Electrotransport properties and relaxation processes in the CdF2-PbF2 system
https://doi.org/10.18384/2949-5067-2026-1-78-91
Abstract
Aim. To conduct a comprehensive study of the electrotransport properties and relaxation processes in CdF2-PbF2 solid solution crystals, and to establish the relationship between their structure, thermodynamic behavior, and ion transport mechanisms.
Methodology. X-ray phase analysis, differential scanning calorimetry, and dielectric spectroscopy in a broad frequency-temperature range (20 Hz – 10 MHz, -60…+100°C) were used. The composition was determined using Vegard's law; relaxation processes were analyzed using the Havriliak-Negami model.
Results. The synthesized crystals were found to have the composition Cd0.326Pb0.674F2 and a fluorite-type structure. A diffuse superionic transition at ~320°C with pronounced hysteresis was detected by thermal analysis. Dielectric spectroscopy revealed a bulk relaxation process associated with F– ion hopping. The activation energies for relaxation time and conductivity were ~0.20 eV and ~0.26 eV, respectively, indicating a significant contribution of correlated ion motion.
Research implications. The relationship between structural parameters, the thermodynamics of the phase transition, and the kinetics of ion transport in the CdF2–PbF2 system has been established. The results are important for understanding the nature of superionic conductivity in fluoride systems and can be used in the development of new solid-state electrolytes.
Keywords
fluorides,
solid solution,
superionic transition,
dielectric spectroscopy,
ionic conductivity,
relaxation processes
Supporting agencies: This work was supported by the grant from the Federal State University of Education in 2025, awarded to the winning research project in the competitive grant program. We also extend our gratitude to the Pedagogical Technopark “Kvantorium” named after I. V. Kurchatov at the Federal State University of Education for providing access to their equipment, which was instrumental in conducting this study.
About the Authors
V. A. Yusim
Federal State University of Education; National Research Centre “Kurchatov Institute”; Prokhorov General Physics Institute of the Russian Academy of Sciences
Russian Federation
Russian Federation
Valentin A. Yusim – Senior Researcher; Leading Researcher; Leading Researcher
Moscow
A. D. Kurilov
Federal State University of Education
Russian Federation
Russian Federation
Alexandr D. Kurilov – Cand. Sci. (Phys.-Math.), Laboratory Head, Laboratory of Theoretical and Applied Nanotechnology
Moscow
S. E. Sarkisov
National Research Centre “Kurchatov Institute”
Russian Federation
Russian Federation
Stepan E. Sarkisov – Cand. Sci. (Phys.-Math.), Deputy Head, Department of the Office for Nonproliferation and Physical Protection of the Kurchatov Complex of Advanced Nuclear Energy (KKPAE)
Moscow
D. S. Kravtsov
Federal State University of Education
Russian Federation
Russian Federation
Daniil S. Kravtsov – Student
Moscow
Yu. D. Kuleshova
Federal State University of Education
Russian Federation
Russian Federation
Yulia D. Kuleshova – Cand. Sci. (Phys.-Math.), Assoc. Prof., Dean, Faculty of Physics and Mathematics
Moscow
References
1. Tarascon J.-M., Armand M. Issues and challenges facing rechargeable lithium batteries // Nature. 2001. Vol. 414. P. 359–367. DOI: 10.1038/35104644.
2. A lithium superionic conductor / N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, T. Kamiyama, Y. Kato, S. Hama, K. Kawamoto, A. Mitsui // Nature Materials. 2011. Vol. 10. No. 9 P. 682–686. DOI: 10.1038/nmat3066.
3. Physics of superionic conductors / ed. M. B. Salamon. Berlin, New York: Springer Science & Business Media, 2013. 255 p. (Series: Topics in Current Physics. Vol. 15).
4. Hull S., Keen D. A. Effect of hydrostatic pressure on the crystal structure and superionic behavior of lead (II) fluoride // Physical Review B. 1998. Vol. 58. No. 22. P. 14837–14844. DOI: 10.1103/PhysRevB.58.14837.
5. Fundamental questions relating to ion conduction in disordered solids / J. C. Dyre, P. Maass, B. Roling, D. L. Sidebottom // Reports on Progress in Physics. 2009. Vol. 72. No. 4. P. 046501. DOI: 10.1088/0034-4885/72/4/046501.
6. Superionic Solids and Solid Electrolytes: Recent Trends / ed. A. L. Laskar, S. Chandra. New York: Elsevier, 1989. 711 p.
7. Applications of Impedance Spectroscopy / J. R. Macdonald, W. B. Johnson, I. D. Raistrick, D. R. Franceschetti, N. Wagner, M. C. H. McKubre, D. D. Macdonald, B. Sayers, N. Bonanos, B. C. H. Steele, E. P. Butler // Impedance Spectroscopy: Theory, Experiment, and Applications. New Jersey: John Wiley & Sons, 2018. P. 205–263.
8. Perkowski P. Dielectric spectroscopy of liquid crystals. Electrodes resistivity and connecting wires inductance influence on dielectric measurements // Opto-Electronics Review. 2012. Vol. 20. No. 1. P. 79–86. DOI: 10.2478/s11772-012-0004-3.
9. Perkowski P. The parasitic effects in high-frequency dielectric spectroscopy of liquid crystals – the review // Liquid Crystals. 2021. Vol. 48. Iss. 6. P. 767–793. DOI: 10.1080/02678292.2020.1852619.
10. The Havriliak-Negami relaxation and its relatives: the response, relaxation and probability density functions / K. Górska, A. Horzela, Ł. Bratek, K. A. Penson // Journal of Physics A: Mathematical and Theoretical. 2018. Vol. 51. Iss. 13. Article no. 135202. DOI: 10.1088/1751-8121/aaafc0.
11. Achary S. N., Tyagi A. K. Synthesis and characterization of mixed fluorides with PbF2 and ScF3 // Powder diffraction. 2005. Vol. 20. Iss. 3. P. 254–258. DOI: 10.1154/1.1948391.
12. Structural studies on lead–cadmium fluoride solid solutions / M. A. P. Silva, Y. Messaddeq, V. Briois, M. Poulain, F. Villain, S. J. L. Ribeiro // Solid State Ionics. 2002. Vol. 147. Iss. 1-2. P. 135–139. DOI: 10.1016/S0167-2738(02)00042-5.
13. Shannon R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides // Foundations of Crystallography. 1976. Vol. 32. Iss. 5. P. 751–767. DOI: 10.1107/S0567739476001551.
14. Boyce J. B., Huberman B. A. Superionic conductors: Transitions, structures, dynamics // Physics Reports. 1979. Vol. 51. Iss. 4. P. 189–265. DOI: 10.1016/0370-1573(79)90067-X.
15. Sorokin N. I., Sobolev B. P., Breiter M. W. Specific features of anion transfer in superionic conductors based on MF2 (M= Pb and Cd) // Physics of the Solid State. 2002. Vol. 44. Iss. 8. P. 1579–1586. DOI: 10.1134/1.1501363.
16. Funke K. Jump relaxation in solid electrolytes // Progress in Solid State Chemistry. 1993. Vol. 22. Iss. 2. P. 111–195. DOI: 10.1016/0079-6786(93)90002-9.
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