Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids

Eric W. Stacy; Catalin P. Gainaru; Mallory Gobet; Zaneta Wojnarowska; Vera Bocharova; Steven G. Greenbaum; Alexei P. Sokolov

doi:10.1021/acs.macromol.8b01221

Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids

Eric W. Stacy, Catalin P. Gainaru, Mallory Gobet, Zaneta Wojnarowska, Vera Bocharova, Steven G. Greenbaum, Alexei P. Sokolov

Soft Materials and Membranes

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111 Scopus citations

Abstract

We present detailed studies of ionic conductivity in several polymerized ionic liquids (PolyILs) with different size of mobile ions. Presented analysis revealed that charge diffusion in PolyILs is about 10 times slower than ion diffusion, suggesting strong ion-ion correlations that reduce ionic conductivity. The activation energy for the ion diffusion shows a nonmonotonous dependence on the mobile ion size, indicating a competition between Coulombic and elastic forces controlling ion transport in PolyILs. The former dominates mobility of small ions (e.g., Li), while the latter controls mobility of large ions (e.g., TFSI). We propose a simple qualitative model describing the activation energy for the ion diffusion. It suggests that an increase in dielectric constant of PolyILs should lead to a significant enhancement of conductivity of small ions (e.g., Li and Na).

Original language	English
Pages (from-to)	8637-8645
Number of pages	9
Journal	Macromolecules
Volume	51
Issue number	21
DOIs	https://doi.org/10.1021/acs.macromol.8b01221
State	Published - Nov 13 2018

Funding

This work was supported by Laboratory Directed Research and Development program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the U.S. Department of Energy. A.P.S. also acknowledges partial financial support for the data analysis by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. The NMR work at Hunter College was supported by the U.S. Office of Naval Research. Z.W. is grateful for the financial support by the National Science Centre within the framework of the Opus 8 project (Grant No. DEC-2014/15/B/ST3/04246). C.P.G. acknowledges financial support from Deutsche Forschungsgemeinschaft under GA2680/1-1 project.

Funders	Funder number
Office of Naval Research
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Laboratory Directed Research and Development
Division of Materials Sciences and Engineering
Deutsche Forschungsgemeinschaft	GA2680/1-1
Narodowe Centrum Nauki	DEC-2014/15/B/ST3/04246

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10.1021/acs.macromol.8b01221

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title = "Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids",

abstract = "We present detailed studies of ionic conductivity in several polymerized ionic liquids (PolyILs) with different size of mobile ions. Presented analysis revealed that charge diffusion in PolyILs is about 10 times slower than ion diffusion, suggesting strong ion-ion correlations that reduce ionic conductivity. The activation energy for the ion diffusion shows a nonmonotonous dependence on the mobile ion size, indicating a competition between Coulombic and elastic forces controlling ion transport in PolyILs. The former dominates mobility of small ions (e.g., Li), while the latter controls mobility of large ions (e.g., TFSI). We propose a simple qualitative model describing the activation energy for the ion diffusion. It suggests that an increase in dielectric constant of PolyILs should lead to a significant enhancement of conductivity of small ions (e.g., Li and Na).",

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AU - Stacy, Eric W.

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AU - Bocharova, Vera

AU - Greenbaum, Steven G.

AU - Sokolov, Alexei P.

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Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids

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