Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids

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

doi:10.1021/acs.macromol.8b01221

Title: Fundamental Limitations of Ionic Conductivity in Polymerized Ionic Liquids

Journal Article · 21 October 2018 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.8b01221 · OSTI ID:1490598

Stacy, Eric W. ^[1]; Gainaru, Catalin P. ^[2];

^[3];

^[4];

^[5]; Greenbaum, Steven G. ^[3];

^[6]

Univ. of Tennessee, Knoxville, TN (United States)
Technische Universität Dortmund (Germany)
City Univ. (CUNY), NY (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); University of Silesia, SMCEBI, Chorzow (Poland)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

In this paper, 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. In conclusion, 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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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1490598

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 21 Vol. 51; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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