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Investigating the Correlation of Segmental Dynamics, Free Volume Characteristics, and Ionic Conductivity in Poly(ethylene oxide)-Based Electrolyte: A Broadband Dielectric and Positron Annihilation Spectroscopy Study

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    Investigating the Correlation of Segmental Dynamics, Free Volume Characteristics, and Ionic Conductivity in Poly(ethylene oxide)-Based Electrolyte: A Broadband Dielectric and Positron Annihilation Spectroscopy Study
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    • P. Utpalla
      P. Utpalla
      Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai, India 400085
      Homi Bhabha National Institute, Anushaktinagar, Mumbai, India 400094
      More by P. Utpalla
    • S. K. Sharma
      S. K. Sharma
      Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai, India 400085
      Homi Bhabha National Institute, Anushaktinagar, Mumbai, India 400094
      More by S. K. Sharma
      Orcidhttp://orcid.org/0000-0002-9285-3793
    • K. Sudarshan
      K. Sudarshan
      Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai, India 400085
      Homi Bhabha National Institute, Anushaktinagar, Mumbai, India 400094
      More by K. Sudarshan
    • S. K. Deshpande
      S. K. Deshpande
      UGC-DAE Consortium for Scientific Research, Mumbai, India 400085
      More by S. K. Deshpande
    • M. Sahu
      M. Sahu
      Radioanalytical Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India 400085
      More by M. Sahu
    • P. K. Pujari*
      P. K. Pujari
      Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai, India 400085
      Homi Bhabha National Institute, Anushaktinagar, Mumbai, India 400094
      *E-mail: [email protected]
      More by P. K. Pujari
      Orcidhttp://orcid.org/0000-0003-1568-4065
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2020, 124, 8, 4489–4501
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    https://doi.org/10.1021/acs.jpcc.9b11722
    Published January 31, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Poly(ethylene oxide), PEO, based solid polymer electrolyte with different loadings of a lithium salt, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), has been investigated to study the role of PEO–Li cross-linking on segmental dynamics and free volume structure of PEO which consequently determine thermal, mechanical, and ion conduction properties of the electrolyte. In order to investigate the interrelation between segmental dynamics, free volume structure, and ion conduction mechanism, broadband dielectric spectroscopy and positron annihilation spectroscopy have been employed. The ion conduction process in the polymer electrolyte has been explained according to Almond–West formalism considering two different universalities dominating at different temperature or frequency regimes. Ionic conductivity was observed to increase in a nonlinear trend with salt loading, confirming the additional role of the ion diffusion process. The present study has shown that segmental dynamics and free volume structure of PEO-electrolyte which primarily govern the ion diffusion process are interrelated. These have been invoked to explain the observed variations in ionic conductivity, crystallinity, ductility, and thermal stability of PEO–LiTFSI electrolytes.

    Copyright © 2020 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.jpcc.9b11722.

    • XRD patterns, FTIR spectra, DSC thermograms, melting point determination from DSC, TGA, SEM images of selected samples, and BDS data at different loadings of LiTFSI (PDF)

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2020, 124, 8, 4489–4501
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.9b11722
    Published January 31, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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