A molecular dynamics study of the binding effectiveness between undoped conjugated polymer binders and tetra-sulfides in lithium–sulfur batteries

Full atomistic molecular dynamics simulations are performed on tetra-sulfides and undoped conjugated polymers pernigraniline base polyaniline (PNB), leucoemeraldine base polyaniline (LEB), poly (3,4-ethylenedioxythiophene) (PEDOT) and polypyrrole (PPY) to investigate the binding effectiveness between polysulfides and polymer binders. The weight ratio between sulfur and binder in lithium–sulfur cells is considered in 1:1 v/v mixture of dioxolane/dimethoxyethane. The simulations reveal that the end group 2 of PNB can effectively bind a lithium tetra-sulfide (i.e. Li₂S₄) cluster or 2 out of 43 Li₂S₄ molecules with the effect of solvent. However, repeat units of PNB, LEB, PEDOT and PPY seem ineffective in binding solvated Li₂S₄ through non-bonded interaction, especially when the concentration of tetra-sulfide/binder in a local domain of the cathode is low. Therefore, polymers with this specific functional group (i.e. the end group 2 of PNB) are suggested to be further studied as potential effective binders to inhibit the shuttle effect of solvated lithium polysulfides. Also, since the solvent has considerable impact on the binding effectiveness between tetra-sulfides and binder, it is suggested to take advantage of the explicit solvation models, such as those built in this work, to predict how other influencing factors affect binding between polysulfides and polymers.