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Title: Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering

Abstract

We have measured the effect of added salt on the chain dimensions of mixtures of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) in the melt state through small-angle neutron scattering (SANS) experiments. Scattering profiles from blends of hydrogenated and deuterated PEO mixed with LiTFSI were measured as a function of salt concentration. Scattering profiles from pure deuterated PEO/LiTFSI mixtures were used for background-subtraction purposes. The densities of PEO/LiTFSI mixtures of varying salt concentrations were measured to calculate partial molar monomer volumes of PEO and LiTFSI to account for nonideal mixing. Kratky plots of the scattering profiles were used to calculate the salt concentration dependence of statistical segment length. At low salt concentrations, segment length decreases with increasing salt concentration, before increasing with increasing salt concentration in the high salt concentration regime. The random phase approximation was used to predict theoretical scattering profiles from the calculated segment lengths and partial molar volumes; there is excellent agreement between the theoretical and measured scattering profiles at all salt concentrations. There appears to be a correlation between chain dimensions and coordination between lithium ions and EO monomers. Finally, the scattering profiles of the pure deuterated PEO/LiTFSI mixtures suggested the presence of ion clustersmore » of characteristic size of 0.6 nm at high salt concentrations.« less

Authors:
ORCiD logo [1];  [1];  [2];  [3]; ORCiD logo [2]
  1. Univ. of California, Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1604713
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; DMR-1508249; DGE-1106400
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 22; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Loo, Whitney S., Mongcopa, Katrina I., Gribble, Daniel A., Faraone, Antonio A., and Balsara, Nitash P.. Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.macromol.9b01509.
Loo, Whitney S., Mongcopa, Katrina I., Gribble, Daniel A., Faraone, Antonio A., & Balsara, Nitash P.. Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering. United States. https://doi.org/10.1021/acs.macromol.9b01509
Loo, Whitney S., Mongcopa, Katrina I., Gribble, Daniel A., Faraone, Antonio A., and Balsara, Nitash P.. Thu . "Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering". United States. https://doi.org/10.1021/acs.macromol.9b01509. https://www.osti.gov/servlets/purl/1604713.
@article{osti_1604713,
title = {Investigating the Effect of Added Salt on the Chain Dimensions of Poly(ethylene oxide) through Small-Angle Neutron Scattering},
author = {Loo, Whitney S. and Mongcopa, Katrina I. and Gribble, Daniel A. and Faraone, Antonio A. and Balsara, Nitash P.},
abstractNote = {We have measured the effect of added salt on the chain dimensions of mixtures of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) in the melt state through small-angle neutron scattering (SANS) experiments. Scattering profiles from blends of hydrogenated and deuterated PEO mixed with LiTFSI were measured as a function of salt concentration. Scattering profiles from pure deuterated PEO/LiTFSI mixtures were used for background-subtraction purposes. The densities of PEO/LiTFSI mixtures of varying salt concentrations were measured to calculate partial molar monomer volumes of PEO and LiTFSI to account for nonideal mixing. Kratky plots of the scattering profiles were used to calculate the salt concentration dependence of statistical segment length. At low salt concentrations, segment length decreases with increasing salt concentration, before increasing with increasing salt concentration in the high salt concentration regime. The random phase approximation was used to predict theoretical scattering profiles from the calculated segment lengths and partial molar volumes; there is excellent agreement between the theoretical and measured scattering profiles at all salt concentrations. There appears to be a correlation between chain dimensions and coordination between lithium ions and EO monomers. Finally, the scattering profiles of the pure deuterated PEO/LiTFSI mixtures suggested the presence of ion clusters of characteristic size of 0.6 nm at high salt concentrations.},
doi = {10.1021/acs.macromol.9b01509},
journal = {Macromolecules},
number = 22,
volume = 52,
place = {United States},
year = {2019},
month = {11}
}

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