Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids

Jordan R. Keith, Nathan J. Rebello, Benjamin J. Cowen, Venkat Ganesan

Research output: Contribution to journalArticlepeer-review

25 Scopus citations

Abstract

We performed long-time all-atom molecular dynamics simulations of cationic polymerized ionic liquids with eight mobile counterions, systematically varying size and shape to probe their influence on the decoupling of conductivity from polymer segmental dynamics. We demonstrated rigorous identification of the dilatometric glass-transition temperature (T g ) for polymerized ionic liquids using an all-atom force field. Polymer segmental relaxation rates are presumed to be consistent for different materials at the same glass-transition-normalized temperature (T g /T), allowing us to extract a relative order of decoupling by examining conductivity at the same T g /T. Size, or ionic volume, cannot fully explain decoupling trends, but within certain geometric and chemical-specific classes, small ions generally show a higher degree of decoupling. This size effect is not universal and appears to be overcome when structural results reveal substantial coordination delocalization. We also reveal a universal inverse correlation between ion-association structural relaxation time and absolute conductivity for these polymerized ionic liquids, supporting the ion-hopping interpretation of ion mobility in polymerized ionic liquids.
Original languageEnglish (US)
Pages (from-to)387-392
Number of pages6
JournalACS Macro Letters
Volume8
Issue number4
DOIs
StatePublished - Mar 25 2019
Externally publishedYes

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics

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