Polysulfides are central compounds in lithium-sulfur battery cells. However, the fundamental redox and diffusion properties of polysulfides are still poorly understood. We try to fill this gap by performing an accurate impedance spectroscopy investigation using symmetrical cells consisting of two planar glassy carbon electrodes separated with catholyte-soaked separator. The catholyte contains a mixture of selected polysulfides with predetermined nominal concentrations. Impedance measurements reveal textbook shapes of spectra for most polysulfide compounds or their mixtures. This allows reliable and accurate determination of the rate constant (exchange current density) for a given redox reaction as well as the diffusion coefficient and diffusion length for the rate-determining polysulfide species. Further, it is confirmed that polysulfides tend to disproportionate with time, which significantly changes the chemistry and electrochemistry of the system. Two approaches are proposed for identification of the prevailing redox mechanism in the resulting mixtures. The values of kinetic and transport parameters obtained for different cases of interest are commented on in significant detail. The study provides a solid basis for better understanding of the complex processes in polysulfide mixtures.
Keywords: diffusion coefficient; disproportionation; impedance spectroscopy; polysulfides; reaction mechanism; redox kinetics.