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Comparing ion transport in ionic liquids and polymerized ionic liquids.

Wangchuan Xiao1, Quan Yang2, Shenlin Zhu3

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Anion transport in polymerized ionic liquids (polyILs) differs significantly from ionic liquids (ILs). In polyILs, anion diffusion is governed by hopping between cages, not ion association lifetime, impacting ion transport mechanisms.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Polymer Science

Background:

  • Polymerized ionic liquids (polyILs) integrate properties of ionic liquids (ILs) and polymers.
  • Anion diffusion in polyILs is notably slower (up to 1000x) than in ILs, hindering their application.
  • Understanding ion transport mechanisms in polyILs is crucial for improving their performance.

Purpose of the Study:

  • To compare ion transport mechanisms in a specific polyIL, poly(1-butyl-3-vinylimidazolium-tetrafluoroborate) (poly([BVIM]-[BF4])), and its corresponding IL, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]-[BF4]).
  • To elucidate the factors governing anion diffusivity in polyILs and ILs.

Main Methods:

  • Molecular dynamics simulations were employed to compute and analyze ion diffusivities.
  • Calculations of average displacements (ADs) of polyIL chains were performed.

Main Results:

  • In ILs, ion diffusivity is determined by coupled ion motion and ion association lifetime.
  • In polyILs, anion diffusion relies on hopping between cages formed by cationic chains, with 'trap time' being the relevant timescale.
  • PolyIL chain dynamics, including oscillation amplitude and translation speed, alongside free volume, influence diffusivity at different temperatures.

Conclusions:

  • The mechanism of anion transport in polyILs is distinct from ILs, involving cage hopping rather than ion association lifetime.
  • Polymer chain dynamics play a significant role in modulating ion transport in polyILs.
  • These findings offer insights for designing polyILs with enhanced ion transport properties.