU aligns with environmental consciousness. These diverse functionalities of CCWPU provide valuable insights for the development of advanced binder for LSBs, ultimately improving the electrochemical performances of LSBs.