High‐Throughput Calculations for Screening d‐ and p‐Block Single‐Atom Catalysts toward Li2S/Na2S Decomposition Guided by Facile Descriptor beyond Brønsted–Evans–Polanyi Relationship

Abstract 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 Li 2 S. In this study, the effects of bond formation and breakage on the kinetics of SAC‐catalyzed Li 2 S decomposition with g‐C 3 N 4 as the substrate are clarified. Furthermore, a new efficient and easily‐obtained descriptor Li─S─Li angle ( A Li─S─Li ) of adsorbed Li 2 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‐C 3 N 4 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 X 2 S (X = Li, Na, and K) and thus accelerate the design of SACs for alkaline‐chalcogenide batteries.