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Title: Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids

Abstract

We performed long-time all-atom molecular dynamics simulations of cationic polymerized ionic liquids with eight mobile counterions, systematically varying size and shape to probe their influence on the decoupling of conductivity from polymer segmental dynamics. We demonstrated rigorous identification of the dilatometric glass-transition temperature ( T g) for polymerized ionic liquids using an all-atom force field. Polymer segmental relaxation rates are presumed to be consistent for different materials at the same glass-transition-normalized temperature ( T g/ T), allowing us to extract a relative order of decoupling by examining conductivity at the same T g/ T. Size, or ionic volume, cannot fully explain decoupling trends, but within certain geometric and chemical-specific classes, small ions generally show a higher degree of decoupling. This size effect is not universal and appears to be overcome when structural results reveal substantial coordination delocalization. Here, we also reveal a universal inverse correlation between ion-association structural relaxation time and absolute conductivity for these polymerized ionic liquids, supporting the ion-hopping interpretation of ion mobility in polymerized ionic liquids.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]
  1. Univ. of Texas at Austin, Austin, TX (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1507409
Report Number(s):
SAND-2019-3066J
Journal ID: ISSN 2161-1653; 673567
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
ACS Macro Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 4; Journal ID: ISSN 2161-1653
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Keith, Jordan R., Rebello, Nathan J., Cowen, Benjamin J., and Ganesan, Venkat. Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids. United States: N. p., 2019. Web. doi:10.1021/acsmacrolett.9b00070.
Keith, Jordan R., Rebello, Nathan J., Cowen, Benjamin J., & Ganesan, Venkat. Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids. United States. doi:10.1021/acsmacrolett.9b00070.
Keith, Jordan R., Rebello, Nathan J., Cowen, Benjamin J., and Ganesan, Venkat. Mon . "Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids". United States. doi:10.1021/acsmacrolett.9b00070.
@article{osti_1507409,
title = {Influence of Counterion Structure on Conductivity of Polymerized Ionic Liquids},
author = {Keith, Jordan R. and Rebello, Nathan J. and Cowen, Benjamin J. and Ganesan, Venkat},
abstractNote = {We performed long-time all-atom molecular dynamics simulations of cationic polymerized ionic liquids with eight mobile counterions, systematically varying size and shape to probe their influence on the decoupling of conductivity from polymer segmental dynamics. We demonstrated rigorous identification of the dilatometric glass-transition temperature (Tg) for polymerized ionic liquids using an all-atom force field. Polymer segmental relaxation rates are presumed to be consistent for different materials at the same glass-transition-normalized temperature (Tg/T), allowing us to extract a relative order of decoupling by examining conductivity at the same Tg/T. Size, or ionic volume, cannot fully explain decoupling trends, but within certain geometric and chemical-specific classes, small ions generally show a higher degree of decoupling. This size effect is not universal and appears to be overcome when structural results reveal substantial coordination delocalization. Here, we also reveal a universal inverse correlation between ion-association structural relaxation time and absolute conductivity for these polymerized ionic liquids, supporting the ion-hopping interpretation of ion mobility in polymerized ionic liquids.},
doi = {10.1021/acsmacrolett.9b00070},
journal = {ACS Macro Letters},
number = 4,
volume = 8,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
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This content will become publicly available on March 25, 2020
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