Dynamical Ion Association and Transport Properties in PEO-LiTFSI Electrolytes: Effect of Salt Concentration

The association of ions describes the formation of ion species in electrolyte solutions and is strongly related to the salt concentration. However, the discussion of ion species and their transport is ambiguous in some studies on electrolyte materials due to the assumption of ideal solutions. Accordingly, in this work, molecular dynamics simulations are used to study ion association and transport properties of poly(ethylene)oxide (PEO)-lithium bis(trifluoromethanesulfonyl)imide electrolytes over a range of salt concentrations (r = [Li]/[EO]) from 0.01 to 0.20. Based on the analysis of the solvation environment and ion species, it is revealed that the distinct ion-ion correlations exist in two different characteristic areas, with a salt concentration of 0.10 as the limit. Below the critical concentration, the dynamic equilibrium between free ions and ion pairs is the most important process affecting the transport properties of electrolytes, but the process may have a minor influence on the applicability of the Nernst-Einstein relation. In concentrated solutions, a large number of ion pairs, triplets, and so forth appear in the electrolytes. The high-order ion clusters, with an average size of 3.95 at r = 0.20, are the main stable structures for transporting Li⁺, but the trapped free ions are the most abundant ion species. Meanwhile, the effect of salt concentrations on the average transport of ion clusters is to increase their average lifetime, but their transport rates remain unchanged. In addition, the coupling dynamics between ions and polymers is also discussed in order to gain a complete insight into the importance of salt concentrations.