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Title: Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity

Abstract

Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.

Authors:
 [1];  [2];  [1];  [3];  [4];  [1];  [3];  [4];  [1];  [5]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. (Germany)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Hunter College of the City University of New York, New York, NY (United States)
  5. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1337501
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: 120; Journal Issue: 42; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Gainaru, Catalin P., Technische Univ. Dortmund, Dortmund, Stacy, Eric W., Bocharova, Vera, Gobet, Mallory, Holt, Adam P., Saito, Tomonori, Greenbaum, Steve, Sokolov, Alexei P., and Oak Ridge National Lab. Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity. United States: N. p., 2016. Web. doi:10.1021/acs.jpcb.6b08567.
Gainaru, Catalin P., Technische Univ. Dortmund, Dortmund, Stacy, Eric W., Bocharova, Vera, Gobet, Mallory, Holt, Adam P., Saito, Tomonori, Greenbaum, Steve, Sokolov, Alexei P., & Oak Ridge National Lab. Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity. United States. doi:10.1021/acs.jpcb.6b08567.
Gainaru, Catalin P., Technische Univ. Dortmund, Dortmund, Stacy, Eric W., Bocharova, Vera, Gobet, Mallory, Holt, Adam P., Saito, Tomonori, Greenbaum, Steve, Sokolov, Alexei P., and Oak Ridge National Lab. Wed . "Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity". United States. doi:10.1021/acs.jpcb.6b08567. https://www.osti.gov/servlets/purl/1337501.
@article{osti_1337501,
title = {Mechanism of conductivity relaxation in liquid and polymeric electrolytes: Direct link between conductivity and diffusivity},
author = {Gainaru, Catalin P. and Technische Univ. Dortmund, Dortmund and Stacy, Eric W. and Bocharova, Vera and Gobet, Mallory and Holt, Adam P. and Saito, Tomonori and Greenbaum, Steve and Sokolov, Alexei P. and Oak Ridge National Lab.},
abstractNote = {Combining broadband impedance spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance we analyzed charge and mass transport in two polymerized ionic liquids and one of their monomeric precursors. In order to establish a general procedure for extracting single-particle diffusivity from their conductivity spectra, we critically assessed several approaches previously employed to describe the onset of diffusive charge dynamics and of the electrode polarization in ion conducting materials. Based on the analysis of the permittivity spectra, we demonstrate that the conductivity relaxation process provides information on ion diffusion and the magnitude of cross-correlation effects between ionic motions. A new approach is introduced which is able to estimate ionic diffusivities from the characteristic times of conductivity relaxation and ion concentration without any adjustable parameters. Furthermore, this opens the venue for a deeper understanding of charge transport in concentrated and diluted electrolyte solutions.},
doi = {10.1021/acs.jpcb.6b08567},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 42,
volume = 120,
place = {United States},
year = {2016},
month = {9}
}

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