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A Rayleighian approach for modeling kinetics of ionic transport in polymeric media

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4975309· OSTI ID:1344272
 [1];  [1];  [1];  [2];  [2];  [1];  [3];  [3];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States)
  3. Hunter College of the City Univ. of New York, New York, NY (United States)
+ Show Author Affiliations
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.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1344272
Alternate ID(s):
OSTI ID: 1987886
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 146; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures journal January 2018
Structure and dynamics of short-chain polymerized ionic liquids journal July 2019

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36 MATERIALS SCIENCE