Influence of molecular weight on ion-transport properties of polymeric ionic liquids
文献情報
Jordan R. Keith, Santosh Mogurampelly, Faisal Aldukhi, Bill K. Wheatle, Venkat Ganesan
We report the results of atomistic molecular dynamics simulations on polymerized 1-butyl-3-vinylimidazolium-hexafluorophosphate ionic liquids, studying the influence of the polymer molecular weight on the ion mobilities and the mechanisms underlying ion transport, including ion-association dynamics, ion hopping, and ion–polymer coordinations. With an increase in polymer molecular weight, the diffusivity of the hexafluorophosphate (PF6−) counterion decreases and plateaus above seven repeat units. The diffusivity is seen to correlate well with the ion-association structural relaxation time for pure ionic liquids, but becomes more correlated with ion-association lifetimes for larger molecular weight polymers. By analyzing the diffusivity of ions based on coordination structure, we unearth a transport mechanism in which the PF6− moves by “climbing the ladder” while associated with four polymeric cations from two different polymers.
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