Abstract
Further understanding of the redox process of lithium polysulfides (PSs) on carbon surface is helpful to design Li/S batteries with better performance. “Shuttle mechanism” can explain the low coulomb efficiency and self-discharge of a Li/S battery, but it cannot explain the fact that battery performance is closely affected by electrolyte volume and sulfur load. This paper aims to reveal main redox process of PSs on surface of carbon by examining cathodic behavior with different electrolyte volume and sulfur load. SEM photos and Impedance Spectra of cathode before and after 1st discharge were compared, it was found that the discharge process is the continuous dissolution of sulfur composited with carbon into the electrolyte to form PSs, at the same time, PSs re-precipitates sulfur on the surface of cathode through disproportionation reaction to form a solid film. CV curves showed that the solid film passivates electrode, and the electrode is activated only when potential sweeps negatively and Li2S is generated. When lean electrolyte is used, there is fluctuation in CV curves, which proves that the dissolution-reprecipitation of sulfur is the main process of cathode. The discharge-charge curves of cathodes with different sulfur load were compared, it was found that there is wavy fluctuation in the discharge curve with high sulfur load, which proves again that the sulfur reaction dominates the electrode process.