Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

Griffin, Phillip J.; Holt, Adam P.; Tsunashima, Katsuhiko; Sangoro, Joshua R.; Kremer, Friedrich; Sokolov, Alexei P.

doi:10.1063/1.4913239

Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

Journal Article · Sun Feb 01 04:00:00 UTC 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4913239· OSTI ID:1347312

Griffin, Phillip J. ^[1]; Holt, Adam P. ^[2]; Tsunashima, Katsuhiko ^[3]; Sangoro, Joshua R. ^[2]; Kremer, Friedrich ^[4]; Sokolov, Alexei P. ^[5]

Univ. of Pennsylvania, Philadelphia, PA (United States)
Univ. of Tennessee, Knoxville, TN (United States)
Wakayama College (Japan)
Univ. of Leipzig (Germany)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range-indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-00OR22725

OSTI ID:: 1347312

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 142; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

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