Advertisement

Ionics

, Volume 24, Issue 5, pp 1415–1428 | Cite as

Dielectric relaxation in PEO-based polymer electrolytes

  • H. W. Kammer
Original Paper

Abstract

Dielectric properties of cross-linked poly(ethylene oxide) (PEO) with different mesh sizes, doped with lithium salt lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), have been studied in frequency region between 0.1 and 107 Hz and in broad temperature range. Results were compared with linear PEO of 1000 g/mol. Dielectric responses of the systems are dependent on frequency and thermally activated. Systems exhibit different responses in semi-crystalline and molten state. Increase of temperature promotes polarization; whereas, increase of frequency lessens it. In other words, polarization is thermally activated and local conductivity reduced. Generally, one observes enhanced dc conductivity in linear PEO as compared to cross-linked PEO at high temperature and the opposite at low temperature. Resonance responses are observed in low-molecular cross-linked PEO and in linear PEO at low temperature. These responses lead to splitting of polarization relaxation at frequencies beyond low-frequency range. Salt-comprising systems display only relaxation-type dielectric response. Imaginary parts of response spectra show distribution of relaxation times. It turns out that this distribution is independent of temperature in the low-frequency range, but depends on concentration of salt in the cross-linked polymer. In both systems, neat cross-linked and linear polymer of low-molecular mass, one observes coexistence of non-local and local motions of charged entities even at very low temperature.

Keywords

Linear and cross-linked PEO Polymer electrolyte with LiTFSI Impedance spectra 

Notes

Acknowledgements

The presentation, analysis, and discussion of impedance spectra are based on data provided by Professor J. Kressler and his students, Martin-Luther University Halle-Wittenberg, Germany. The author expresses his thanks for collecting and granting of the data.

References

  1. 1.
    Bruce PG, Vincent CA (1993) Polymer electrolytes. J Chem Soc Faraday Trans 89:3187–3191CrossRefGoogle Scholar
  2. 2.
    Shi J, Vincent CA (1993) Dc polarization of polymer electrolytes. Solid State Ionics 60:11–18CrossRefGoogle Scholar
  3. 3.
    Bernson A, Lindgren J, Huang W, Frech R (1995) Coordination and conformation in PEO, PEGM and PEG systems containing lithium or lanthanum triflate. Polymer 36:4471–4478CrossRefGoogle Scholar
  4. 4.
    Marzantowicz M, Dygas JR, Krok F, Florjanczyk Z, Zygadlo-Monikowska E (2006) Influence of crystallization on dielectric properties of PEO:LiTFSI polymer electrolyte. J Non-Cryst Solids 35:5216–5223CrossRefGoogle Scholar
  5. 5.
    Polu AR, Kumar R (2011) Impedance spectroscopy and FTIR studies of PEG-based polymer electrolyte. E-J Chem 8:347–353CrossRefGoogle Scholar
  6. 6.
    Sun J, Stone GM, Belsara NB, Zuckermann RN (2012) Structure-conductivity relationships for peptoid-based PEO-mimetic polymer electrolytes. Macromolecules 45:5151–5156CrossRefGoogle Scholar
  7. 7.
    Florjanczyk Z, Zygadlo-Monikowska E, Ostrowska J, Frydrych A (2014) Solid polymer electrolytes based on ethylene oxide polymers. Polimery 59:80–87CrossRefGoogle Scholar
  8. 8.
    Das S, Ghosh A (2015) Ionic conductivity and dielectric permittivity of PEO-LiClO4 solid polymer electrolytes plasticized with polypropylene carbonate. AIP Adv 5:027125CrossRefGoogle Scholar
  9. 9.
    Liu W, Liu N, Sun J, Hsu PC, Li Y, Lee HW, Cui Y (2015) Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers. Nano Lett 15:2740–2745CrossRefGoogle Scholar
  10. 10.
    Golodnitzky D, Strauss E, Peled E, Greenbaum S (2015) Review on order and disorder in polymer electrolytes. J Electrochem Soc 162:A2551–A2566CrossRefGoogle Scholar
  11. 11.
    Chan CH, Kammer HW (2017) Impedance spectra of polymer electrolytes. Ionics 23:2327–2337CrossRefGoogle Scholar
  12. 12.
    Shen M, Lin Y, Li M, Nan CW (2007) High dielectric performance of polymer composite films induced by a percolating inter-particle barrier. Adv Mater 19:1418–1422CrossRefGoogle Scholar
  13. 13.
    Smith RC, Liang C, Landry M, Nelson JK, Schadler LS (2008) The mechanism leading to useful electric properties of polymer dielectrics. IEEE Dielct El In 15:187–196CrossRefGoogle Scholar
  14. 14.
    Lin W, Song MS, Kong B, Cui Y (2017) Flexible and stretchable energy storage: advances and future perspectives. Adv Mater 29(1-34):1603436Google Scholar
  15. 15.
    Carvalho M, Guegan P, Cheradame H, Gomes AS (2000) Variation of the mesh size of PEO-based networks filled with TFSILi: from an Arrhenius to WLF type conductivity behavior. Eur Polym J 36:401–409CrossRefGoogle Scholar
  16. 16.
    Samiullah MH, Reichert D, Zinkevich T, Kressler J (2013) NMR characterization of PEG networks synthsized by CuAAC using reactive oligomers. Macromolecules 46:6922–6930CrossRefGoogle Scholar
  17. 17.
    Pulst M, Kressler J (2014) Characterization of linear and cross-linked poly(ethylene oxide), MSc Thesis M. Pulst, Martin-Luther University Halle-Wittenberg, Halle, GermanyGoogle Scholar
  18. 18.
    Fetters LF, Lohse DJ, Millner ST, Grasley WW (1999) Packing length in linear polymer melts on the entanglement. Macromolecules 32:6847–6851CrossRefGoogle Scholar
  19. 19.
    Nazmul H (2016) Master thesis, Martin-Luther-University, Halle/SaaleGoogle Scholar
  20. 20.
    Cheng S, Smith DM, Li CY (2015) Anisotropic ion transport in poly(ethylene oxide)/LiClO4 solid state electrolyte tempered by grapheme oxide. Macromolecules 48:4503–4510CrossRefGoogle Scholar
  21. 21.
    Cheng S, Smith DM, Pan QW, Wang SJ, Li CY (2015) Anisotropic ion transport in nano-structured solid polymer electrolytes. RSC Adv 5:48793–48810CrossRefGoogle Scholar
  22. 22.
    Debye P (1929) Polar Molecules. Chemical Catalog Company, New York reprinted by Dover Publishers New York, 1945Google Scholar
  23. 23.
    Liang YH, Wang CC, Chen CY (2008) Synthesis and characterization of a new network polymer electrolyte containing polyether in the main chains and side chains. Eur Polym J 44:2376–2384CrossRefGoogle Scholar
  24. 24.
    Brandrup J, Immergut EH, Eds (1989) Polymer handbook 3rd ed., PEO. Wiley Interscience, New York, p 545Google Scholar
  25. 25.
    Walter R, Selser JC, Smith M, Bogoslovov R, Piet G (2002) Network viscoelastic behavior in poly(ethylene oxide) melts: effects of temperature and dissolved LiClO4 on network structure and dynamic behavior. J Chem Phys 117:427–440CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.University Teknologi MARAShah AlamMalaysia

Personalised recommendations