Importance of the Ion-Pair Lifetime in Polymer Electrolytes

[Image: see text] Ion pairing is commonly considered as a culprit for the reduced ionic conductivity in polymer electrolyte systems. However, this simple thermodynamic picture should not be taken literally, as ion pairing is a dynamical phenomenon. Here we construct model poly(ethylene oxide)–bis(trifluoromethane)sulfonimide lithium salt systems with different degrees of ion pairing by tuning the solvent polarity and examine the relation between the cation–anion distinct conductivity σ(+–)(d) and the lifetime of ion pairs τ(+–) using molecular dynamics simulations. It is found that there exist two distinct regimes where σ(+–)(d) scales with 1/τ(+–) and τ(+–), respectively, and the latter is a signature of longer-lived ion pairs that contribute negatively to the total ionic conductivity. This suggests that ion pairs are kinetically different depending on the solvent polarity, which renders the ion-pair lifetime highly important when discussing its effect on ion transport in polymer electrolyte systems.