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Title: Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt

Abstract

© 2019 American Chemical Society. We examine the phase behavior of a hybrid organic-inorganic diblock copolymer/salt mixtures. The experimental system comprises poly(ethylene oxide)-block-polyhedral oligomeric silsesquioxane (PEO-POSS) mixed with a lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) salt. Although the diblock copolymers without salt exhibit a classical order-to-disorder transition behavior with increasing temperature, the PEO-POSS/salt mixtures exhibit disorder-to-order transitions with increasing temperature. The analysis of a small-angle X-ray scattering data from the disordered state using Leibler's random phase approximation enables the determination of an effective Flory-Huggins interaction parameter, χeff , for the electrolytes. Unlike conventional systems, χeff increases with increasing temperature. A simple expression is proposed to describe the dependence of χeff on temperature and salt concentration. This enables the calculation of the segregation strength, χeffN, for both ordered and disordered electrolytes. The composition of the electrolytes is quantified by fEO/LiTFSI , the volume fraction of the salt-containing poly(ethylene oxide)-rich phase. The morphology of electrolytes is presented on a χ eff N versus fEO/LiTFSI phase diagram. Finally, over the values of fEO/LiTFSI studied (0.61-0.91), only two ordered phases were found: lamellae and co-existing lamellae/hexagonally packed cylinders.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [3]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [4]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Pohang Univ. of Science and Technology (POSTECH) (Korea)
  3. Univ. of California, Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1604684
Grant/Contract Number:  
AC02-05CH11231; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 9; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; salt; scattering; electrolytes; x-ray scattering; copolymers

Citation Formats

Sethi, Gurmukh K., Jung, Ha Young, Loo, Whitney S., Sawhney, Simar, Park, Moon Jeong, Balsara, Nitash P., and Villaluenga, Irune. Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt. United States: N. p., 2019. Web. doi:10.1021/acs.macromol.9b00042.
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Sethi, Gurmukh K., Jung, Ha Young, Loo, Whitney S., Sawhney, Simar, Park, Moon Jeong, Balsara, Nitash P., & Villaluenga, Irune. Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt. United States. https://doi.org/10.1021/acs.macromol.9b00042
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Sethi, Gurmukh K., Jung, Ha Young, Loo, Whitney S., Sawhney, Simar, Park, Moon Jeong, Balsara, Nitash P., and Villaluenga, Irune. Wed . "Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt". United States. https://doi.org/10.1021/acs.macromol.9b00042. https://www.osti.gov/servlets/purl/1604684.
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@article{osti_1604684,
title = {Structure and Thermodynamics of Hybrid Organic–Inorganic Diblock Copolymers with Salt},
author = {Sethi, Gurmukh K. and Jung, Ha Young and Loo, Whitney S. and Sawhney, Simar and Park, Moon Jeong and Balsara, Nitash P. and Villaluenga, Irune},
abstractNote = {© 2019 American Chemical Society. We examine the phase behavior of a hybrid organic-inorganic diblock copolymer/salt mixtures. The experimental system comprises poly(ethylene oxide)-block-polyhedral oligomeric silsesquioxane (PEO-POSS) mixed with a lithium bis(trifluoromethane sulfonyl) imide (LiTFSI) salt. Although the diblock copolymers without salt exhibit a classical order-to-disorder transition behavior with increasing temperature, the PEO-POSS/salt mixtures exhibit disorder-to-order transitions with increasing temperature. The analysis of a small-angle X-ray scattering data from the disordered state using Leibler's random phase approximation enables the determination of an effective Flory-Huggins interaction parameter, χeff , for the electrolytes. Unlike conventional systems, χeff increases with increasing temperature. A simple expression is proposed to describe the dependence of χeff on temperature and salt concentration. This enables the calculation of the segregation strength, χeffN, for both ordered and disordered electrolytes. The composition of the electrolytes is quantified by fEO/LiTFSI , the volume fraction of the salt-containing poly(ethylene oxide)-rich phase. The morphology of electrolytes is presented on a χ eff N versus fEO/LiTFSI phase diagram. Finally, over the values of fEO/LiTFSI studied (0.61-0.91), only two ordered phases were found: lamellae and co-existing lamellae/hexagonally packed cylinders.},
doi = {10.1021/acs.macromol.9b00042},
journal = {Macromolecules},
number = 9,
volume = 52,
place = {United States},
year = {Wed Apr 17 00:00:00 EDT 2019},
month = {Wed Apr 17 00:00:00 EDT 2019}
}
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https://doi.org/10.1021/acs.macromol.9b00042
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