Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids
Abstract
Polymerized ionic liquids (PolyILs) are promising candidates for a broad range of technologies. However, the relatively low conductivity of PolyILs at room temperature has strongly limited their applications. In this work, we provide new insights into the roles of various microscopic parameters controlling ion transport in these polymers, which are crucial for their rational design and practical applications. Using broadband dielectric spectroscopy and neutron and light scattering techniques, we found a clear connection between the activation energy for conductivity, fast dynamics, and high-frequency shear modulus in PolyILs at their glass transition temperature (Tg). In particular, our analysis reveals a correlation between conductivity and the amplitude of fast picosecond fluctuations at Tg, suggesting the possible involvement of fast dynamics in lowering the energy barrier for ion conductivity. We also demonstrate that both the activation energy for ion transport and the amplitude of the fast fluctuations depend on the high-frequency shear moduli of PolyILs, thus identifying a practically important parameter for tuning conductivity. Finally, the parameters recognized in this work and their connection to the ionic conductivity of PolyILs set the stage for a deeper understanding of the mechanism of ion transport in PolyILs in the glassy state.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Montpellier (France)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
- OSTI Identifier:
- 1755297
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Volume: 124; Journal Issue: 46; Journal ID: ISSN 1520-6106
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; charge transport; energy; electrical conductivity; ions; polymers
Citation Formats
Bocharova, Vera, Genix, Anne-Caroline, Kisliuk Estate, Alexander, Sala, Gabriele, Osti, Naresh C., Mamontov, Eugene, and Sokolov, Alexei P. Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids. United States: N. p., 2020.
Web. doi:10.1021/acs.jpcb.0c07549.
Bocharova, Vera, Genix, Anne-Caroline, Kisliuk Estate, Alexander, Sala, Gabriele, Osti, Naresh C., Mamontov, Eugene, & Sokolov, Alexei P. Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids. United States. https://doi.org/10.1021/acs.jpcb.0c07549
Bocharova, Vera, Genix, Anne-Caroline, Kisliuk Estate, Alexander, Sala, Gabriele, Osti, Naresh C., Mamontov, Eugene, and Sokolov, Alexei P. Sat .
"Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids". United States. https://doi.org/10.1021/acs.jpcb.0c07549. https://www.osti.gov/servlets/purl/1755297.
@article{osti_1755297,
title = {Role of Fast Dynamics in Conductivity of Polymerized Ionic Liquids},
author = {Bocharova, Vera and Genix, Anne-Caroline and Kisliuk Estate, Alexander and Sala, Gabriele and Osti, Naresh C. and Mamontov, Eugene and Sokolov, Alexei P.},
abstractNote = {Polymerized ionic liquids (PolyILs) are promising candidates for a broad range of technologies. However, the relatively low conductivity of PolyILs at room temperature has strongly limited their applications. In this work, we provide new insights into the roles of various microscopic parameters controlling ion transport in these polymers, which are crucial for their rational design and practical applications. Using broadband dielectric spectroscopy and neutron and light scattering techniques, we found a clear connection between the activation energy for conductivity, fast dynamics, and high-frequency shear modulus in PolyILs at their glass transition temperature (Tg). In particular, our analysis reveals a correlation between conductivity and the amplitude of fast picosecond fluctuations at Tg, suggesting the possible involvement of fast dynamics in lowering the energy barrier for ion conductivity. We also demonstrate that both the activation energy for ion transport and the amplitude of the fast fluctuations depend on the high-frequency shear moduli of PolyILs, thus identifying a practically important parameter for tuning conductivity. Finally, the parameters recognized in this work and their connection to the ionic conductivity of PolyILs set the stage for a deeper understanding of the mechanism of ion transport in PolyILs in the glassy state.},
doi = {10.1021/acs.jpcb.0c07549},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 46,
volume = 124,
place = {United States},
year = {Sat Nov 07 00:00:00 EST 2020},
month = {Sat Nov 07 00:00:00 EST 2020}
}
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