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

Gainaru, Catalin P.; Stacy, Eric W.; Bocharova, Vera; Gobet, Mallory; Holt, Adam P.; Saito, Tomonori; Greenbaum, Steve; Sokolov, Alexei P.

doi:10.1021/acs.jpcb.6b08567

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

Journal Article · Wed Sep 28 00:00:00 EDT 2016 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.6b08567· OSTI ID:1337501

Gainaru, Catalin P. ^[1]; Stacy, Eric W. ^[1]; Bocharova, Vera ^[2]; Gobet, Mallory ^[3]; Holt, Adam P. ^[1]; Saito, Tomonori ^[2]; Greenbaum, Steve ^[3]; Sokolov, Alexei P. ^[1]

Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Hunter College of the City University of New York, New York, NY (United States)

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.

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

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1337501

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 120, Issue 42; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 94 works

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