Entropy Engineering‐Modulated D‐Band Center of Transition Metal Nitrides for Catalyzing Polysulfide Conversion in Lithium‐Sulfur Batteries

Abstract The sluggish sulfur redox kinetics and severe polysulfide shuttle effect seriously restrict the cycling stability and lower the sulfur utilization of lithium‐sulfur (Li‐S) batteries. Efficient catalytic conversion of polysulfides is deemed a crucial strategy to address these issues, but still suffers from an unclear electronic structure‐activity relationship and a limited catalysis performance. Herein, entropy engineering‐induced electronic state modulation of metal nitride nanoparticles embedded within hollow N‐doped carbon (HNC) polyhedra are theoretically and experimentally constructed as a catalyst to accelerate the redox process of sulfur and suppress polysulfide migration in Li‐S batteries. By introducing V, Cr, and Nb elements to engineer the entropy of TiN, the metal d‐band center is optimized to approach the Fermi level, significantly facilitating the conversion of sulfur species. Accordingly, the TiVCrNbN@HNC catalyst enables Li‐S batteries to achieve a high initial capacity (1299 mAh g −1 at 0.1 C) and excellent cycling stability with a low capacity decay rate of 0.086% per cycle after 500 cycles. This work may provide a new insight into entropy engineering in catalyst design for high‐performance Li‐S batteries.