Importance of the ion-pair lifetime in polymer electrolytes

TL;DR

This study uses molecular dynamics simulations to explore how ion-pair lifetime influences ionic conductivity in polymer electrolytes, revealing two regimes where ion-pair dynamics either hinder or enhance ion transport.

Contribution

It demonstrates the significance of ion-pair lifetime in polymer electrolytes and identifies two distinct regimes affecting ionic conductivity based on ion-pair dynamics.

Findings

Longer ion-pair lifetimes reduce ionic conductivity.

Ion-pair behavior varies with solvent polarity.

Two regimes of ion-pair influence on conductivity are identified.

Abstract

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.