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arXiv · 2107.14722

Importance of the ion-pair lifetime in polymer electrolytes

Harish Gudla·Yunqi Shao·Supho Phunnarungsi·Daniel Brandell·Chao Zhang
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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.

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Harish Gudla, Yunqi Shao, Supho Phunnarungsi, Daniel Brandell, Chao Zhang. 2021-07-30. Importance of the ion-pair lifetime in polymer electrolytes. https://doi.org/10.1021/acs.jpclett.1c02474

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