High Entropy Sulfide Nanoparticles as Lithium Polysulfide Redox Catalysts

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, Zn0.30Co0.31Cu0.19In0.13Ga0.06S. 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 Zn0.30Co0.31Cu0.19In0.13Ga0.06S 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.

A Review on Engineering Transition Metal Compound Catalysts to Accelerate the Redox Kinetics of Sulfur Cathodes for Lithium–Sulfur Batteries

“…As a result, the high-entropy sulfide exhibited superior catalytic properties than any constituent metal sulfides in both discharge and charge stages. It was noteworthy that although GuGaS 2 and CuInS 2 had catalyzed the reduction reaction, no metal sulfides catalyzed the oxidation reaction, and the high-entropy sulfide showed significantly improved oxidation kinetics due to the synergistic interaction between the components of the high-entropy sulfide [ 109 ]. Qiao designed high-entropy oxide composed of highly dispersive Ni, Mg, Cu, Zn and Co, which exposed abundant active sites, and could strong anchor LiPSs with Li–O and S–Ni bonds and catalyze LiPSs conversion of (Fig.…”

“…In addition, the chemical and structural stability of high-entropy materials in the charging and discharging process of LSBs should be considered. It was found that the copper in Zn 0.30 Co 0.31 Cu 0.19 In 0.13 Ga 0.06 S was leached out as an ionic species, accompanied with the smaller particles and lower crystallinity of high-entropy sulfide, gives a good indication that stabilizing cations could prolong the life of catalysts and improve the capacity retention ability [ 109 ]. Furthermore, the significant lattice distortion is also one of the key factors for the excellent catalytic performance of high-entropy materials.…”

A Review on Catalytic Progress of Polysulfide Redox Reactions on Transition Metal Sulfides in Li‐S Batteries from Structural Perspective

“…[26][27][28] Moreover, the inherent electronic/ion insulation, shuttle effect, growth of lithium dendrites, volume expansion, and other issues of polysulfides also affect the performance of LiÀ S batteries, especially under high sulfur loads, these problems become more severe, leading to rapid capacity decay of LiÀ S batteries. [29][30][31][32][33] Therefore, well-designed electrodes with the ability to accelerate charge transfer, suppress shuttle effects, and enhance conversion kinetics are crucial for achieving the practical application of high energy density LiÀ S batteries. [34][35][36][37][38] Reasonably designing efficient media and integrating them into batteries is a promising method for constructing high energy density LiÀ S batteries.…”

Electrochemical Restructuring Driven Catalytic Cycle of Bi-Based Heterojunctions for High-Performance Lithium–Sulfur Batteries

“…With elaborate structure modulation, considerable hosts possessing high active sites, such as metals, − oxides, − sulfides, − selenide, , and carbides, , have exhibited high catalytic activity toward the conversion of the sulfur species. In addition, many composite catalysts could also enhance the conductivity, retard the volume fluctuation of the cathode, and provide chemical and physical limitations for LiPS. ,, Particularly, some heterostructures and amorphous hosts with various catalytic sites show good catalytic capability for the bidirectional sulfur conversion reactions. ,,− However, two critical issues associated with the catalytic hosts remain to be solved to further improve the performance of the sulfur cathodes, which are fabricated with a high sulfur content and high areal loading to meet the practical standards.…”