Rational Design of Non-Noble Metal Single-Atom Catalysts in Lithium-Sulfur Batteries through First Principles Calculations.

Lithium-sulfur (Li-S) batteries with a high theoretical energy density of 2600 Wh·kg-1 are hindered by challenges such as low S conductivity, the polysulfide shuttle effect, low S reduction conversion rate, and sluggish Li2 S oxidation kinetics. Herein, single-atom non-noble metal catalysts (SACs) loaded on two-dimensional (2D) vanadium disulfide (VS2 ) as the potential host materials for the cathode in Li-S batteries were investigated systematically by using first-principles calculations. Based on the comparisons of structural stability, the ability to immobilize sulfur, electrochemical reactivity, and the kinetics of Li2 S oxidation decomposition between these non-noble metal catalysts and noble metal candidates, Nb@VS2 and Ta@VS2 were identified as the potential candidates of SACs with the decomposition energy barriers for Li2 S of 0.395 eV (Nb@VS2 ) and of 0.162 eV (Ta@VS2 ), respectively. This study also identified an exothermic reaction for Nb@VS2 and the Gibbs free energy of 0.218 eV for Ta@VS2 . Furthermore, the adsorption and catalytic mechanisms of the VS2 -based SACs in the reactions were elucidated, presenting a universal case demonstrating the use of unconventional graphene-based SACs in Li-S batteries. This study presents a universal surface regulation strategy for transition metal dichalcogenides to enhance their performance as host materials in Li-S batteries.