Ao Huang, Linglong Kong, Bowen Zhang, Xuefan Liu, Lu Wang*, Lifang Li*, and Jing Xu*

Abstract

Restructuring is an important phenomenon in catalytic reactions. Conversion-type materials with suitable redox potential may undergo in situ electrochemically driven restructurings and induce highly active catalytic sites in a working lithium–sulfur battery. Herein, driven by the electrochemical conversion reaction of BiVO4, a reversible catalytic cycle of Bi/amorphous Li3VO4 (a-Li3VO4) and Bi2S3/a-Li3VO4 heterojunctions is constructed, which targets the oxidation of Li2S and the conversion of polysulfide, respectively. The heterostructures and electrochemically driven size confinement provide abundant sites for shuttle restraining and sulfur conversion. Especially, the p-block Bi and Bi2S3 could dramatically reduce the conversion energy barriers of Li2S and polysulfide by virtue of the p–p orbital hybridization, promoting bidirectional reactions of the sulfur cathode. As a result, the corresponding sulfur cathode possesses a high reversible capacity of 7.5 mAh cm–2 after 120 cycles under a high sulfur loading of 10.3 mg cm–2 with a current density of 0.38 mA cm–2. This study furnishes a feasible scheme to obtain highly effective catalysts for bidirectional sulfur redox by utilizing the electrochemically induced restructuring.

Paper Linkage:https://pubs.acs.org/doi/full/10.1021/acsnano.3c12279