A Rayleighian approach for modeling kinetics of ionic transport in polymeric media
Abstract
Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes from the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Univ. of Tennessee, Knoxville, TN (United States)
- Hunter College of the City Univ. of New York, New York, NY (United States)
- (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1344272
- Alternate Identifier(s):
- OSTI ID: 1987886
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 146; Journal Issue: 6; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Kumar, Rajeev, Mahalik, Jyoti P., Bocharova, Vera, Stacy, Eric W., Gainaru, Catalin, Saito, Tomonori, Gobet, Mallory P., Greenbaum, Steve, Sumpter, Bobby G., Sokolov, Alexei P., and Univ. of Tennessee, Knoxville, TN. A Rayleighian approach for modeling kinetics of ionic transport in polymeric media. United States: N. p., 2017.
Web. doi:10.1063/1.4975309.
Kumar, Rajeev, Mahalik, Jyoti P., Bocharova, Vera, Stacy, Eric W., Gainaru, Catalin, Saito, Tomonori, Gobet, Mallory P., Greenbaum, Steve, Sumpter, Bobby G., Sokolov, Alexei P., & Univ. of Tennessee, Knoxville, TN. A Rayleighian approach for modeling kinetics of ionic transport in polymeric media. United States. https://doi.org/10.1063/1.4975309
Kumar, Rajeev, Mahalik, Jyoti P., Bocharova, Vera, Stacy, Eric W., Gainaru, Catalin, Saito, Tomonori, Gobet, Mallory P., Greenbaum, Steve, Sumpter, Bobby G., Sokolov, Alexei P., and Univ. of Tennessee, Knoxville, TN. Tue .
"A Rayleighian approach for modeling kinetics of ionic transport in polymeric media". United States. https://doi.org/10.1063/1.4975309. https://www.osti.gov/servlets/purl/1344272.
@article{osti_1344272,
title = {A Rayleighian approach for modeling kinetics of ionic transport in polymeric media},
author = {Kumar, Rajeev and Mahalik, Jyoti P. and Bocharova, Vera and Stacy, Eric W. and Gainaru, Catalin and Saito, Tomonori and Gobet, Mallory P. and Greenbaum, Steve and Sumpter, Bobby G. and Sokolov, Alexei P. and Univ. of Tennessee, Knoxville, TN},
abstractNote = {Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes from the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.},
doi = {10.1063/1.4975309},
journal = {Journal of Chemical Physics},
number = 6,
volume = 146,
place = {United States},
year = {Tue Feb 14 00:00:00 EST 2017},
month = {Tue Feb 14 00:00:00 EST 2017}
}
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Works referencing / citing this record:
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