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Title: Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers

Abstract

Here, in order to design more effective solid polymer electrolytes, it is important to decouple ion conductivityfrom polymer segmental motion. To that end, novel polymers based on oxanorbornene dicarboximidemonomers with varying lengths of oligomeric ethylene oxide side chains have been synthesized usingring opening metathesis polymerization. These unique polymers have a fairly rigid and bulky backboneand were used to investigate the decoupling of ion motion from polymer segmental dynamics. Ionconductivity was measured using broadband dielectric spectroscopy for varying levels of added lithiumsalt. The conductivity data demonstrate six to seven orders of separation in timescale of ion conductivityfrom polymer segmental motion for polymers with shorter ethylene oxide side chains. However,commensurate changes in the glass transition temperatures T g reduce the effect of decoupling in ionconductivity and lead to lower conductivity at ambient conditions. These results suggest that both anincrease in decoupling and a reduction in T g might be required to develop solid polymer electrolytes withhigh ion conductivity at room temperature.

Authors:
 [1];  [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Pacific Lutheran Univ., Tacoma, WA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Tennessee, Knoxville, TN (United States)
  4. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, 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) (SC-22)
OSTI Identifier:
1435316
Alternate Identifier(s):
OSTI ID: 1396507
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Polymer
Additional Journal Information:
Journal Volume: 116; Journal Issue: C; Journal ID: ISSN 0032-3861
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Solid polymer electrolytes; Ionic conductivity; Decoupling of segmental dynamics

Citation Formats

Adams, Marisa, Richmond, Victoria, Smith, Douglas, Wang, Yangyang, Fan, Fei, Sokolov, Alexei P., and Waldow, Dean A. Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers. United States: N. p., 2017. Web. doi:10.1016/j.polymer.2017.03.054.
Adams, Marisa, Richmond, Victoria, Smith, Douglas, Wang, Yangyang, Fan, Fei, Sokolov, Alexei P., & Waldow, Dean A. Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers. United States. doi:10.1016/j.polymer.2017.03.054.
Adams, Marisa, Richmond, Victoria, Smith, Douglas, Wang, Yangyang, Fan, Fei, Sokolov, Alexei P., and Waldow, Dean A. Fri . "Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers". United States. doi:10.1016/j.polymer.2017.03.054. https://www.osti.gov/servlets/purl/1435316.
@article{osti_1435316,
title = {Decoupling of ion conductivity from segmental dynamics in oligomeric ethylene oxide functionalized oxanorbornene dicarboximide homopolymers},
author = {Adams, Marisa and Richmond, Victoria and Smith, Douglas and Wang, Yangyang and Fan, Fei and Sokolov, Alexei P. and Waldow, Dean A.},
abstractNote = {Here, in order to design more effective solid polymer electrolytes, it is important to decouple ion conductivityfrom polymer segmental motion. To that end, novel polymers based on oxanorbornene dicarboximidemonomers with varying lengths of oligomeric ethylene oxide side chains have been synthesized usingring opening metathesis polymerization. These unique polymers have a fairly rigid and bulky backboneand were used to investigate the decoupling of ion motion from polymer segmental dynamics. Ionconductivity was measured using broadband dielectric spectroscopy for varying levels of added lithiumsalt. The conductivity data demonstrate six to seven orders of separation in timescale of ion conductivityfrom polymer segmental motion for polymers with shorter ethylene oxide side chains. However,commensurate changes in the glass transition temperatures Tg reduce the effect of decoupling in ionconductivity and lead to lower conductivity at ambient conditions. These results suggest that both anincrease in decoupling and a reduction in Tg might be required to develop solid polymer electrolytes withhigh ion conductivity at room temperature.},
doi = {10.1016/j.polymer.2017.03.054},
journal = {Polymer},
number = C,
volume = 116,
place = {United States},
year = {Fri Mar 24 00:00:00 EDT 2017},
month = {Fri Mar 24 00:00:00 EDT 2017}
}

Journal Article:
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  • Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less
  • Conductivity in polymer electrolytes has been generally discussed with the assumption that the segmental motions control charge transport. However, much less attention has been paid to the mechanism of ion conductivity where the motions of ions are less dependent (decoupled) on segmental dynamics. We present that this phenomenon is observed in ionic materials as they approach their glass transition temperature and becomes essential for design and development of highly conducting solid polymer electrolytes. In this paper, we study the effect of chain rigidity on the decoupling of ion transport from segmental motion in three polymerized ionic liquids (polyILs) containing themore » same cation–anion pair but differing in flexibility of the polymer backbones and side groups. Analysis of dielectric and rheology data reveals that decoupling is strong in vinyl-based rigid polymers while almost negligible in novel siloxane-based flexible polyILs. To explain this behavior, we investigated ion and chain dynamics at ambient and elevated pressure. Our results suggest that decoupling has a direct relationship to the frustration in chain packing and free volume. Finally, these conclusions are also supported by coarse-grained molecular dynamics simulations.« less
  • We present detailed studies of the relationship between ionic conductivity and segmental relaxation in polymer electrolytes. The analysis shows that the ionic conductivity can be decoupled from segmental dynamics and the strength of the decoupling correlates with the fragility but not with the glass transition temperature. These results call for a revision of the current picture of ionic transport in polymer electrolytes. We relate the observed decoupling phenomenon to frustration in packing of rigid polymers, where the loose local structure is also responsible for the increase in their fragility.