Importance of the Ion-Pair Lifetime in Polymer Electrolytes.

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.