High Entropy Sulfide Nanoparticles as Lithium Polysulfide Redox Catalysts

M J Theibault; Connor R McCormick; Shuangyan Lang; Raymond E Schaak; Hèctor D Abruña

doi:10.1021/acsnano.3c05869

High Entropy Sulfide Nanoparticles as Lithium Polysulfide Redox Catalysts

ACS Nano. 2023 Sep 26;17(18):18402-18410. doi: 10.1021/acsnano.3c05869. Epub 2023 Sep 17.

Authors

M J Theibault¹, Connor R McCormick², Shuangyan Lang¹, Raymond E Schaak², Hèctor D Abruña¹

Affiliations

¹ Department of Chemistry and Chemical Biology, Cornell University, 245 Feeney Way, Ithaca, New York 14850, United States.
² Department of Chemistry, Department of Chemical Engineering, and Materials Research Institute, The Pennsylvania State University, 104 Chemistry Building, University Park, Pennsylvania 16802, United States.

PMID: 37717254
DOI: 10.1021/acsnano.3c05869

Abstract

The polysulfide shuttle contributes to capacity loss in lithium-sulfur batteries, which limits their practical utilization. Materials that catalyze the complex redox reactions responsible for the polysulfide shuttle are emerging, but foundational knowledge that enables catalyst development remains limited with only a small number of catalysts identified. Here, we employ a rigorous electrochemical approach to show quantitatively that the lithium polysulfide redox reaction is catalyzed by nanoparticles of a high entropy sulfide material, Zn_0.30Co_0.31Cu_0.19In_0.13Ga_0.06S. When 2% by weight of the high entropy sulfide is added to the lithium sulfur cathode composite, the capacity and Coulombic efficiency of the resulting battery are improved at both moderate (0.2 C) and high (1 C) charge/discharge rates. Surface analysis of the high entropy sulfide nanoparticles using X-ray photoelectron spectroscopy provides important insights into how the material evolves during the cycling process. The Zn_0.30Co_0.31Cu_0.19In_0.13Ga_0.06S nanoparticle catalyst outperformed the constituent metal sulfides, pointing to the role that the high-entropy "cocktail effect" can play in the development of advanced electrocatalytic materials for improved lithium sulfur battery performance.

Keywords: battery catalysis; cocktail effect; electrochemical catalysis; high entropy materials; high entropy sulfide; lithium sulfur; polysulfide shuttle.