An Electrocatalytic Model of the Sulfur Reduction Reaction in Lithium–Sulfur Batteries

Abstract Lithium–sulfur (Li–S) battery is strongly considered as one of the most promising energy storage systems due to its high theoretical energy density and low cost. However, the sluggish reduction kinetics from Li 2 S 4 to Li 2 S during discharge hinders the practical application of Li–S batteries. Although various electrocatalysts have been proposed to improve the reaction kinetics, the electrocatalytic mechanism is unclear due to the complexity of sulfur reduction reactions (SRR). It is crucial to understand the electrocatalytic mechanism thoroughly for designing advanced electrocatalysts. Herein an electrocatalytic model is constructed to reveal the chemical mechanism of the SRR in Li–S batteries based on systematical density functional theory calculations, taking heteroatoms‐doped carbon materials as an example. The adsorption energy of LiS y ⋅ ( y =1, 2, or 3) radicals is used as a key descriptor to predict the reaction pathway, rate‐determining step, and overpotential. A diagram for designing advanced electrocatalysts is accordingly constructed. This work establishes a theoretical model, which is an intelligent integration for probing the complicated SRR mechanisms and designing advanced electrocatalysts for high‐performance Li–S batteries.