Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers

Roach, David J.; Dou, Shichen; Colby, Ralph H.; Mueller, Karl T.

doi:10.1063/1.3669449

Nuclear magnetic resonance investigation of dynamics in poly(ethylene oxide)-based lithium polyether-ester-sulfonate ionomers

Journal Article · Fri Jan 06 00:00:00 EST 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3669449· OSTI ID:1076446

Roach, David J. ^[1]; Dou, Shichen ^[1]; Colby, Ralph H. ^[1]; Mueller, Karl T. ^[2]

Pennsylvania State University, University Park, PA (United States)
Pacific Northwest Lab., Richland, WA (United States). Environmental Molecular Sciences Lab.

Nuclear magnetic resonance (NMR) spectroscopy has been utilized to investigate the dynamics of poly(ethylene oxide)-based lithium sulfonate ionomer samples that have low glass transition temperatures. ¹H and ⁷Li spin-lattice relaxation times (T₁) of the bulk polymer and lithium ions, respectively, were measured and analyzed in samples with a range of ion contents. The temperature dependence of T₁ values along with the presence of minima in T₁ as a function of temperature enabled correlation times and activation energies to be obtained for both the segmental motion of the polymer backbone and the hopping motion of lithium cations. Similar activation energies for motion of both the polymer and lithium ions in the samples with lower ion content indicate that the polymer segmental motion and lithium ion hopping motion are correlated in these samples, even though their respective correlation times differ significantly. A divergent trend is observed for correlation times and activation energies of the highest ion content sample with 100% lithium sulfonation due to the presence of ionic aggregation. Details of the polymer and cation dynamics on the nanosecond timescale are discussed and complement the findings of X-ray scattering and Quasi Elastic Neutron Scattering experiments.

View Accepted Manuscript (DOE)

Research Organization:: Pennsylvania State University, University Park, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: FG02-07ER46409

OSTI ID:: 1076446

Alternate ID(s):: OSTI ID: 1035417

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 136; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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