Electrochemical properties of superionic conductors CsAg4Br3-хI2+х

Cover Page

Cite item

Full Text

Open Access Open Access
Restricted Access Access granted
Restricted Access Subscription Access

Abstract

CsAg4Br3–хI2+х solid solutions with x=0.38; 0.50; 0.63 were prepared by solid-phase synthesis; the single-phase of the products was confirmed by X-ray diffraction and differential scanning calorimetry. Studies of the electrical transport characteristics of CsAg4Br3–хI2+х included measurements of the ionic conductivity by the four-probe method in the range of –50…+120°C and an evaluation of the electronic component of the conductivity by the Hebb-Wagner method. It was shown that the ionic conductivity of CsAg4Br3–хI2+х solid solutions in the studied range of compositions is practically independent of x and is very close to that of the well-known superionic conductor RbAg4I5. The activation energy of conduction for all studied compounds is about 10 kJ mol–1. The oxidation potential determined by the stepwise polarization technique for CsAg4Br3–хI2+х solid solutions is noticeably higher than that of RbAg4I5, and is in the range of 0.75–0.78 V (vs. Ag0/Ag+). The high electrochemical characteristics of CsAg4Br3–хI2+х (0.38≤x≤0.63) and the absence of polymorphic transitions in the studied range from –160°C to the melting point (175 – 178°С) make these materials promising for use in electrochemical devices based on solid electrolytes, especially for low temperature applications.

Full Text

Restricted Access

About the authors

A. A. Glukhov

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Author for correspondence.
Email: 0511alex@mail.ru
Russian Federation, Chernogolovka

O. G. Reznitskikh

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: 0511alex@mail.ru
Russian Federation, Yekaterinburg

T. V. Yaroslavtseva

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: tanya_yaroslavtseva@mail.ru
Russian Federation, Yekaterinburg

N. V. Urusova

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: 0511alex@mail.ru
Russian Federation, Yekaterinburg

A. E. Ukshe

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Email: 0511alex@mail.ru
Russian Federation, Chernogolovka

Yu. A. Dobrovolsky

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Email: 0511alex@mail.ru
Russian Federation, Chernogolovka

O. V. Bushkova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Email: 0511alex@mail.ru
Russian Federation, Chernogolovka

References

  1. Geller, S., Crystal structure of the solid electrolyte, RbAg 4 I 5 , Science, 1967, vol. 157, no. 3786, p. 310. doi: 10.1126/science.157.3786.310
  2. Topol, L.E. and Owens, B.B., Thermodynamic studies in the high-conducting solid systems rubidium iodide-silver iodide, potassium iodide-silver iodide, and ammonium iodide-silver iodide, J. Phys. Chem., 1968, vol. 72, no. 6, p. 2106. https://doi.org/10.1021/j100852a038
  3. Bradley, J.N. and Greene, P.D., Solids with high ionic conductivity in Group 1 halide systems, Trans. Faraday Soc., 1967, vol. 63, p. 424. https://doi.org/10.1039/TF9676300424
  4. Owens, B.B. and Argue, G.R., High-conductivity solid electrolytes: MAg 4 I 5 , Science, 1967, vol. 157, p. 308. https://doi.org/10.1126/science.157.3786.308
  5. Иванов-Шиц, А.К., Мурин, И.В. Ионика твердого тела, в 2 т. Т.I, Cпб.: Изд-во С.- Петерб. ун-та, 2000. 616 с. [Ivanov-Shits, A.K. and Murin, I.V. Solid state Ionics, in 2 vols. (in Russian), vol. I, St. Petersburg: Publ. House of St. Petersburg Univer., 2000. 616 p.]
  6. Деспотули, А.Л., Личкова, Н.В., Миненкова, Н.А., Носенко, С.В. Получение и некоторые свойства тонких пленок твердых электролитов CsAg 4 Br 3-x I 2+x   и RbAg 4 I 5 . Электрохимия. 1990. Т. 26. С. 1524. [Despotuli, A.L., Lichkova, H.V., Minenkova, H.A., and Nosenko, S.V., Preparation and Certain Properties of CsAg 4 Br 3-x I 2+x   и RbAg 4 I 5 Thin Film Solid Electrolytes, Elektrokhimiya (in Russian), 1990, vol. 26, p. 1524.]
  7. Личкова, Н.В., Деспотули, А.Л., Загороднев, В.Н., Миненкова, Н.А., Шахлевич, К.В. Ионная проводимость твердых электролитов в двух- и трехкомпонентых стеклообразующих системах AgX-CsX (X=Cl, Br, I). Электрохимия. 1989. Т. 25. С. 1636. [Lichkova, H.V., Despotuli, A.L., Zagorodnev, V.N., Minenkova, H.A., and Shakhlevich, K.V., Ionic conductivity of solid electrolytes in two- and three-component glass-forming systems AgX-CsX (X=Cl, Br, I), Elektrokhimiya (in Russian), 1989, vol. 25, p. 1636.]
  8. Деспотули, А.Л., Загороднев, В.Н., Личкова, Н.В., Миненкова, Н.А. Новые высокопроводящие твердые электролиты: CsAg 4 Br 3-x I 2+x 0,25≤х≤1. Физика твердого тела. 1989. Т. 31. № 9. С. 242. [Despotuli, A.L., Zagorodnev, V.N., Lichkova, N.V., and Minenkova, N.A., New high conductive CsAg 4 Br 3-x I 2+x (0.25 < x < 1) solid electrolytes, Fiz. Tverd. Tela (Leningrad) (in Russian), 1989, vol. 31, no. 9, p. 242.]
  9. Lichkova, N.V., Despotuli, A.L., Zagorodnev, V.N., and Minenkova, N.A., Superionic glasses based on silver and cesium monohalides, Mater. Sci. Forum, 1991, vol. 67-68, p. 601. https://doi.org/10.4028/www.scientific.net/MSF.67-68.601
  10. Личкова, Н.В., Деспотули, А.Л., Загороднев, В.Н., Миненкова, Н.А. Твердый электролит, Пат. RU 1 697 573 С. H01M 6/18 (1995.01) (Россия). 1989. [Lichkova, N.V., Despotuli, A.L., Zagorodnev, V.N., and Minenkova, N.A. Solid electrolyte, Patent RU 1 697 573 P. H01M 6/18 (1995.01) (Russia), 1989.]
  11. Деспотули, А.Л., Личкова, Н.В. Ионистор, Пат. RU 2 012 105 C1, МПК H01M 6/18. Россия, 1991. [Despotuli, A.L. and Lichkova, N.V., Ionistor, Patent RU 2,012 105 C1, IPC H01M 6/18 (Russia), 1991.]
  12. Толстогузов, А.Б., Белых, С.Ф., Гололобов, Г.П., Гуров, В.С., Гусев, С.И., Суворов, Д.В., Таганов, А.И., Fu, D.J., Ai, Z., Liu, C.S. Ионные источники на твердых электролитах для аэрокосмического применения и ионно-лучевых технологий (обзор). Приборы и техника эксперимента. 2018. № 2. С. 5. [Tolstoguzov, A.B., Belykh, S.F., Gololobov, G.P., Gurov, V.S., Gusev, S.I., Suvorov, D.V., Taganov, A.I., Fud, D.J., Ai, Z., and Liu, C.S., Ion-beam sources based on solid electrolytes for aerospace applications and ion-beam technologies (Review), Instruments and Experimental Techniques, 2018, vol. 61, no. 2, p. 159.] https://doi.org/10.7868/S0032816218020106
  13. Деспотули, А.Л., Андреева, А.В. Наноионика: новые материалы и суперконденсаторы. Рос. нанотехнологии. 2010. Т. 5. № 7-8. С. 89. [Despotuli, A.L. and Andreeva, A.V., Nanoionics: New Materials and Supercapacitors, Nanotechnologies in Russia, 2010, vol. 5, no. 7–8, p. 506.] doi: 10.1134/S1995078010070116
  14. Owens, B.B., Solid state electrolytes: overview of materials and applications during the last third of the Twentieth Century, J. Power Sources, 2000, vol. 90, p. 2. https://doi.org/10.1016/S0378-7753(00)00436-5
  15. Palakkathodi Kammampata, S. and Thangadurai, V., Cruising in ceramics – discovering new structures for all-solid-state batteries – fundamentals, materials, and performances, Ionics, 2018, vol. 24, no. 3, p. 639. https://doi.org/10.1007/s11581-017-2372-7
  16. Glukhov, A.A., Belmesov, A.A., Nechaev, G.V., Ukshe, A.E., Reznitskikh, O.G., Bukun, N.G., Shmygleva, L.V., and Dobrovolsky, Y.A., Anode material for all-solid-state battery based on solid electrolyte CsAg 4 Br 2.5 I 2.5 : Theory and experiment, Mater. Sci. and Engineering: B, 2022, vol. 278, art. 115617. https://doi.org/10.1016/j.mseb.2022.115617
  17. Резницких, О.Г., Ярославцева, Т.В., Глухов, А.А., Попов, Н.А., Урусова, Н.В., Букун, Н.Г., Добровольский, Ю.А., Бушкова О.В. Синтез и сравнительное исследование электрохимических характеристик твердых электролитов CsAg 4 Br 2.5 I 2.5 и RbAg 4 I 5 . Электрохимия. 2022. Т. 58. С. 676. doi: 10.31857/S0424857022100103. [Reznitskikh, O.G., Yaroslavtseva, T.V., Glukhov, A.A., Popov, N.A., Urusova, N.V., Bukun, N.G., Dobrovolsky, Yu. A., and Bushkova, O.V., Synthesis and comparative investigation of the electrochemical characteristics of CsAg 4 Br 2.5 I 2.5 and RbAg 4 I 5 solid electrolytes, Russ. J. Electrochem., 2022, vol. 58, p. 927.] https://doi.org/10.1134/S102319352210010X
  18. Rodríguez-Carvajal, J., Recent advances in magnetic structure determination by neutron powder diffraction, Physica B, 1993, vol. 192, no. 1–2, p. 55. https://doi.org/10.1016/0921-4526(93)90108-I
  19. Valverde, N., Thermodynamic stabilization of the solid electrolyte RbAg 4 I 5 , J. Electrochem. Soc.: Solid State Sci. and Technol., 1980, vol. 127, no. 11, p. 2425. https://doi.org/10.1149/1.2129487
  20. Бушкова, О.В., Резницких, О.Г., Ярославцева, Т.В., Попов, Н.А., Непомилуев, А.М., Новиков, Д.В., Добровольский, Ю.А. Способ получения твердого электролита. Пат. 2720349 (Россия), 2019. [Bushkova, O.V., Reznitskikh, O.G., Yaroslavtseva, T.V., Popov, N.A., Nepomiluev, A.M., Novikov, D.V., and Dobrovolsky, Yu.A., Method of obtaining a solid electrolyte, Patent 2720349 (Russia), 2019.]
  21. Shahi, K. and Chandra, S., Thermoelectric power of the superionic conductors Ag 4 MI 5 (M= K and Rb), J. Phys. C: Solid State Phys., 1976, vol. 9, no. 16, p. 3105. https://doi.org/10.1088/0022-3719/9/16/016
  22. Scrosati, B., Germano, G., and Pistoia, G., Electrochemical properties of RbAg 4 I 5 solid electrolyte: I. Conductivity studies. J. Electrochem. Soc., 1971, vol. 118, no. 1, p. 86. https://doi.org/10.1149/1.2407958
  23. Укше, Е.А., Букун, Н.Г. Твердые электролиты, М.: Наука, 1977. 176 с. [Ukshe, E.A. and Bukun, N.G., Solid Electrolytes, Moscow: Nauka, 1977. 176 p.]
  24. Zolotoyabko, E.V. and Ovanesyan, N.S., Moessbauer diffraction in the superionic conductor RbAg 4 I 5 , Phys. Status Solidi. B, B. Research., 1985, vol. 129, no. 2, p. 587. https://doi.org/10.1002/pssb.2221290216

Supplementary files

Supplementary Files
Action
1. JATS XML
Download
2. Fig. 1. Experimental (dots) and calculated (line) X-ray diffraction patterns of solid electrolytes CsAg4Br3-хI2+х, where x = 0.38 (a), 0.50 (b) and 0.63 (c). Dashes are the angular positions of Bragg reflections. Below is the difference between calculation and experiment.

Download (268KB)
Indexing metadata
3. Fig. 2. DSC curves for synthesized samples of solid electrolytes CsAg4Br3-хI2+х (x = 0.38; 0.50; 0.63) and RbAg4I5.

Download (87KB)
Indexing metadata
4. Fig. 3. Temperature dependences of the conductivity of solid electrolytes RbAg4I5 and CsAg4Br3-хI2+х (where x = 0.38; 0.50; 0.63).

Download (106KB)
Indexing metadata
5. Fig. 4. Volt-ampere characteristics of solid electrolytes CsAg4Br3-xI2+x (a) and assessment of the oxidation potential Eox using the example of CsAg4Br2.37I2.63 (b). (For ease of comparison of curves in Fig. 4a, the current density values ​​are multiplied by the thickness of the electrolyte; the cross-sectional areas of all electrolyte samples are the same and equal to 0.20 cm2.)

Download (101KB)
Indexing metadata

Copyright (c) 2024 Russian Academy of Sciences