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Title: Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids

Abstract

Understanding the mechanisms controlling ionic conductivity is critical for the development of the next generation of batteries and supercapacitors. This paper discusses the significant role played by ionic correlations in conductivity of concentrated ionic systems. Our studies of an organic ionic plastic crystal reveal that correlations in ions dynamics suppress conductivity by 25–100 times in comparison to the expected uncorrelated ionic conductivity estimated from the Nernst–Einstein relationship. Furthermore, additional analysis also demonstrates that ionic correlations suppress conductivity in polymerized ionic liquids and gel by ~10 times. Thus, ionic correlations, usually neglected in many studies, play a very important role in conductivity of concentrated ionic systems. These results cannot be explained by a diffusion of ion pairs because all these systems are essentially single ion conductors. In contrast, strongly correlated motions of mobile ions with the same charge (cation–cation or anion–anion correlations) are the major mechanism suppressing the ionic conductivity in these systems. Finally, on the basis of these results, we emphasize that charge transport rather than ion diffusion is critical for electrolyte performance and suggest the potential design of plastic crystals and polymer electrolytes with enhanced ionic conductivity.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Deakin Univ., Burwood, VIC (Australia). Inst. for Frontier Materials
  3. Kazan Federal Univ. (Russia)
  4. Technische Univ., Dortmund (Germany)
  5. Deakin Univ., Burwood, VIC (Australia). Inst. for Frontier Materials; Deakin Univ., Burwood, VIC (Australia). ARC Centre of Excellence for Electromaterials Science (ACES)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1651268
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 33; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; plastics; diffusion; ions; electrical conductivity

Citation Formats

Popov, Ivan, Biernacka, Karolina, Zhu, Haijin, Nti, Frederick, Porcarelli, Luca, Wang, Xiaoen, Khamzin, Airat, Gainaru, Catalin, Forsyth, Maria, and Sokolov, Alexei P. Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids. United States: N. p., 2020. Web. doi:10.1021/acs.jpcc.0c03297.
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Popov, Ivan, Biernacka, Karolina, Zhu, Haijin, Nti, Frederick, Porcarelli, Luca, Wang, Xiaoen, Khamzin, Airat, Gainaru, Catalin, Forsyth, Maria, & Sokolov, Alexei P. Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids. United States. https://doi.org/10.1021/acs.jpcc.0c03297
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Popov, Ivan, Biernacka, Karolina, Zhu, Haijin, Nti, Frederick, Porcarelli, Luca, Wang, Xiaoen, Khamzin, Airat, Gainaru, Catalin, Forsyth, Maria, and Sokolov, Alexei P. Mon . "Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids". United States. https://doi.org/10.1021/acs.jpcc.0c03297. https://www.osti.gov/servlets/purl/1651268.
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@article{osti_1651268,
title = {Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids},
author = {Popov, Ivan and Biernacka, Karolina and Zhu, Haijin and Nti, Frederick and Porcarelli, Luca and Wang, Xiaoen and Khamzin, Airat and Gainaru, Catalin and Forsyth, Maria and Sokolov, Alexei P.},
abstractNote = {Understanding the mechanisms controlling ionic conductivity is critical for the development of the next generation of batteries and supercapacitors. This paper discusses the significant role played by ionic correlations in conductivity of concentrated ionic systems. Our studies of an organic ionic plastic crystal reveal that correlations in ions dynamics suppress conductivity by 25–100 times in comparison to the expected uncorrelated ionic conductivity estimated from the Nernst–Einstein relationship. Furthermore, additional analysis also demonstrates that ionic correlations suppress conductivity in polymerized ionic liquids and gel by ~10 times. Thus, ionic correlations, usually neglected in many studies, play a very important role in conductivity of concentrated ionic systems. These results cannot be explained by a diffusion of ion pairs because all these systems are essentially single ion conductors. In contrast, strongly correlated motions of mobile ions with the same charge (cation–cation or anion–anion correlations) are the major mechanism suppressing the ionic conductivity in these systems. Finally, on the basis of these results, we emphasize that charge transport rather than ion diffusion is critical for electrolyte performance and suggest the potential design of plastic crystals and polymer electrolytes with enhanced ionic conductivity.},
doi = {10.1021/acs.jpcc.0c03297},
journal = {Journal of Physical Chemistry. C},
number = 33,
volume = 124,
place = {United States},
year = {Mon Jul 20 00:00:00 EDT 2020},
month = {Mon Jul 20 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acs.jpcc.0c03297
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