Skip to main content
SpringerLink
Log in

Synthesis, Ion Mobility, and Superionic Conductivity of (1 − x)PbF2 ⋅ xMF n (M = Li, Na, K, Rb, Cs, Zr) Solid Solutions

  • Published:
Inorganic Materials Aims and scope

Abstract

Ionic motion and conduction in (1 − x)PbF2 ⋅ xZrF4 and (1 − x)PbF2 ⋅ xMF (M = alkali-metal cation) solid solutions are studied by 19F and 207Pb NMR and impedance spectroscopy. The factors determining ionic motion in the solid solutions and their structure and energetics in the range 170–550 K are analyzed. The ionic conductivity of (1 − x)PbF2 ⋅ xZrF4 with x ≤ 0.4 and 0.93PbF2 ⋅ 0.07MF is shown to be 10−4 to 10−2 S/cm at temperatures above 425 K, which places these materials among superionics.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

REFERENCES

  1. Gurevich, Yu.Ya., Tverdye elektrolity (Solid Electrolytes), Moscow: Nauka, 1986.

    Google Scholar 

  2. Gurevich, Yu.Ya. and Kharkats, Yu.I., Superionnye provodniki (Superionic Conductors), Moscow: Nauka, 1992.

    Google Scholar 

  3. Ivanov-Shits, A.K. and Murin, I.V., Ionika tverdogo tela (Solid-State Ionics), St. Petersburg: S.-Peterburgskii Univ., 2000, vol. 1.

    Google Scholar 

  4. Reau, J.M., Portier, J., Levasseur, A., et al., Characteristic Properties of New Solid Electrolytes, Mater. Res. Bull., 1978, vol. 13, no.12, pp. 1415–1423.

    Article  CAS  Google Scholar 

  5. Sorokin, N.I., Fedorov, P.P., and Sobolev, B.P., Superionic Materials Based on Lead Fluoride, Neorg. Mater., 1997, vol. 33, no.1, pp. 5–16 [Inorg. Mater. (Engl. Transl.), vol. 33, no. 1, pp. 1–11].

    Google Scholar 

  6. Sorokin, N.I., Anion-Conducting Fluoride and Oxyfluoride Glasses, Usp. Khim., 2001, vol. 70, no.9, pp. 901–908.

    Google Scholar 

  7. Agrawal, R.C. and Gurta, R.K., Superionic Solids: Composite Electrolyte Phase—An Overview, J. Mater. Sci., 1999, vol. 34, pp. 1131–1162.

    Article  CAS  Google Scholar 

  8. Hull, S. and Berastegui, P., Superionic Phases in the (PbF2)1 − x -(MF) x , M = K, Rb, and Cs, Systems, J. Phys.: Condens. Matter, 1999, vol. 11, no.11, pp. 5257–5272.

    CAS  Google Scholar 

  9. Aniya, M., Average Electronegativity, Medium-Range-Order, and Ionic Conductivity in Superionic Glasses, Solid State Ionics, 2000, vol. 136/137, pp. 1085–1089.

    Article  Google Scholar 

  10. Kavun, V.Ya., Uvarov, N.F., Slobodyuk, A.B., et al., Ionic Mobility, Phase Transitions, and Superionic Conductivity in (1 − x)PbF2-xZrF4 Solid Solutions and (NH4)2ZrF6, KSnZrF7, and M(NH4)6Zr4F23 (M = Li, Na) Crystals, Doklady 7-ogo mezhdunarodnogo soveshchaniya po fundamental'nym problemam ioniki tverdogo tela (Proc. 7th Int. Conf. on Fundamental Issues in Solid-State Ionics), Chernogolovka, 2004, p. 38.

  11. Murin, I.V., Superionic Conductors: Anomalously High Ionic Conductivity in Inorganic Fluorides, Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk, 1984, no. 1, pp. 53–61.

  12. Gabuda, S.P. and Pletnev, R.N., Primenenie YaMR v khimii tverdogo tela (NMR Applications in Solid-State Chemistry), Yekaterinburg: Ekaterinburg, 1996.

    Google Scholar 

  13. Kavun, V.Ya. and Sergienko, V.I., Diffuzionnaya podvizhnost' i ionnyi transport v kristallicheskikh i amorfnykh ftoridakh elementov IV gruppy i sur'my(III) (Diffusional Mobility and Ionic Transport in Crystalline and Amorphous Group IV and Antimony(III) Fluorides), Vladivostok: Dal'nauka, 2004.

    Google Scholar 

  14. Lundin, A.G. and Fedin, E.I., YaMR-Spektroskopiya (NMR Spectroscopy), Moscow: Nauka, 1986.

    Google Scholar 

  15. Buznik, V.M., Yadernaya spektroskopiya neorganicheskikh ftoridov (Nuclear Spectroscopy of Inorganic Fluorides), Vladivostok: Dal'nauka, 1997.

    Google Scholar 

  16. Schoonman, J., Ebert, L.B., Hsieh, C.H., and Huggins, R.A., Ionic Motion in β-PbF2, J. Appl. Phys., 1975, vol. 46, no.7, pp. 2873–2876.

    Article  CAS  Google Scholar 

  17. Mahajan, M. and Nageswara Rao, B.D., Motional Narrowing of 19F Nuclear Magnetic Resonance in Lead Fluoride, Chem. Phys. Lett., 1971, vol. 10, no.1, pp. 29–30.

    Article  CAS  Google Scholar 

  18. Hogg, R.D., Vernon, S.P., and Jaccarino, V., Magnetic “Tagging” of Superionic Conductors, Phys. Rev. Lett., 1977, vol. 39, no.8, pp. 481–484.

    Article  CAS  Google Scholar 

  19. Hwang, T.Y., Engelsberg, M., and Lowe, I.J., Nuclear Magnetic Resonance Study of 19F Diffusion in Lead Difluoride, Chem. Phys. Lett., 1975, vol. 30, no.2, pp. 303–305.

    Article  CAS  Google Scholar 

  20. Gordon, R.E. and Strange, J.H., NMR Relaxation and Self-diffusion in PbF2, J. Phys. C: Solid State Phys., 1978, vol. 11, no.15, pp. 3213–3223.

    Article  CAS  Google Scholar 

  21. Wang, F. and Grey, C.P., High-Resolution Solid State 19F MAS NMR Study of Ionic Motion in α-PbF2, J. Am. Chem. Soc., 1995, vol. 117, no.24, pp. 6637–6638.

    Article  CAS  Google Scholar 

  22. Wang, F. and Grey, C.P., A 1-and 2-D 19F MAS NMR Study of Fluoride-Ion Mobility in α-PbF2, J. Am. Chem. Soc., 1998, vol. 120, no.5, pp. 970–980.

    CAS  Google Scholar 

  23. Chebotin, V.N. and Perfil'ev, M.V., Elektrokhimiya tverdykh elektrolitov (Electrochemistry of Solid Electrolytes), Moscow: Khimiya, 1976.

    Google Scholar 

  24. Boldrini, H. and Loopstra, B.O., Neutron Diffraction Investigation of Orthorhombic Lead(II) Fluoride, Acta Crystallogr., 1967, vol. 22, no.5, pp. 744–745.

    Article  CAS  Google Scholar 

  25. Bouznik, V.M., Moskvich, Yu.N., and Voronov, V.N., Nuclear Magnetic Resonance Study of 19F Motion in CsPbF3, Chem. Phys. Lett., 1976, vol. 37, no.3, pp. 464–466.

    Article  CAS  Google Scholar 

  26. Kennedy, J.H. and Miles, R.C., Ionic Conductivity of Doped Beta-Lead-Fluoride, J. Electrochem. Soc., 1976, vol. 123, no.1, pp. 47–51.

    CAS  Google Scholar 

  27. Murin, I.V., Glumov, A.V., and Glumov, O.V., Mechanisms of Ionic Transport in PbF2-based Solid Electrolytes, Elektrokhimiya, 1979, vol. 15, no.8, pp. 1119–1123.

    CAS  Google Scholar 

  28. Bonne, R.W. and Schoonman, J., The Ionic Conductivity of Beta Lead Fluoride, J. Electrochem. Soc., 1977, vol. 124, no.1, pp. 28–35.

    CAS  Google Scholar 

  29. Chadwick, A.V., High-Temperature Transport in Fluorites, Solid State Ionics, 1983, vol. 8, pp. 209–220.

    Article  CAS  Google Scholar 

  30. Reau, J.M. and Hagenmuller, P., Correlations between Clusterization and Electrical Properties within Fluorite-Type Anions Excess Solutions: Setting a Model, Appl. Phys. A, 1989, vol. 49, pp. 3–12.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Chemistry, Far East Division, Russian Academy of Sciences, pr. Stoletiya Vladivostoka 159, Vladivostok, 690022, Russia

    V. Ya. Kavun, A. B. Slobodyuk, E. A. Tararako, E. Yu. Mikhteeva, V. K. Goncharuk & V. I. Sergienko

  2. Institute of Solid-State Chemistry and Mechanochemistry, Siberian Division, Russian Academy of Sciences, ul. Kutateladze 18, Novosibirsk, 630128, Russia

    N. F. Uvarov

Authors
  1. V. Ya. Kavun
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. B. Slobodyuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. E. A. Tararako
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. E. Yu. Mikhteeva
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. V. K. Goncharuk
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. N. F. Uvarov
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. V. I. Sergienko
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

__________

Translated from Neorganicheskie Materialy, Vol. 41, No. 11, 2005, pp. 1388–1396.

Original Russian Text Copyright © 2005 by Kavun, Slobodyuk, Tararako, Mikhteeva, Goncharuk, Uvarov, Sergienko.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Kavun, V.Y., Slobodyuk, A.B., Tararako, E.A. et al. Synthesis, Ion Mobility, and Superionic Conductivity of (1 − x)PbF2 ⋅ xMF n (M = Li, Na, K, Rb, Cs, Zr) Solid Solutions. Inorg Mater 41, 1228–1235 (2005). https://doi.org/10.1007/s10789-005-0292-9

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10789-005-0292-9

Keywords

Search

Navigation