Role of solvation site segmental dynamics on ion transport in ethylene-oxide based side-chain polymer electrolytes
Abstract
Ion conducting capability is often imparted to polymeric materials through short polyether side-chains, and yet the impact of this graft polymer architecture on ion solvation and conduction has not been fully explored. Here, we use a combination of impedance spectroscopy, vibrational spectroscopy, and atomistic molecular dynamics (MD) to compare the conductivity, ionic interactions, and polymer dynamics in a series of graft polyether electrolytes. We find that in poly[(oligo ethylene oxide)methyl ether methacrylate] (POEM), a widely used graft polymer electrolyte, the ionic conductivity drops more than an order of magnitude as the side-chain length is decreased from nine ethylene oxide (EO) units to three. This difference in conductivity is unexplained by differences in the calorimetric glass transition temperature (Tg), which varies only slightly with side-chain length. Furthermore, through vibrational spectroscopy and MD simulations we demonstrate that both linear and graft polyethers solvate Li⁺ ions effectively and dissociate them from large counterions, irrespective of side-chain length. Li⁺ ions do, however, show preferential solvation by EO units far from the methacrylate backbone. Similarly, EO units far from the backbone show enhanced segmental dynamics, while those near the immobile methacrylate group move substantially more slowly, as quantified by bond vector autocorrelation relaxation times. Thismore »
- Authors:
-
[1];
[1];
[2];
[3];
[4];
[1]
- Univ. of Chicago, IL (United States)
- Hebrew Univ. of Jerusalem (Israel). Inst. of Chemistry
- Princeton Univ., NJ (United States)
- Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1821196
- Alternate Identifier(s):
- OSTI ID: 1776386
- Grant/Contract Number:
- AC02-06CH11357; ECCS-1542205; DMR-1420709
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 15; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Bennington, Peter, Deng, Chuting, Sharon, Daniel, Webb, Michael A., de Pablo, Juan J., Nealey, Paul F., and Patel, Shrayesh N. Role of solvation site segmental dynamics on ion transport in ethylene-oxide based side-chain polymer electrolytes. United States: N. p., 2021.
Web. doi:10.1039/d1ta00899d.
Bennington, Peter, Deng, Chuting, Sharon, Daniel, Webb, Michael A., de Pablo, Juan J., Nealey, Paul F., & Patel, Shrayesh N. Role of solvation site segmental dynamics on ion transport in ethylene-oxide based side-chain polymer electrolytes. United States. https://doi.org/10.1039/d1ta00899d
Bennington, Peter, Deng, Chuting, Sharon, Daniel, Webb, Michael A., de Pablo, Juan J., Nealey, Paul F., and Patel, Shrayesh N. Mon .
"Role of solvation site segmental dynamics on ion transport in ethylene-oxide based side-chain polymer electrolytes". United States. https://doi.org/10.1039/d1ta00899d. https://www.osti.gov/servlets/purl/1821196.
@article{osti_1821196,
title = {Role of solvation site segmental dynamics on ion transport in ethylene-oxide based side-chain polymer electrolytes},
author = {Bennington, Peter and Deng, Chuting and Sharon, Daniel and Webb, Michael A. and de Pablo, Juan J. and Nealey, Paul F. and Patel, Shrayesh N.},
abstractNote = {Ion conducting capability is often imparted to polymeric materials through short polyether side-chains, and yet the impact of this graft polymer architecture on ion solvation and conduction has not been fully explored. Here, we use a combination of impedance spectroscopy, vibrational spectroscopy, and atomistic molecular dynamics (MD) to compare the conductivity, ionic interactions, and polymer dynamics in a series of graft polyether electrolytes. We find that in poly[(oligo ethylene oxide)methyl ether methacrylate] (POEM), a widely used graft polymer electrolyte, the ionic conductivity drops more than an order of magnitude as the side-chain length is decreased from nine ethylene oxide (EO) units to three. This difference in conductivity is unexplained by differences in the calorimetric glass transition temperature (Tg), which varies only slightly with side-chain length. Furthermore, through vibrational spectroscopy and MD simulations we demonstrate that both linear and graft polyethers solvate Li⁺ ions effectively and dissociate them from large counterions, irrespective of side-chain length. Li⁺ ions do, however, show preferential solvation by EO units far from the methacrylate backbone. Similarly, EO units far from the backbone show enhanced segmental dynamics, while those near the immobile methacrylate group move substantially more slowly, as quantified by bond vector autocorrelation relaxation times. This heterogeneity in both ion solvation and local segmental relaxation explains variation in ion conductivity where material-averaged properties such as Tg and number of free ions fail to do so. Importantly, the ionic conductivity is dictated primarily by the segmental mobility of the EO units which form effective solvation sites, rather than system-wide dynamics.},
doi = {10.1039/d1ta00899d},
journal = {Journal of Materials Chemistry. A},
number = 15,
volume = 9,
place = {United States},
year = {Mon Apr 12 00:00:00 EDT 2021},
month = {Mon Apr 12 00:00:00 EDT 2021}
}
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