Investigation of high-temperature oxygen release from LA2NiO4+δ oxide in quasi-equilibrium mode

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Resumo

A continuous phase diagram δ (pO2, T) of a nonstoichiometric oxide La2NiO4+δ with a layered perovskite-related Ruddlesden-Popper structure was obtained by the method of quasi-equilibrium oxygen release. The thermodynamic parameters are determined as functions of oxide nonstoichiometry δ. The calculation was carried out within the framework of the models of a localized electron and a free electron, which are used to describe the defect structure of ferrites and cobaltites, respectively. It is shown that the features of the phase diagram can be related to the density of electronic states near the Fermi level of electrons.

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Sobre autores

E. Tropin

Institute of Solid State Chemistry and Mechanochemistry of Siberian Branch of Russian Academy of Sciences

Autor responsável pela correspondência
Email: evg2306@mail.ru
Rússia, Novosibirsk

M. Popov

Institute of Solid State Chemistry and Mechanochemistry of Siberian Branch of Russian Academy of Sciences

Email: popov@solid.nsc.ru
Rússia, Novosibirsk

R. Guskov

Institute of Solid State Chemistry and Mechanochemistry of Siberian Branch of Russian Academy of Sciences

Email: evg2306@mail.ru
Rússia, Novosibirsk

A. Nemudry

Institute of Solid State Chemistry and Mechanochemistry of Siberian Branch of Russian Academy of Sciences

Email: evg2306@mail.ru
Rússia, Novosibirsk

Bibliografia

  1. Adler, S.B., Chen, X.Y., and Wilson, J.R., Mechanisms and rate laws for oxygen exchange on mixed-conducting oxide surfaces, J. Catal., 2007, vol. 245, p. 91.
  2. Lankhorst, M.H.R., Bouwmeester, H.J.M., and Vervweij, H., High-temperature coulometric titration of La 1-x Sr x CoO 3-δ , J. Solid State Chem., 1997, vol. 133, p. 555.
  3. Ananyev, M.V., Tropin, E.S., Eremin, V.A., Farlenkov, A.S., Smirnov, A.S., Kolchugin, A.A., Porotnikova, N.M., Khodimchuk, A.V., Berenov, A.V., and Kurumchin, E.Kh, Oxygen isotope exchange in La 2 NiO 4+δ , Phys. Chem. Chem. Phys., 2016, vol. 18, p. 9102.
  4. Petrov, A.N., Kononchuk, O.F., Andreev, A.V., Cherepanov, V.A., and Kofstad, P., Crystal structure, electric and magnetic properties of La 1-x Sr x CoO 3 , J. Solid State Ionics, 1995, vol. 80, p. 189.
  5. Nakamura, T., Yashiro, K., Sato, K., and Mizusaki, J., Oxygen nonstoichiometry and defect equilibrium in La 2-x Sr x NiO 4+δ , J. Solid State Ionics, 2009, vol. 180, p. 348.
  6. Starkov, I., Bychkov, S., Matvienko, A., and Nemudry, A., A new technique from the research group of As featured in: Oxygen release technique as a method for the determination of “δ – p O 2 – T ” diagrams for MIEC oxides, Phys. Chem. Chem. Phys., 2014, vol. 16, p. 5527.
  7. Chizhik, S.A., Bychkov, S.F., Popov, M.P., and Nemudry, A.P., Brønsted-Evans-Polanyi relationship in oxygen exchange of non-stoichiometric oxides with gas phase, Chem. Eng. J., 2019, vol. 371, p. 319.
  8. Chizhik, S.A., Bychkov, S.F., Voloshin, B.V., Popov, M.P., and Nemudry, A.P., The Brønsted –Evans –Polanyi relationship in oxygen exchange of fuel cell cathode material SrCo 0.9 Ta 0.1 O 3-δ with the gas phase, Phys. Chem. Chem. Phys., 2021, vol. 23, p. 1072.
  9. Chizhik, S.A., Kovalev, I.V., Popov, M.P., Bychkov, S.F., and Nemudry, A.P., Study of the isobaric and isostoichiometric kinetic parameters of oxygen exchange reaction of SrFe 0.98 Mo 0.02 O 3-δ MIEC perovskite, Chem. Eng. J., 2021, vol. 445, p. 136724.
  10. Lankhorst, M.H.R., Bouwmeester, H.J.M., and Vervweij, H., Chemical diffusion and oxygen exchange of La 0.6 Sr 0.4 Co 0.6 Fe 0.4 O 3-δ , J. Ceram. Soc., 1997, vol. 80, p. 2175.
  11. Lankhorst, M.H.R. and Elshof, J.E., The Significance of Gas-Phase Mass Transport in Assessment of kchem and Dchem, J. Solid State Chem., 1997, vol. 130, p. 302.
  12. Bychkov, S.F., Sokolov, A.G., Popov, M.P., and Nemudry, A.P., Relation between oxygen stoichiometry and thermodynamic properties and electronic structure of nonstoiciometric perovskite La 0.6 Sr 0.4 CoO 3-δ , Phys. Chem. Chem. Phys., 2016, vol. 18, p. 29543.

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2. Fig. 1. Setup for measuring oxygen exchange in SIEP oxides.

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3. Fig. 2. X-ray diffraction pattern of a slowly air-cooled LNO sample.

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4. Fig. 3. Initial experimental data on oxygen evolution from LNO.

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5. Fig. 4. Dependence of pO2 on time for a temperature of 850°C at different helium flow rates (a) and its affine transformation (b).

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6. Fig. 5. Equilibrium phase diagram 4+δ – ln pO2 – T LNO (T = 600–850°C) in comparison with literature data [5].

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7. Fig. 6. LNO isotherms at 600°C (a) and 850°C (b).

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8. Fig. 7. Dependence of the parameter β on temperature.

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Nota

Публикуется по материалам IX Всероссийской конференции с международным участием “Топливные элементы и энергоустановки на их основе”, Черноголовка, 2022.


Declaração de direitos autorais © Russian Academy of Sciences, 2024