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 PEO-LiTFSI systems with different degree of ion-pairing by tuning solvent polarity, and examine the relation between the cation-anion distinct conductivity \sigma^\rm{d}_{+-} and the lifetime of ion-pairs $\tau_{+-}$ using molecular dynamics simulations. It is found that there exist two distinct regimes where \sigma^\rm{d}_{+-} scales with $1/\tau_{+-}$ and $\tau_{+-}$ respectively, and the latter is a signature of longer-lived ion-pairs which 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.