Ion transport in backbone-embedded polymerized ionic liquids
JR Keith and V Ganesan, JOURNAL OF CHEMICAL PHYSICS, 151, 124902 (2019).
We use atomistic computer simulations to examine ion-transport phenomena for backbone polymerized cationic liquids with bistrifluoromethylesulfonylimide (TFSI-) counterions. We consider a system in which the polymerized cation moiety is the imidazolium ring and study the structural characteristics and ion mobilities for cases in which the cations are separated by four, six, and eight methylene units on the backbone. A pendant polymerized ionic liquid, 1-butyl-3-vinylimidazolium, is compared to the backbone series across ion coordination and hopping features. The anion diffusivity in backbone polymerized cationic liquids is found to decrease with increasing spacer length, which is shown to result from a decrease in intramolecular and intermolecular hopping frequencies due to an increasing distance separating imidazolium moieties. In comparison with pendant polymerized ionic liquids, we observe that the participation rates of intermolecular hopping events in the backbone polymers far exceed that of the pendant, and the intrapolymeric ionic coordination profile shows the TFSI- of the pendant polymer with a high propensity for coordination by multiple imidazolium, compared with one monomer from a given polymer for the backbone series. Despite these differences, backbone polymerized ionic liquids are seen to possess correlated diffusivity and ion-association relaxation times, in a manner similar to the results observed in past studies for pendant variants.
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