Rational Design of Highly Stable and Active Single‐Atom Modified S‐MXene as Cathode Catalysts for Li‐S Batteries

Abstract The practical application of Li‐S batteries is hindered by the shuttle effect and sluggish sulfur conversion kinetics. To address these challenges, this work proposes an efficient strategy by introducing single atoms (SAs) into sulfur‐functionalized MXenes (S‐MXenes) catalysts and evaluate their potential in Li‐S batteries through first‐principles calculations. Using high‐throughput screening of various SA‐modified S‐MXenes, this work identifies 73 promising candidates that exhibit exceptional thermodynamic and kinetic stability, along with the effective immobilization of polysulfides. Notably, the incorporation of Ni, Cu, or Zn as SAs into S‐MXenes results in a significant Gibbs free energy barrier reduction by 51%–75%, outperforming graphene‐based catalysts. This reduction arises from SA‐induced surface electron density that influences the adsorption energies of intermediates and thereby disrupts the scaling relations between Li₂S₂ and other key intermediates. Further enhancement in catalytic performance is achieved through strain engineering by shifting the d‐band center of metal atoms to higher energy levels, increasing the chemical affinity for intermediates. To elucidate the intrinsic adsorption properties of intermediates, this work develops a machine learning model with high accuracy (R 2 = 0.88), which underscores the pivotal roles of SA electronegativity and local coordination environment in determining adsorption strength, offering valuable insights for the rational design of catalysts.