Elucidating the Electrochemical Activity of Electrolyte-Insoluble Polysulfide Species in Lithium-Sulfur Batteries

The direct synthesis of Li2 S2 , a proposed solid intermediate in the discharge of lithium-sulfur (Li-S) batteries, was accomplished by treating elemental lithium with sulfur in liquid ammonia at -41?? C. The as-synthesized product was analyzed by X-ray photoelectron spectroscopy (XPS) as well as X-ray diffraction (XRD) and determined to be a mixture of crystalline Li2 S, amorphous Li2 S2, and higher-order polysulfides (Li2 Sx , x > 2). Monitored filtration followed by a tailored electrochemical approach was used to successfully remove the higher-order polysulfides and yielded a powder, which was determined by XPS to be comprised of 9 mol% insoluble polysulfide species (mainly Li2 S2 ) and 91 mol% Li2 S. This material was discharged galvanostatically in an electrochemical cell and, despite the lack of soluble polysulfide species, was shown to exhibit a discharge plateau at 2.1 V vs. Li/Li+ . This result confirmed the electrochemical reducibility of electrolyte-insoluble polysulfides in Li-S batteries. Moreover, it was determined that the reduction of solid polysulfides was confined to areas where the sulfur-sulfur bonds were in intimate contact with the conductive current collector. Finally, it was observed that commercially available Li2 S samples contain significant quantities of polysulfide-type impurities.