In operando Raman and optical study of lithium polysulfides dissolution in lithium–sulfur cells with carrageenan binder

Abstract In operando Raman and optical studies have been performed on lithium–sulfur (Li–S) batteries containing carrageenan binder in the sulfur cathode for chemical trapping of the polysulfides (PSs). Three different types of cells were used: coin cells, EL-cell and capillary cells to examine the PS speciation. With the coin cell we confirm the stability and cyclability of the carrageenan based Li–S cells and the improved capacity retention when compared to conventional polyvinylidene fluoride based Li–S cells. With the EL-Cell, the PS speciation at the cathode is documented but only weak evidences of the nucleophilic trapping of the PS are found. The in operando Raman and optical studies on the capillary cell revealed the dissolution and diffusion of the PS in the whole electrolyte volume. We confirm the disproportionation of S 4 − into S 3 − in the electrolyte. Strong inhomogeneous PS concentration in the electrolyte are found to develop in the course of the cell charge–discharge cycling which must be detrimental to the performances of the battery.