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Ionic Conductivity of a Solid Polymer Electrolyte Confined in Nanopores
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    Ionic Conductivity of a Solid Polymer Electrolyte Confined in Nanopores
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    • Chien-Hua Tu
      Chien-Hua Tu
      Max Planck Institute for Polymer Research, 55128 Mainz, Germany
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    • Lothar Veith
      Lothar Veith
      Max Planck Institute for Polymer Research, 55128 Mainz, Germany
      More by Lothar Veith
    • Hans-Jürgen Butt
      Hans-Jürgen Butt
      Max Planck Institute for Polymer Research, 55128 Mainz, Germany
    • George Floudas*
      George Floudas
      Max Planck Institute for Polymer Research, 55128 Mainz, Germany
      Department of Physics, University of Ioannina, 45110 Ioannina, Greece
      University Research Center of Ioannina (URCI)─Institute of Materials Science and Computing, 45110 Ioannina, Greece
      *Email: [email protected]
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    Macromolecules

    Cite this: Macromolecules 2022, 55, 4, 1332–1341
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    https://doi.org/10.1021/acs.macromol.1c02490
    Published February 7, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Using in situ nanodielectric spectroscopy, we investigate if and how the ionic conductivity of the archetypal polymer electrolyte poly(ethylene oxide)/lithium bis(trifluoromethane sulfone)imide (PEO/LiTFSI) is affected during and after imbibition in nanopores. We identify two distinct stages of imbibition. In the first stage, up to the complete pore filling, ion conductivity increased above the bulk value. In the second stage, after imbibition, ion conductivity decreased following a stretched exponential dependence. Time-of-flight secondary ion mass spectroscopy revealed a uniform distribution of Li+ and TFSI ions in the templates. The timescale of conductivity reduction was very long. For a given molar mass, the characteristic times strongly depend on the ratio 2Rg/D where Rg is the radius of gyration and D is the pore diameter. For a given pore diameter, the characteristic times were some 9 orders of magnitude slower than the PEO terminal relaxation and more than 11 orders of magnitude slower than the segmental relaxation. The reduced ionic conductivity is explained by the adsorption of polymer segments on the pore walls. Polymer adsorption inevitably affects ion dynamics by (i) increasing the glass temperature and (ii) reducing the number of mobile ions. The molar mass dependence of the characteristic adsorption times (τadsN2) was in agreement with a scaling theory proposed by de Gennes. Possible consequences of the current study to energy conversion are discussed.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.1c02490.

    • Dc-conductivity data for the bulk and confined PEO/LiTFSI, rheology data for the bulk polymer electrolytes, and ToF-SIMS analysis (PDF)

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    Cited By

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    This article is cited by 9 publications.

    1. Shreyas Pathreeker, Hyeongjun Koh, Weiwei Kong, Richard Robinson, Gillian Weissman, Eric A. Stach, Eric Detsi, Russell J. Composto. Effect of Confinement on the Structure–Conductivity Relationship in PEO/LiTFSI Electrolytes in 3D Microporous Scaffolds. ACS Macro Letters 2024, Article ASAP.
    2. Yun Dong, Martin Steinhart, Hans-Jürgen Butt, George Floudas. Demixing of Polymerized Ionic Liquid/Ionic Liquid Mixtures by Infiltration in Nanopores. Macromolecules 2024, 57 (11) , 5409-5420. https://doi.org/10.1021/acs.macromol.4c00391
    3. Tiago S. Domingues, Ronald Coifman, Amir Haji-Akbari. Estimating Position-Dependent and Anisotropic Diffusivity Tensors from Molecular Dynamics Trajectories: Existing Methods and Future Outlook. Journal of Chemical Theory and Computation 2024, 20 (11) , 4427-4455. https://doi.org/10.1021/acs.jctc.4c00148
    4. Panagiotis Kardasis, Georgios Sakellariou, George Floudas. Ultraslow Adsorption of Star cis-1,4-Polyisoprenes by In Situ Imbibition in Nanopores. Macromolecules 2024, 57 (2) , 481-489. https://doi.org/10.1021/acs.macromol.3c01760
    5. S. S. Sørensen, M. M. Smedskjaer, M. Micoulaut. Evidence for Complex Dynamics in Glassy Fast Ion Conductors: The Case of Sodium Thiosilicates. The Journal of Physical Chemistry B 2023, 127 (47) , 10179-10188. https://doi.org/10.1021/acs.jpcb.3c02909
    6. Mingwang Pan, Shaofeng Song, Xiaomeng Guo, Jinfeng Yuan, Zhicheng Pan. Surface Nucleation-Induced Raspberry-like PVDF@P(St-co-MPS-co-AA) Core–Shell Latex Particles via Seeded Emulsion Polymerization and Their High Efficiency for Confined Crystallization of PVDF in Nanospheres. Industrial & Engineering Chemistry Research 2023, 62 (43) , 17731-17742. https://doi.org/10.1021/acs.iecr.3c02493
    7. Jiyoung Lee, Seonho Kim, Hyeoksu Kwon, Seungyun Jo, Du Yeol Ryu, U Hyeok Choi, Byeong-Su Kim. Single-Ion-Conducting Polyether Electrolytes via Orthogonal Postpolymerization Modification. Macromolecules 2023, 56 (18) , 7520-7531. https://doi.org/10.1021/acs.macromol.3c00985
    8. Yun Dong, Martin Steinhart, Hans-Jürgen Butt, George Floudas. Conductivity of Ionic Liquids In the Bulk and during Infiltration in Nanopores. The Journal of Physical Chemistry B 2023, 127 (31) , 6958-6968. https://doi.org/10.1021/acs.jpcb.3c01216
    9. Achilleas Pipertzis, Martha Kafetzi, Despoina Giaouzi, Stergios Pispas, George A. Floudas. Grafted Copolymer Electrolytes Based on the Poly(acrylic acid-co-oligo ethylene glycol acrylate) (P(AA-co-OEGA)) Ion-Conducting and Mechanically Robust Block. ACS Applied Polymer Materials 2022, 4 (10) , 7070-7080. https://doi.org/10.1021/acsapm.2c00987

    Macromolecules

    Cite this: Macromolecules 2022, 55, 4, 1332–1341
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.1c02490
    Published February 7, 2022
    Copyright © 2022 American Chemical Society

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