Chimney-Shaped Phase Diagram in a Polymer Blend Electrolyte

Neel J. Shah; Marwan Shalaby; Lilin He; Xin Wang; David Deslandes; Bruce A. Garetz; Nitash P. Balsara

doi:10.1021/acsmacrolett.3c00285

Chimney-Shaped Phase Diagram in a Polymer Blend Electrolyte

Neel J. Shah, Marwan Shalaby, Lilin He, Xin Wang, David Deslandes, Bruce A. Garetz, Nitash P. Balsara

SANS & Spin Echo

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

The phase behavior of polymer blend electrolytes comprising poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was determined using a combination of light and small angle neutron scattering (SANS) experiments. The results at a fixed temperature (110 °C) are presented on a PEO concentration versus salt (LiTFSI) concentration plot. The blends are miscible at all PEO concentrations in the absence of salt. With added salt, a region of immiscibility is obtained in PEO-lean polymer blend electrolytes; blends rich in PEO remain miscible at most salt concentrations. A narrow region of immiscibility juts into the miscible region, giving the phase diagram a chimney-like appearance. The data are qualitatively consistent with a simple extension of Flory-Huggins theory with a composition-dependent Flory-Huggins interaction parameter, χ, that was determined independently from SANS data from homogeneous blend electrolytes. Phase diagrams like the one we obtained were anticipated by self-consistent field theory calculations that account for correlations between ions. The relationship between these theories and measured χ remains to be established.

Original language	English
Pages (from-to)	874-879
Number of pages	6
Journal	ACS Macro Letters
Volume	12
Issue number	7
DOIs	https://doi.org/10.1021/acsmacrolett.3c00285
State	Published - Jul 18 2023

Funding

This work was supported by the National Science Foundation grant DMR 1904508 to the University of California, Berkeley, and grant DMR 1904537 to New York University. Any opinions, findings, and conclusions or recommendations expressed in this paper are those of the authors and do not necessarily reflect the views of the National Science Foundation. We thank Dr. David Halat for insightful discussions. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory.

Funders	Funder number
National Science Foundation	DMR 1904508
Office of Science
Oak Ridge National Laboratory
University of California Berkeley	DMR 1904537

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title = "Chimney-Shaped Phase Diagram in a Polymer Blend Electrolyte",

abstract = "The phase behavior of polymer blend electrolytes comprising poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was determined using a combination of light and small angle neutron scattering (SANS) experiments. The results at a fixed temperature (110 °C) are presented on a PEO concentration versus salt (LiTFSI) concentration plot. The blends are miscible at all PEO concentrations in the absence of salt. With added salt, a region of immiscibility is obtained in PEO-lean polymer blend electrolytes; blends rich in PEO remain miscible at most salt concentrations. A narrow region of immiscibility juts into the miscible region, giving the phase diagram a chimney-like appearance. The data are qualitatively consistent with a simple extension of Flory-Huggins theory with a composition-dependent Flory-Huggins interaction parameter, χ, that was determined independently from SANS data from homogeneous blend electrolytes. Phase diagrams like the one we obtained were anticipated by self-consistent field theory calculations that account for correlations between ions. The relationship between these theories and measured χ remains to be established.",

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AU - Deslandes, David

AU - Garetz, Bruce A.

AU - Balsara, Nitash P.

PY - 2023/7/18

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N2 - The phase behavior of polymer blend electrolytes comprising poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was determined using a combination of light and small angle neutron scattering (SANS) experiments. The results at a fixed temperature (110 °C) are presented on a PEO concentration versus salt (LiTFSI) concentration plot. The blends are miscible at all PEO concentrations in the absence of salt. With added salt, a region of immiscibility is obtained in PEO-lean polymer blend electrolytes; blends rich in PEO remain miscible at most salt concentrations. A narrow region of immiscibility juts into the miscible region, giving the phase diagram a chimney-like appearance. The data are qualitatively consistent with a simple extension of Flory-Huggins theory with a composition-dependent Flory-Huggins interaction parameter, χ, that was determined independently from SANS data from homogeneous blend electrolytes. Phase diagrams like the one we obtained were anticipated by self-consistent field theory calculations that account for correlations between ions. The relationship between these theories and measured χ remains to be established.

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Chimney-Shaped Phase Diagram in a Polymer Blend Electrolyte

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