ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

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

View Author Information
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
Copyright © 2017 American Chemical Society

    Article Views





    Other access options
    Supporting Info (1)»


    Abstract Image

    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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    Jump To

    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)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 11 publications.

    1. Anuradha, Anupam Das, Sandip Pal, Suresh K. Jewrajka. Physical, Electrochemical, and Solvent Permeation Properties of Amphiphilic Conetwork Membranes Formed through Interlinking of Poly(vinylidene fluoride)-Graft-Poly[(2-dimethylamino)ethyl Methacrylate] with Telechelic Poly(ethylene glycol) and Small Molecular Weight Cross-Linkers. Langmuir 2022, 38 (49) , 15340-15352.
    2. Georgia Nikolakakou, Christos Pantazidis, Georgios Sakellariou, Emmanouil Glynos. Ion Conductivity–Shear Modulus Relationship of Single-Ion Solid Polymer Electrolytes Composed of Polyanionic Miktoarm Star Copolymers. Macromolecules 2022, 55 (14) , 6131-6139.
    3. Mahati Chintapalli, Ksenia Timachova, Kevin R. Olson, Sue J. Mecham, Joseph M. DeSimone, Nitash P. Balsara. Lithium Salt Distribution and Thermodynamics in Electrolytes Based on Short Perfluoropolyether-block-Poly(ethylene oxide) Copolymers. Macromolecules 2020, 53 (4) , 1142-1153.
    4. Chenxi Zhai, Huanhuan Zhou, Teng Gao, Lingling Zhao, Shangchao Lin. Electrostatically Tuned Microdomain Morphology and Phase-Dependent Ion Transport Anisotropy in Single-Ion Conducting Block Copolyelectrolytes. Macromolecules 2018, 51 (12) , 4471-4483.
    5. Jacob L. Thelen, Andrew A. Wang, X. Chelsea Chen, Xi Jiang, Eric Schaible, Nitash P. Balsara. Correlations between Salt-Induced Crystallization, Morphology, Segmental Dynamics, and Conductivity in Amorphous Block Copolymer Electrolytes. Macromolecules 2018, 51 (5) , 1733-1740.
    6. Evgeniia A. Nikitina, Erfan Dashtimoghadam, Sergei S. Sheiko, Dimitri A. Ivanov. Bottlebrush Elastomers with Crystallizable Side Chains: Monolayer-like Structure of Backbones Segregated in Intercrystalline Regions. Polymers 2024, 16 (2) , 296.
    7. Bradley J. Grim, Matthew D. Green. Thermodynamics and Structure–Property Relationships of Charged Block Polymers. Macromolecular Chemistry and Physics 2022, 223 (14)
    8. Kyoungmin Kim, Nam Nguyen, Stephanie F. Marxsen, Sage Smith, Rufina G. Alamo, Justin G. Kennemur, Daniel T. Hallinan. Ionic Transport and Thermodynamic Interaction in Precision Polymer Blend Electrolytes for Lithium Batteries. Macromolecular Chemistry and Physics 2021, 222 (22)
    9. Miso Kang, Hyo Jun Min, Na Un Kim, Jong Hak Kim. Amphiphilic micelle-forming PDMS-PEGBEM comb copolymer self-assembly to tailor the interlamellar nanospaces of defective poly(ethylene oxide) membranes. Separation and Purification Technology 2021, 257 , 117892.
    10. Clémence Nicolas, Wenhao Zhang, Émilie Choppé, Laurent Fontaine, Véronique Montembault. Polynorbornene‐ g ‐poly(ethylene oxide) Through the Combination of ROMP and Nitroxide Radical Coupling Reactions. Journal of Polymer Science 2020, 58 (5) , 645-653.
    11. Ryan M. Van Horn, Maxwell R. Steffen, Dana O'Connor. Recent progress in block copolymer crystallization. POLYMER CRYSTALLIZATION 2018, 1 (4)

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect