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Importance of the Ion-Pair Lifetime in Polymer Electrolytes.

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 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.

SUBMITTER: Gudla H

PROVIDER: S-EPMC8436209 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Importance of the Ion-Pair Lifetime in Polymer Electrolytes.

Gudla Harish H Shao Yunqi Y Phunnarungsi Supho S Brandell Daniel D Zhang Chao C

The journal of physical chemistry letters 20210827 35

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<sub>+-</sub><sup>d</sup> an ...[more]

PMID: 34449227

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