High‐Entropy Metal Nitride Embedded in Concave Porous Carbon Enabling Polysulfide Conversion in Lithium–Sulfur Batteries

Abstract The practical implementation of lithium–sulfur batteries is severely hindered by the rapid capacity fading due to the solubility of the intermediate lithium polysulfides (LiPSs) and the sluggish redox kinetics. Herein, high‐entropy metal nitride nanocrystals (HEMN) embedded within nitrogen‐doped concave porous carbon (N‐CPC) polyhedra are rationally designed as a sulfur host via a facile zeolitic imidazolate framework (ZIF)‐driven adsorption‐nitridation process toward this challenge. The configuration of high‐entropy with incorporated metal manganese (Mn) and chromium (Cr) will optimize the d‐band center of active sites with more electrons occupied in antibonding orbitals, thus promoting the adsorption and catalytic conversion of LiPSs. While the concave porous carbon not only accommodates the volume change upon the cycling processes but also physically confines and exposes active sites for accelerated sulfur redox reactions. As a result, the resultant HEMN/N‐CPC composites‐based sulfur cathode can deliver a high specific capacity of 1274 mAh g −1 at 0.2 C and a low capacity decay rate of 0.044% after 1000 cycles at 1 C. Moreover, upon sulfur loading of 5.0 mg cm −2 , the areal capacity of 5.0 mAh cm −2 can still be achieved. The present work may provide a new avenue for the design of high‐performance cathodes in Li–S batteries.