High-Throughput Calculations for Screening d- and p-Block Single-Atom Catalysts toward Li₂ S/Na₂ S Decomposition...

Single-atom catalysts (SACs) are promising cathode materials for addressing issues faced by lithium-sulfur batteries. Considering the ample chemical space of SACs, high-throughput calculations are efficient strategies for their rational design. However, the high throughput calculations are impeded by the time-consuming determination of the decomposition barrier (E_b ) of Li₂ S. In this study, the effects of bond formation and breakage on the kinetics of SAC-catalyzed Li₂ S decomposition with g-C₃ N₄ as the substrate are clarified. Furthermore, a new efficient and easily-obtained descriptor Li─S─Li angle (A_Li─S─Li ) of adsorbed Li₂ S, different from the widely accepted thermodynamic data for predicting E_b , which breaks the well-known Brønsted-Evans-Polanyi relationship, is identified. Under the guidance of A_Li─S─Li , several superior SACs with d- and p-block metal centers supported by g-C₃ N₄ are screened to accelerate the sulfur redox reaction and fix the soluble lithium polysulfides. The newly identified descriptor of A_Li─S─Li can be extended to rationally design SACs for Na─S batteries. This study opens a new pathway for tuning the performance of SACs to catalyze the decomposition of X₂ S (X = Li, Na, and K) and thus accelerate the design of SACs for alkaline-chalcogenide batteries.