Cover Image

Oxygen diffusion and surface exchange kinetics for the mixed-conducting oxide La0.6Sr0.4Co0.8Fe0.2O3-δ

Natalia M. Porotnikova, Ekaterina P. Antonova, Anna V. Khodimchuk, Eugene S. Tropin, Andrey S. Farlenkov, Maxim V. Ananyev


Studies of oxygen surface exchange kinetics for La0.6Sr0.4Co0.8Fe0.2O3-δ oxide were performed using the technique of isotopic exchange of molecular oxygen with analysis of gas phase isotopic composition in a static circulation system at the temperatures of 600-800 °С in the oxygen pressure range of 0.27-2.13 kPa. The values of interphase exchange rate and oxygen diffusion coefficient were determined. The effective activation energies for oxygen exchange and diffusion processes as well as the exponents in the dependence of these values versus oxygen pressure in the double logarithmic coordinates were calculated. The process of oxygen dissociative adsorption at the surface of La0.6Sr0.4Co0.8Fe0.2O3-δ oxide was found to be the rate-determining stage.


oxygen isotope exchange; oxygen diffusion; lanthanum- strontium cobaltite-ferrite; rate-determining stage

Full Text:



Petrov AN, Cherepanov VA, Zuyev AYu, Zhukovsky VM. Thermodynamic stability of ternary oxides in Ln–M–O systems (Ln = La, Pr, Nd; M = Co, Ni, Cu). J Solid State Chem. 1988;77(1):1–14. doi:10.1016/0022-4596(88)90083-7

Kharton VV, Figueiredo FM, Kovalevsky AV, Viskup AP, Naumovich EN, Yaremchenko AA, Bashmakov IA, Marques FM. Processing, microstructure and properties of LaCoO3–δ ceramics. J Eur Ceram Soc. 2001;21(13):2301–9. doi:10.1016/S0955-2219(01)00199-6

Yang M, Zhong Y, Liu ZK. Defect analysis and thermodynamic modeling of LaCoO3. Solid State Ionics. 2007;178(15-18):1027–32. doi:10.1016/j.ssi.2007.04.014

Zuev AYu, Petrov AN, Vylkov AI, Tsvetkov DS. Oxygen nonstoichiometry and defect structure of undoped and doped lanthanum cobaltites. Journal of Material Sciences. 2007;42(6):1901–8. doi:10.1007/s10853-006-0345-8

Tai LW, Nasrallah MM, Anderson HU, Sparlin DM, Sehlin SR. Structure and electrical properties of La1−xSrxCo1−yFeyO3. Part 1. The system La0.8Sr0.2Co1−yFeyO3 // Solid State Ionics. 1995;76(3-4):259-71. doi:10.1016/0167-2738(94)00244-M

Stevenson JW, Armstrong TR, Carneim RD, Pederson LR, Weber WJ. Electrochemical properties of mixed conducting perovskites La1 − xMxCo1 − yFeyO3 − δ (M = Sr, Ba, Ca). J Electrochem Soc. 1996;143(9) 2722–9. doi:10.1149/1.1837098

Aksenova TV, Anan’ev MV, Gavrilova LYa, Cherepanov VA. Phase equilibria and crystal structures of solid solutions in the system LaCoO3–δ – SrCoO2.5±δ– SrFeO3–δ–LaFeO3–δ. Inorg Mater. 2007;43(3):296–300. doi:10.1134/S0020168507030168

Lankhorst MHR, Elshof JE. Thermodynamic quantities and defect structure of La0.6Sr0.4Co1 yFeyO3-δ (y=0–0.6) from high-temperature coulometric titration experiments. J Solid State Chem. 1997;130(2):302-10. doi:10.1006/jssc.1997.7378

Choi MB, Lim DK, Wachsman ED, Song SJ. Oxygen nonstoichiometry and chemical expansion of mixed conducting La0.1Sr0.9Co0.8Fe0.2O3−δ. Solid State Ionics. 2012;221:22–7. doi:10.1016/j.ssi.2012.06.012

Hashimoto S, Fukuda Y, Kuhn M, Sato K, Yashiro K, Mizusaki J. Oxygen nonstoichiometry and thermo-chemical stability of La0.6Sr0.4Co1 yFeyO3-δ (y=0.2, 0.4, 0.6, 0.8). Solid State Ionics. 2010;181(37-38):1713–9. doi:10.1016/j.ssi.2010.09.024

Elshof JE, Lankhorst MHR, Bouwmeester HJM. Chemical diffusion and oxygen exchange of La0.6Sr0.4Co0.6Fe0.4O3−δ. Solid State Ionics. 1997;99(1-2):15–22. doi:10.1016/S0167-2738(97)00263-4

Ananyev MV, Kurumchin EKh. Interphase exchange and diffusion of oxygen in lanthanum-strontium cobaltites doped with iron. Russ J Phys Chem A. 2010;84(6):1039–44. doi:10.1134/S0036024410060269

Bouwmeester HJM, den Otter MW, Boukamp BA. Oxygen transport in La0.6Sr0.4Co1-yFeyO3 δ. J Solid State Electrochem. 2004;8(9):599–605. doi:10.1007/s10008-003-0488-3

Kurumchin EKh, Ananjev MV, Vdovin GK, Surkova MG. Exchange kinetics and diffusion of oxygen in systems based on lanthanum gallate. Russ J Electrochem. 2010;46(2): 205–11. doi:10.1134/S1023193510020126

Ananyev MV, Kurumchin EKh, Porotnikova NM. Effect of oxygen nonstoichiometry on kinetics of oxygen exchange and diffusion in lanthanum-strontium cobaltites. Russ J Electrochem. 2010;46(7):789–97. doi:10.1134/S1023193510070128

Ezin AN, Tsidilkovski VI, Kurumchin EKh. Isotopic exchange and diffusion of oxygen in oxides with different bulk and subsurface diffusivities. Solid State Ionics. 1996;84(1-2):105–12. doi:10.1016/S0167-2738(96)83012-8

Klier K, Kucera E. Theory of Exchange Reactions between Fluids and Solids with Tracer Diffusion in the Solid. J Phys Chem Solids. 1966;27:1087–95. doi:10.1016/0022-3697(66)90084-9

Boreskov GK, Kasatkina LA. Catalysis of Isotope Exchange in Molecular Oxygen and Its Application to the Study of Catalysts. Russ Chem Rev. 1968;37(8):613–28. doi:10.1070/RC1968v037n08ABEH001686

Porotnikova NM, Anan’ev MV, Kurumchin EKh. Effect of Defect Structure of Lanthanum Manganite on Kinetics of Oxygen Exchange and Diffusion. Russ J Electrochem. 2011;47(11):1250–6. doi:10.1134/S1023193511110139

Anan'ev MV, Bershitskaya NM, Plaksin SV, Kurumchin EKh. Phase equilibriums, oxygen exchange kinetics and diffusion in oxides CaZr 1-xSc xO 3-x/2-δ. Russ J Electrochem. 2012;48(9):879–86. doi:10.1134/S1023193512090030

Anan'ev MV, Kurumchin EKh, Vdovin GK, Bershitskaya NM. Kinetics of interaction of gas phase oxygen with cerium-gadolinium oxide. Russ J Electrochem. 2012;48(9):871–8. doi:10.1134/S1023193512090029

Bershitskaya NM, Ananyev MV, Kurumchin EKh, Gavrilyuk AL, Pankratov AA. Effect of oxygen nonstoichiometry on kinetics of oxygen exchange and diffusion in lanthanum-strontium manganites. Russ J Electrochem. 2013;49(10):963–74. doi:10.1134/S1023193512100047

Wang S, Katsuki M, Dokiya M, Hashimoto T. High temperature properties of La0.6Sr0.4Co0.8Fe0.2O3−δ phase structure and electrical conductivity. Solid State Ionics. 2003;159(1-2):71–8. doi:10.1016/S0167-2738(03)00027-4

Li Y, Gerdes K, Horita T, Liu X. Surface exchange and bulk diffusivity of LSCF as SOFC cathode: electrical conductivity relaxation and isotope exchange characterizations. J Electrochem Soc. 2013;160(4):F343-50. doi:10.1149/2.044304jes

Katsuki M, Wang S, Dokiya M, Hashimoto T. High temperature properties of La0.6Sr0.4Co0.8Fe0.2O3−δ oxygen nonstoichiometry and chemical diffusion constant. Solid State Ionics. 2003;156(3-4):453–61.doi:10.1016/S0167-2738(02)00733-6

Ananyev MV. Izotopnii obmen kisloroda. Teoreticheskie osnovy metoda i ego primenenie k analizy kinetiki obmena kisloroda s stehiometricheskimi oksidami [Oxygen isotope exchange. Theoretical basis of the method and its application to the analysis of the kinetics of oxygen exchange with non-stoichiometric oxides] Saarbrucken: Lambert Academic Publishing; 2012. 205 p. Russian.

Porotnikova NM, Khodimchuk AV, Ananyev MV, Eremin VA, Tropin ES, Farlenkov AS, Pikalova EYu, Fetisov AV. J Solid State Electrochem. 2018;22(7):2115–26. doi:10.1007/s10008-018-3919-x

Ananyev MV, Tropin ES, Eremin VA, Farlenkov AS, Smirnov AS, Kolchugin AA, Porotnikova NM, Khodimchuk AV, Berenov AV, Kurumchin EK. Oxygen isotope exchange in La2NiO4±δ. Phys Chem Chem Phys. 2016;18(13):9102–11. doi:10.1039/c5cp05984d

Ananyev MV, Eremin VA, Tsvetkov DS, Porotnikova NM, Farlenkov AS, Zuev AYu, Fetisov AV, Kurumchin EKh. Oxygen isotope exchange and diffusion in LnBaCo2O6 − δ (Ln = Pr, Sm, Gd) with double perovskite structure. Solid State Ionics. 2017;304:96–106. doi:10.1016/j.ssi.2017.03.022


Copyright (c) 2018 Natalia Porotnikova, Ekaterina Antonova, Anna Khodimchuk, Eugene Tropin, Andrey Farlenkov, Maxim Ananyev

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

Scopus logo WorldCat logo DOAJ logo CAS logo BASE logo eLibrary logo

Chimica Techno Acta, 2014-2024
ISSN 2411-1414 (Online)
Copyright Notice