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Influence of Miscibility on Poly(ethylene oxide) Crystallization from Disordered Melts of Block Copolymers with Lithium and Magnesium Counterions

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Department of Chemical and Biomolecular Engineering, University of California, Berkeley, Berkeley, California 94720, United States
‡ § ∥ Materials Sciences Division, §Joint Center for Energy Storage Research (JCESR), and Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
*E-mail: [email protected] (N.P.B.).
Cite this: Macromolecules 2017, 50, 12, 4827–4839
Publication Date (Web):June 15, 2017
https://doi.org/10.1021/acs.macromol.7b00735
Copyright © 2017 American Chemical Society

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    Abstract

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    Crystallization within block copolymers is a subject of considerable interest; however, little is understood about how the presence of an ion-containing block, such as poly[(styrene-4-sulfonyltrifluoromethylsulfonyl)imide (P[(STFSI)]), influences the crystallization behavior of single-ion conducting block copolymers derived from poly(ethylene oxide)-b-poly[(styrene-4-sulfonyltrifluoromethylsulfonyl)imide (PEO–P[(STFSI)]). In this study, we report on the crystallization behavior of PEO in a matched-set library of lithiated (PEO–P[(STFSI)Li]) and magnesiated (PEO–P[(STFSI)2Mg]) single-ion conducting block copolymers that are disordered in the melt. Structural and thermal analysis of semicrystalline samples prepared by quenching amorphous melts reveals that total PEO crystallinity is independent of cation identity. Furthermore, crystallization induces the formation of lamellar nanostructures regardless of the counterion present. However, the quality of the PEO crystallites and concomitant nanostructures appears to be strongly influenced by counterion identity; magnesiated samples demonstrate more disorder at both the crystalline and nanostructural level. By monitoring PEO crystallization with in situ small and wide-angle X-ray scattering, we show that PEO crystallizes from a homogeneous melt within PEO–P[(STFSI)Li] but is hindered by the presence of disordered concentration fluctuations within the magnesiated samples. Thus, counterion identity influences PEO crystallization by controlling the miscibility of the polymer blocks within the crystallizing melt.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.7b00735.

    • SI 1: differential scanning calorimetry (DSC) data and analysis from the single-ion conducting block copolymers and PEO(5); SI 2: details about the SAXS/WAXS setup and data reduction procedure; SI 3: a detailed derivation of the angle-dependent absorbance correction applied to the WAXS data, as well the procedure used to calibrate scattering intensities to absolute units; SI 4: details regarding the quantitative analysis of the SAXS/WAXS data, including a derivation of our recast Goppel approximation for determining absolute crystallinity from WAXS of block copolymers with one crystallizable block; SI 5: all of the scattering data collected in this study along with the results from the peak fitting described in SI 4 and the values extracted from the WAXS data that were used to calculate PEO crystallinity (PDF)

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