Transport Properties of Polysulfide Species in Lithium–Sulfur Battery Electrolytes: Coupling of Experiment and Theory

[Image: see text] A comprehensive experimental and theoretical analysis of the isothermal transport of species for the two model ternary-electrolytes with LiTFSI-Li(2)S(4)/dioxolane (DOL)-dimethoxyethane (DME) and LiTFSI-Li(2)S(6)/DOL-DME formulations is presented. An unambiguous picture of the polysulfide’s mobility is set forth after a detailed investigation of the macroscopic transference number and diffusion coefficients. The new findings of incongruent diffusion for Li(2)S(4) species and high significance of cross-term diffusion coefficients reformulate a fledgling view of the prevalent redox-shuttle phenomena. The practical implications of this complex mechanism are discussed in detail.