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

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 (Eb) of Li2S. In this study, the effects of bond formation and breakage on the kinetics of SAC-catalyzed Li2S decomposition with g-C3N4 as the substrate are clarified. Furthermore, a new efficient and easily-obtained descriptor Li -S -Li angle (A(Li -S -Li)) of adsorbed Li2S, different from the widely accepted thermodynamic data for predicting Eb, which breaks the well-known Bronsted-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-C3N4 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 X2S (X = Li, Na, and K) and thus accelerate the design of SACs for alkaline-chalcogenide batteries.

Automated summary

Single-atom catalysts (SACs) are promising cathode materials for lithium-sulfur batteries. This study identifies a new effective descriptor A(Li -S -Li) for accelerating the screening of superior SACs by clarifying the effects of bond formation and breakage on the kinetics of Li2S decomposition. The results open up a new pathway for designing SACs for alkaline-chalcogenide batteries.