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Title: Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes

Abstract

Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.

Authors:
 [1];  [2];  [3];  [1];  [1];  [2];  [4];  [1];  [1]
+ Show Author Affiliations
  1. California Institute of Technology, Pasadena, CA (United States). Div. of Chemistry and Chemical Engineering.
  2. Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology.
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering.
  4. Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab., Berkeley, CA (United States). Materials Science Div. and Environmental Energy Technology Div.
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1214211
Grant/Contract Number:  
AC02-05CH11231; NSF-CHE-1335486
Resource Type:
Accepted Manuscript
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 1; Journal Issue: 4; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 25 ENERGY STORAGE

Citation Formats

Webb, Michael A., Jung, Yukyung, Pesko, Danielle M., Savoie, Brett M., Yamamoto, Umi, Coates, Geoffrey W., Balsara, Nitash P., Wang, Zhen -Gang, and Miller, III, Thomas F. Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes. United States: N. p., 2015. Web. doi:10.1021/acscentsci.5b00195.
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Webb, Michael A., Jung, Yukyung, Pesko, Danielle M., Savoie, Brett M., Yamamoto, Umi, Coates, Geoffrey W., Balsara, Nitash P., Wang, Zhen -Gang, & Miller, III, Thomas F. Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes. United States. https://doi.org/10.1021/acscentsci.5b00195
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Webb, Michael A., Jung, Yukyung, Pesko, Danielle M., Savoie, Brett M., Yamamoto, Umi, Coates, Geoffrey W., Balsara, Nitash P., Wang, Zhen -Gang, and Miller, III, Thomas F. Fri . "Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes". United States. https://doi.org/10.1021/acscentsci.5b00195. https://www.osti.gov/servlets/purl/1214211.
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@article{osti_1214211,
title = {Systematic computational and experimental investigation of lithium-ion transport mechanisms in polyester-based polymer electrolytes},
author = {Webb, Michael A. and Jung, Yukyung and Pesko, Danielle M. and Savoie, Brett M. and Yamamoto, Umi and Coates, Geoffrey W. and Balsara, Nitash P. and Wang, Zhen -Gang and Miller, III, Thomas F.},
abstractNote = {Understanding the mechanisms of lithium-ion transport in polymers is crucial for the design of polymer electrolytes. We combine modular synthesis, electrochemical characterization, and molecular simulation to investigate lithium-ion transport in a new family of polyester-based polymers and in poly(ethylene oxide) (PEO). Theoretical predictions of glass-transition temperatures and ionic conductivities in the polymers agree well with experimental measurements. Interestingly, both the experiments and simulations indicate that the ionic conductivity of PEO, relative to the polyesters, is far higher than would be expected from its relative glass-transition temperature. The simulations reveal that diffusion of the lithium cations in the polyesters proceeds via a different mechanism than in PEO, and analysis of the distribution of available cation solvation sites in the various polymers provides a novel and intuitive way to explain the experimentally observed ionic conductivities. This work provides a platform for the evaluation and prediction of ionic conductivities in polymer electrolyte materials.},
doi = {10.1021/acscentsci.5b00195},
journal = {ACS Central Science},
number = 4,
volume = 1,
place = {United States},
year = {Fri Jul 10 00:00:00 EDT 2015},
month = {Fri Jul 10 00:00:00 EDT 2015}
}
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https://doi.org/10.1021/acscentsci.5b00195
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