The diffusion and conduction of lithium in poly(ethylene oxide)-based sulfonate ionomers

Nikki H. Lafemina, Quan Chen, Ralph H. Colby, Karl T. Mueller

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

Pulsed field gradient nuclear magnetic resonance spectroscopy and dielectric relaxation spectroscopy have been utilized to investigate lithium dynamics within poly(ethylene oxide) (PEO)-based lithium sulfonate ionomers of varying ion content. The ion content is set by the fraction of sulfonated phthalates and the molecular weight of the PEO spacer, both of which can be varied independently. The molecular level dynamics of the ionomers are dominated by either Vogel-Fulcher-Tammann or Arrhenius behavior depending on ion content, spacer length, temperature, and degree of ionic aggregation. In these ionomers the main determinants of the self-diffusion of lithium and the observed conductivities are the ion content and ionic states of the lithium ion, which are profoundly affected by the interactions of the lithium ions with the ether oxygens of the polymer. Since many lithium ions move by segmental polymer motion in the ion pair state, their diffusion is significantly larger than that estimated from conductivity using the Nernst-Einstein equation.

Original languageEnglish (US)
Article number114903
JournalJournal of Chemical Physics
Volume145
Issue number11
DOIs
StatePublished - Sep 21 2016

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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