Topological Engineering Pre‐Integrated Lithium Enabling Desolvation and Conversion of Polysulfides

ABSTRACT The practical application of lithium‐sulfur batteries (LSBs) is hindered by several challenges, such as lithium polysulfides (LiPSs) shuttle effect and sluggish sulfur redox kinetics, which is caused by the mismatch between charge‐electron transport and reaction at the confined scale. To address the issues, a highly crystalline and ordered C 3 N 4 topological network was designed. Theoretical simulations together with Raman spectroscopy reveal that this ordered C 3 N 4 framework effectively reduces the Li + solvation‐desolvation energy barrier and facilitates the pre‐integration of free Li + . These active sites, with cationic lithium ion, attracts anionic polysulfides through electrostatic interactions. Spontaneously, the CN‐MS‐2 topological network with flexible porosity parameter exerts the responsiveness transformation of LiPSs in a micro‐chemical environment, suppressing the migration of polysulfides. Consequently, LSBs employing CN‐MS‐2 on the separator‐facing side of the cathode deliver excellent electrochemical performances of 1192 mAh g −1 at 1 C and maintain 743 mAh g −1 after 500 cycles, and its practical application highlight the advantages of a high sulfur loading of 7.791 mg cm −2 and pouch cell energy density of 254 Wh kg −1 . This work has clarified the mass transfer reaction kinetics of ion‐type polysulfides in topological networks and expanded their applications.