NMR studies of nanoscale organization and dynamics in polymer electrolytes

William S. Price, Yuichi Aihara, Kikuko Hayamizu

    Research output: Contribution to journalArticle

    Abstract

    Multinuclear (i.e., 7Li, 19F, and 1H) NMR relaxation and pulsed field gradient spin-echo (PGSE) NMR translational diffusion measurements have been used to study the reorientational and translational dynamics of the polymeric, anionic, and cationic species in a polymer electrolyte system composed of high-molecular-weight comb-branched polyethers and their precursor macromonomers of cross-linked random copolymers, with and without LiN(SO2CF3)2 (LiTFSI) doping. The macromonomers are derivatives of glycerol bonded to ethylene oxide-co-propylene oxide (m(EO-PO)) and are viscous liquids with a molecular weight of approximately 8000. The results were consistent with a picture of the lithium ions undergoing local motions near the polymer chains, whereas the anions diffuse through a slowly fluctuating three-dimensional porous polymer matrix. Four years later, the macromonomer electrolyte samples were re-measured to investigate the effects of long-term aging. The NMR data revealed that the electrolyte has undergone sigficant structural relaxation. The findings shed light on the evolving molecular architectures that influence conductivity and help to explain the non-ideal conductivity behaviour.
    Original languageEnglish
    Number of pages6
    JournalAustralian Journal of Chemistry
    DOIs
    Publication statusPublished - 2004

    Keywords

    • electrolytes
    • ions
    • lithium
    • nuclear magnetic resonance
    • polyelectrolytes
    • relaxation (Nuclear physics)

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