Unraveling Shuttle Effect and Suppression Strategy in Lithium/Sulfur Cells by In Situ/Operando X-ray Absorption Spectroscopic Characterization

The polysulfides shuttle effect represents a great challenge in achieving high capacity and long lifespan of lithium/sulfur (Li/S) cells. A comprehensive understanding of the shuttle-related sulfur speciation and diffusion process is vital for addressing this issue. Herein, we employed in situ/operando X-ray absorption spectroscopy (XAS) to trace the migration of polysulfides across the Li/S cells by precisely monitoring the sulfur chemical speciation at the cathodic electrolyte-separator and electrolyte-anode interfaces, respectively, in a real-time condition. After we adopted a shuttle-suppressing strategy by introducing an electrocatalytic layer of twinborn bismuth sulfide/bismuth oxide nanoclusters in a carbon matrix (BSOC), we found the Li/S cell showed greatly improved sulfur utilization and longer life span. The operando S K-edge XAS results revealed that the BSOC modification was bi-functional: trapping polysulfides and catalyzing conversion of sulfur species simultaneously. We elucidated that the polysulfide trapping-and-catalyzing effect of the BSOC electrocatalytic layer resulted in an effective lithium anode protection. Our results could offer potential stratagem for designing more advanced Li/S cells.

Automated summary

The polysulfides shuttle effect poses a significant challenge for the high capacity and long lifespan of Li/S cells. By utilizing in situ/operando XAS, the migration of polysulfides across the Li/S cells was traced, leading to the discovery that introducing a BSOC electrocatalytic layer can effectively suppress the shuttle effect and improve sulfur utilization and lifespan of the cells. The bi-functional nature of the BSOC modification, trapping polysulfides and catalyzing sulfur species conversion simultaneously, provides an effective lithium anode protection mechanism.