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Defect chemistry and charge transfer in praseodymium-barium cobaltites

Roman Yagovitin, Dmitry Tsvetkov, Ivan Ivanov, Vladimir Sereda, Dmitry Malyshkin, Andrey Zuev

Abstract


The conductivity of Pr1-xBaxCoO3-δ (x = 0 – 1/3) was measured in air as a function of temperature using a four-probe DC technique. The obtained data indicate that conductivity is governed by the following factors: hole concentration, hole mobility, oxygen exchange with the atmosphere, sample’s magnetic and phase state. The total conductivity was shown to be dominated by the small polaron holes over the whole temperature range studied. A combined defect chemical model based on the small polaron hopping mechanism was developed to quantitatively describe the conductivity temperature dependence. A novel approach was suggested for estimating the parameters of the model, yielding, among other quantities, the electron and hole mobilities, mobility activation energies, and transference numbers. This approach is not limited to the studied compounds and can be applied to the wide range of similar systems. The results obtained also demonstrate that praseodymium-barium cobaltites are promising cathode materials for solid oxide fuel cells due to their high conductivity and low activation energy of conduction.

Keywords


cobaltites; defect structure; oxygen nonstoichiometry; conductivity; small polaron hopping model

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References


Park S., Choi S., Shin J., Kim G. Electrochemical investigation of strontium doping effect on high performance Pr1 − xSrxCoO3 − δ (x = 0.1, 0.3, 0.5, and 0.7) cathode for intermediate-temperature solid oxide fuel cells. J. Power Sources 2012;210:172–177. doi:10.1016/j.jpowsour.2012.03.018

Setevich C., Mogni L., Caneiro A., Prado F. Characterization of the La1−xBaxCoO3−δ (0 ≤ x ≤ 1) System as Cathode Material for IT-SOFC. J. Electrochem. Soc. 2011;159:B72–B79. doi:10.1149/2.043201jes

Gwon O., Yoo S., Shin J., Kim G. Optimization of La1-xSrxCoO3-δ perovskite cathodes for intermediate temperature solid oxide fuel cells through the analysis of crystal structure and electrical properties. Int. J. Hydrog. Energy 2014;39:20806–20811. doi:10.1016/j.ijhydene.2014.07.137

Garcés D., Soldati A.L., Troiani H., Montenegro-Hernández A., Caneiro A., Mogni L.V. La/Ba-based cobaltites as IT-SOFC cathodes: a discussion about the effect of crystal structure and microstructure on the O2-reduction reaction. Electrochim. Acta 2016;215:637–646. doi:10.1016/J.ELECTACTA.2016.08.132

Yi K., Sun L., Li Q., Xia T., Huo L., Zhao H., Li J., Lü Z., Bassat J.-M., Rougier A., Fourcade S., Grenier J.-C. Effect of Nd-deficiency on electrochemical properties of NdBaCo2O6−δ cathode for intermediate-temperature solid oxide fuel cells. Int. J. Hydrog. Energy 2016;41:10228–10238. doi:10.1016/j.ijhydene.2016.04.248

Suntsov A.Yu., Politov B.V., Leonidov I.A., Patrakeev M.V., Kozhevnikov V.L. Improved stability and defect structure of yttrium doped cobaltite PrBaCo2O6–δ. Solid State Ion. 2016;295:90–95. doi:10.1016/j.ssi.2016.08.003

Wu Y.-C., Huang P.-Y., Xu G. Properties and microstructural analysis of La1−xSrxCoO3−δ (x=0–0.6) cathode materials. Ceram. Int. 2017;43:2460–2470. doi:10.1016/j.ceramint.2016.11.041

Vereshchagin S.N., Dudnikov V.A., Zharkov S.M., Zeer G.M., Solovyov L.A. Electrochemical Performance of Dysprosium-Doped Strontium Cobaltite with Perovskite Structure. Mol. 2025;30:4437. doi:10.3390/molecules30224437

Luo H., Hu Q., Yue B., Du S. Perovskite-type RCoO3 (R = Pr, Eu, Gd) nanofibers for supercapacitor electrodes and antiferromagnet. J. Mater. Sci. 2024;59:2258–2272. doi:10.1007/s10853-024-09343-8

Tripathi H.S., Karmakar R., Bhowmik T.K., Halder S., Dutta A., Sinha T.P. RCoO3 {R=Pr, Nd and Sm} electrode-based for efficient solid-state symmetric supercapacitor. Solid State Sciences 2022;134:107065. doi:10.1016/j.solidstatesciences.2022.107065

Alyousef H.A., Abdelmohsen S.A.M., Alqarny A.S., Alotaibi N., Abdullah M., Imran M., Ijaz Y. Fabrication of barium-doped SrCoO3 perovskite as an efficient supercapacitor electrode material. J. Nanoparticle Research. 2025;27:298. doi:10.1007/s11051-025-06458-0

Liu Q., Li R., Feng W., Li J., Zhang X., Lv H., Shen Y., Song Y., Wang G., Bao X. Promoting High-Temperature Oxygen Evolution Reaction via Infiltration of PrCoO3−δ Nanoparticles. ACS Appl. Energy Mater. 2022;5:11604–11612. doi:10.1021/acsaem.2c02089

Zhang W., Shiraiwa M., Wang N., Ma T., Fujii K., Niwa E., Yashima M. Pr/Ba cation-disordered perovskite Pr2/3Ba1/3CoO3−δ as a new bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. J. Ceram. Soc. Jpn. 2018;126:814–819. doi:10.2109/jcersj2.18076

Kostogloudis G.Ch., Vasilakos N., Ftikos Ch. Crystal structure, thermal and electrical properties of Pr1−xSrxCoO3−δ (x=0, 0.15, 0.3, 0.4, 0.5) perovskite oxides. Solid State Ionics 1998;106:207–218. doi:10.1016/S0167-2738(97)00506-7

Takami T., Zhou J.-S., Goodenough J. B., Ikuta H. Correlation between the structure and the spin state in R1−xSrxCoO3 (R=La, Pr, and Nd). Phys. Rev. B 2007;76:144116. doi:10.1103/PhysRevB.76.144116

Leighton C., Stauffer D. D., Huang Q., Ren Y., El-Khatib S., Torija M.A., Wu J., Lynn J.W., Wang L., Frey N.A., Srikanth H., Davies J.E., Liu K., Mitchell J.F. Coupled structural/magnetocrystalline anisotropy transitions in the doped perovskite cobaltite Pr1−xSrxCoO3. Phys. Rev. B 2009;79:214420. doi:10.1103/PhysRevB.79.214420

Vlasova M.A., Volkova N.E., Ivanov I.L., Aksenova T.V., Cherepanov V.A. Crystal structure, oxygen nonstoichiometry and properties of Pr1-xSrxCoO3-δ. Ceram. Int. 2024;50:30785–30793. doi:10.1016/j.ceramint.2024.05.379

Brinks H.W., Fjellvåg H., Kjekshus A., Hauback B.C. Structure and Magnetism of Pr1−xSrxCoO3−δ. J. Solid State Chem. 1999;147:464–477. doi:10.1006/jssc.1999.8384

Modi A., Ahmad Bhat M., Bhattacharya S., Okram G.S., Gaur N.K. Magnetic and transport properties driven by Sr substitution in polycrystalline Pr1-xSrxCoO3 (0.1 ≤ x ≤ 0.5) cobaltites. J. Appl. Phys. 2018;123:205114. doi:10.1063/1.5039617

Moon J.-W., Masuda Y., Seo W.-S., Koumoto K. Influence of ionic size of rare-earth site on the thermoelectric properties of RCoO3-type perovskite cobalt oxides. Mater. Sci. Eng. 2001;B85:70–75. doi:10.1016/S0921-5107(01)00645-6

Yagovitin R.E., Tsvetkov D.S., Sereda V.V., Ivanov I.L., Malyshkin D.A., Zuev A.Yu. Crystal and defect structure of advanced Pr1-xBaxCoO3-δ oxide ceramics studied by thermal analysis: A new approach to oxygen exchange energetics. Ceram. Int. 2025;51:5890–5898. doi:10.1016/j.ceramint.2024.12.034

Ivanov I.L., Zakiryanov P.O., Sereda V.V., Mazurin M.O., Malyshkin D.A., Zuev A.Yu., Tsvetkov D.S. Nonstoichiometry, Defect Chemistry and Oxygen Transport in Fe-Doped Layered Double Perovskite Cobaltite PrBaCo2−xFexO6−δ (x=0–0.6) Membrane Materials. Membr. 2022;12:1200. doi:10.3390/membranes12121200

Petrov A.N., Zuev A.Yu., Vylkov A.I., Tsvetkov D.S. Equilibrium of point defects and charge transfer in lanthanum cobaltite. Russ. J. Phys. Chem. 2006;80:S128–S133. doi:10.1134/S003602440613022X

Yagovitin R.E., Ivanov I.L., Sereda V.V., Tsvetkov D.S., Malyshkin D.A., Zuev A.Yu. Thermodynamics of advanced Pr1-xBaxCoO3-δ ceramics: enthalpy increments and heat capacity, Ceram. Int. 2026;52:6215–6222. doi:10.1016/j.ceramint.2025.12.380

Knížek K., Hejtmánek J., Jirák Z., Tomeš P., Henry P., André G. Neutron diffraction and heat capacity studies of PrCoO3 and NdCoO3. Phys. Rev. 2009;B79:134103. doi:10.1103/PhysRevB.79.134103

Knížek K., Jirák Z., Hejtmánek J., Veverka M., Maryško M., Maris G., Palstra T.T.M. Structural anomalies associated with the electronic and spin transitions in LnCoO3. Solid and Condensed State Phys. 2005;47:213–220. doi:10.1140/epjb/e2005-00320-3

Berggold K., Kriener M., Becker P., Benomar M., Reuther M., Zobel C., Lorenz T. Anomalous expansion and phonon damping due to the Co spin-state transition in RCoO3 (R=La, Pr, Nd, and Eu). Phys. Rev. B 2008;78:134402. doi:10.1103/PhysRevB.78.134402

Kobayashi Y., Mogi T., Asai K. Spin-State Transition in La1-xPrxCoO3. J. Phys. Soc. Jpn. 2006;75:104703. doi:10.1143/jpsj.75.104703

Tsvetkov D.S., Sereda V.V., Zuev A.Yu. Defect structure and charge transfer in the double perovskite GdBaCo2O6−δ. Solid State Ionics 2011;192:215–219. doi:10.1016/j.ssi.2010.03.022

Petrov A.N., Zuev A.Yu., Vylkov A.I., Tsvetkov D.S. Defect structure and charge transfer in undoped and doped lanthanum cobaltites. J. Mater. Sci. 2007;42:1909–1914. doi:10.1007/s10853-006-0346-7

Politov B.V., Antipinskaya E.A., Shein I.R., Suntsov A.Yu. High-temperature polaronic transport in PrBaCoTa(Nb)O6 perovskite-like phases. J. Phys. Chem. Solids 2020;147:109645. doi:10.1016/j.jpcs.2020.109645

Suntsov A.Yu., Leonidov I.A., Patrakeev M.V., Kozhevnikov V.L. High-temperature electron–hole transport in PrBaCo2O5+δ. J. Solid State Chem. 2011;184:1951–1955. doi:10.1016/j.jssc.2011.05.045

Kostogloudis G.Ch., Ftikos Ch. Characterization of Nd1-xSrxMnO3±δ SOFC Cathode Materials. J. Eur. Ceram. Soc. 1999;19:497–505. doi:10.1016/S0955-2219(98)00221-0

Bucher E., Sitte W. Defect chemical analysis of the electronic conductivity of strontium-substituted lanthanum ferrite. Solid State Ion. 2004;173:23–28. doi:10.1016/j.ssi.2004.07.047

Sukhanov K.S., Gilev A.R., Kiselev E.A., Cherepanov V.A. Functional properties and structure-size factor in La1.4A0.6Ni0.6Fe0.4O4+δ (A=Ca, Sr, Ba). J. Alloys Compd. 2024;990:174369. doi:10.1016/j.jallcom.2024.174369

Davydova M.V., Volkova N.E., Aksenova T.V., Gavrilova L.Ya., Cherepanov V.A. Nonstoichiometry, thermal expansion and conductivity of Ba1-xPrxFe1-yCoyO3-δ solid solutions. Solid State Sciences. 2024;154:107580. doi:10.1016/j.solidstatesciences.2024.107580

Tsvetkov D.S., Tsvetkova N.S., Ivanov I.L., Malyshkin D.A., Sereda V.V., Zuev A.Yu. PrBaCo2O6-δ – Ce0.8Sm0.2O1.9 Composite Cathodes for Intermediate Temperature Solid Oxide Fuel Cells. ECS Transactions. 2015;68:965–976. doi:10.1149/06801.0965ecst

Shu K., Wang C.‑H., Chen G.‑T., Ji Z.‑L., Yan W.‑X., Luo F. Crystal structure and electrical properties of LnCoO3 (Ln=La, Pr, Tb) perovskite. J Mater Sci: Mater Electron 2024;35:2107. doi:10.1007/s10854-024-13874-w

Scherrer B., Harvey A.S., Tanasescu S., Teodorescu F., Botea A., Conder K., Grundy A.N., Martynczuk J., Gauckler L.J. Correlation between electrical properties and thermodynamic stability of ACoO3−δ perovskites (A = La, Pr, Nd, Sm,Gd). Phys. Rev. B. 2011;84:085113. doi:10.1103/PhysRevB.84.085113

Ren Y., Li B., Wang J., Xu X. Synthesis and electrical conductivity of perovskite-type PrCo1-xMgxO3. J. Solid State Chem. 2004;177:3977–3980. doi:10.1016/j.jssc.2004.07.023

Hashimoto H., Kusunose T., Sekino T. Temperature dependence of electrical and thermal properties for perovskite-type rare earth cobalt oxide solid solutions Pr1−xTbxCoO3 and their metal–insulator transition behavior. J. Alloy. Compd. 2010;494:L3–L6. doi:10.1016/j.jallcom.2010.01.011

Hashimoto H., Kusunose T., Sekino T. Influence of ionic sizes of rare earths on thermoelectric properties of perovskite-type rare earth cobalt oxides RCoO3 (R = Pr, Nd, Tb, Dy). J. Alloy. Compd. 2009;484:246–248. doi:10.1016/j.jallcom.2009.04.100




DOI: https://doi.org/10.15826/chimtech.10068

Copyright (c) 2026 Roman Yagovitin, Dmitry Tsvetkov, Ivan Ivanov, Vladimir Sereda, Dmitry Malyshkin, Andrey Zuev

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