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Impedance spectroscopy in investigation of the charge transfer processes. S.V.GNEDENKOV, S.L.SINEBRUKHOV (Institute of Chemistry, FEB RAS, Vladivostok).
A mechanism of charge transfer at solid/electrolyte and solid/gas phase interfaces has been studied using the method of impedance spectroscopy. It has been established that there is a close interconnection between charge transfer
processes and properties of functional materials. It has been shown that impedance spectroscopy has high capabilities
for investigation of anticorrosion heterostructures, electrode materials, and ionic solid solutions.

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14

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15


1. .., .., .. , () // . . 2002. 3. . 2139.
2. .., .., .., .C. ,
- // .
1998. . 34, 9. . 10461051.
3. .., .. ,
// : , . 2004. 2. . 28.
4. .., .. // . 2005. . 41, 8. . 979987.
5. .., .., .. / // . 2006. . 42, 3. . 235250.
6. .., .. . : , 1997. 183 .
7. .., .. . .: , 1983. 312 .
8. .., .., p . ., p B..
p . I. pp pp p p // : , .
2005. 10. . 1925.
9. .., .., - ., .. . .: ,
1991. 336 .
10. Abreu C.M., Cristobal M.J., Losada R., Novoa X.R., Pena G., Perez M.C. Comparative study of passive lms of
different stainless steels developed on alkaline medium // Electrochim. Acta. 2004. Vol. 49. P. 30493056.
11. Ahmad M.M., Yamada K., Okuda T. Fluoride ion diffusion of superionic PbSnF4 studied by nuclear magnetic
resonance and impedance spectroscopy // J. Phys.: Condens. Matter. 2002. Vol. 14. P. 72337244.
12. Al-Khara F.M., Badawy W.A. Electrochemical behaviour of vanadium in aqueous solution of different pH //
Electrochim. Acta. 1997. Vol. 42. P. 579586.
13. Alves V.A., Brett C.M.A. Characterisation of passive lms formed on mild steels in bicarbonate solution by EIS
// Electrochim. Acta. 2002. Vol. 47. P. 20812091.
14. Barsoukov E., Macdonald J.R. Impedance spectroscopy: theory, experiment and application. N.Y.: Willey, 2005. 595 p.
15. Bessler W.G. A new computational approach for SOFC impedance from detailed electrochemical reaction
diffusion models // Solid State Ionics. 2005. Vol. 176. P. 9971011.
16. Bisquert J. Inuence of the boundaries in the impedance of porous electrodes // Phys. Chem. Chem. Phys. 2000.
Vol. 2. P. 41854192.
17. Boukamp B.A. A nonlinear least squares t procedure for analysis of immittance data of electrochemical systems
// Solid State Ionics. 1986. Vol. 20. P. 3144.
18. Easton E.B., Pickup P.G. An electrochemical impedance spectroscopy study of fuel cell electrodes // Electrochim. Acta. 2005. Vol. 50. P. 24692474.
19. Gabrielli C., Keddam M. Contribution of electrochemical impedance spectroscopy to the investigation of the
electrochemical kinetics // Electrochim. Acta. 1996. Vol. 41. P. 957965.
20. Gabrielli C. Identication of electrochemical processes by frequency response analysis. Farmborough: Solartron,
1984. 120 p.
21. Gnedenkov S.V., Gordienko P.S., Sinebrukhov S.L., Khrisanphova O.A., Skorobogatova T.M. Anticorrosion,
antiscale coatings obtained on the surface of titanium alloys by microarc oxidation method and used in seawater // Corrosion. 2000. N 1 (56). P. 2431.
22. Gomes W.P., Vanmaekelbergh D. Impedance spectroscopy at semiconductor electrodes: review and recent
developments // Electrochim. Acta. 1996. Vol. 41. P. 967973.
23. Hornkjol S., Hornkjol I.M. Anodic behaviour of vanadium in acid solutions // Electrochim. Acta. 1991. Vol. 36.
P. 577580.
24. Huet F. A review of impedance measurement for determination of the state-of-charge or state-of-health of secondary batteries // J. Power Sources. 1998. Vol. 70. P. 5969.
25. Karden E., Buller S., De Doncker R.W. A method for measurement and interpretation of impedance spectra for
industrial batteries // J. Power Sources. 2000. Vol. 85. P. 7278.
26. Kramer F. Dielectric spectroscopy yesterday, today and tomorrow // J. Non-Cryst. Solids. 2002. Vol. 305. P. 19.
27. Krewer U., Christov M., Vidakovic T., Sundmacher K. Impedance spectroscopic analysis of the electrochemical
methanol oxidation kinetics // J. Electroanal. Chem. 2006. Vol. 589. P. 148159.
28. Lasia A. Impedance of porous electrodes // J. Electroanal. Chem. 1995. Vol. 397. P. 2733.
29. Loveday D., Peterson P., Rodgers B. Evaluation of organic coatings with electrochemical impedance spectroscopy // JCT Coatings Tech. 2004. Vol. 8. P. 4652.
30. Macdonald D.D. Reections on the history of electrochemical impedance spectroscopy // Electrochim. Acta.
2006. Vol. 51. P. 13761388.
31. Macdonald J.R. Analysis of dispersed, conducting-system frequency-response data // J. Non-Cryst. Solids. 1996.
Vol. 197. P. 83110.
32. Metikos-Hukovic M., Kwokal A., Piljac J. The inuence of nibium and vanadium on passivity of titanium-based
implants in physiological solution // Biomaterials. 2003. Vol. 24. P. 37653775.
33. Park S.M., Yoo J.S. Electrochemical impedance spectroscopy for better electrochemical measurements // Anal.
Chem. 2003. Vol. 75. P. 455A461A.
34. Zplot for Windows. Electrochemical Impedance Software. Operating Manual version 2.4. Scribner Associates,
Inc., 2001.

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