Influence of Added Salt on Chain Conformations in Poly(ethylene oxide) Melts: SANS Analysis with Complications

Shuyi Xie, Bo Zhang, Yimin Mao, Lilin He, Kunlun Hong, Frank S. Bates, Timothy P. Lodge

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Abstract

Poly(ethylene oxide) (PEO)-based electrolytes have gained increasing attention in both the rechargeable battery industry and fundamental research, but any influence of the ions on the polymer conformation is not fully understood. Small-angle neutron scattering (SANS) is a powerful means to determine single-polymer chain conformations. We conducted SANS experiments on 50:50 blends of perdeuterated PEO (dPEO) and hydrogenous PEO (hPEO) of two different molecular weights (20 and 40 kDa) doped with two different salts (LiTFSI and LiClO4) at various concentrations. An additional measurement with LiI is also reported. The scattering profiles of salt-doped dPEO/hPEO blends were measured, and the incoherent scattering from dPEO and hPEO doped with salt was measured separately. A strong low q upturn was observed in some of the blends and in the pure dPEO homopolymers. The statistical segment lengths of PEO-salt mixtures were derived using a Kratky analysis. The segment length decreases modestly with increasing amounts of LiTFSI but apparently first increases then decreases with added LiClO4. At the highest salt concentration examined (r = [Li+]/[EO] = 0.125), a roughly 10% decrease in the statistical segment length was observed in both LiTFSI and LiClO4-doped PEOs, for both molecular weights. This work confirms that added salt causes a contraction of the PEO chain dimensions, but the effect appears slightly weaker than reported recently. Certain difficulties in data analysis are also discussed, including the unexplained low q scattering even in pure deuterated polymers, uncertainties in background subtraction, and inappropriate application of the Debye function.

Original languageEnglish (US)
Pages (from-to)7141-7149
Number of pages9
JournalMacromolecules
Volume53
Issue number16
DOIs
StatePublished - Aug 25 2020

Bibliographical note

Funding Information:
This work was supported by the Office of Basic Energy Sciences (BES) of the U.S. Department of Energy (DoE), under Contract No. DE-FOA-0001664. Protonated and deuterated PEO were synthesized at the CNMS, which is a DOE Office of Science User Facility. This research used resources at the High Flux Isotope Reactor, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. We acknowledge the support of the National Institute of Standards and Technology, U.S. Department of Commerce, in providing the neutron research facilities used in this work. Access to the USANS instrument was provided by the Center for High Resolution Neutron Scattering, a partnership between the National Institute of Standards and Technology and the National Science Foundation under Agreement No. DMR-1508249. S.X. thanks Aaron Lindsay for proposing this study and acknowledges partial funding from a Doctoral Dissertation Fellowship at the University of Minnesota.

Publisher Copyright:
© 2020 American Chemical Society.

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