Transport features in layered nickelates: correlation between structure, oxygen diffusion, electrical and electrochemical properties
Oxygen migration is increasingly acknowledged as playing an important role in the ionic transport in mixed conductors and influencing the electrode electrochemical performance. The aim of this work was to establish correlations between the structural and electrical properties of undoped (Ln2NiO4 + δ, Ln = La, Pr) and doped (La1.7M0.3NiO4 + δ, M = Ca, Sr, Ba, La0.85Pr0.85Ca0.3NiO4 + δ, Pr1.7Ca0.3NiO4 + δ) layered nickelates and the oxygen diffusion in these materials to determine what influences their electrochemical response. A new technique for temperature programmed isotope exchange of oxides with C18O2 in a flow reactor was applied to investigate oxygen mobility and surface reactivity in the polycrystalline powder samples which provided the means to experimentally demonstrate the appearance of two channels of oxygen migration in the doped materials via cooperative mechanism and via near-dopant position. The electrochemical performance of the electrodes based on the developed materials was found to exhibit a strong dependence on their oxygen transport characteristics.
KeywordsSOFC cathode Ln2NiO4 + δ Ruddlesden–Popper phase Isotope exchange Electrochemical performance
The investigations of oxygen diffusion were supported by the Russian Science Foundation (project 16-13-00112) and structural, electrical, and electrochemical study were supported by the Russian Science Foundation (project 16-19-00104). The work was done using the facilities of the shared-access centers “Composition of compounds,” IHTE and “Ural-M,” IMET UB RAS. Financial support from the Government of the Russian Federation (Agreement 02.A03.21.0006, Act 211) is gratefully acknowledged. We are thankful to Bogdanovich N.M. and Demyanenko T.A. for the sample preparation and to Pelipenko V.V. for the temperature-programmed isotope exchange in closed reactors studies.
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Conflict of interest
The authors declare that they have no conflict of interest.
- 5.Philippeau B, Mauvy F, Mazataud C et al (2013) Comparative study of electrochemical properties of mixed conducting Ln2NiO4+δ (Ln=La, Pr and Nd) and La0.6Sr0.4Fe0.8Co0.2O3−δ as SOFC cathodes associated to Ce0.9Gd0.1O2−δ, La0.8Sr0.2Ga0.8Mg0.2O3−δ and La9Sr1Si6O26.5 electrolytes. Solid State Ionics 249:17–25. https://doi.org/10.1016/j.ssi.2013.06.009 CrossRefGoogle Scholar
- 8.Sadykov VA, Eremeev NF, Usol’tsev VV et al (2013) Mechanism of oxygen transfer in layered lanthanide nickelates Ln2−xNiO4+δ (Ln=La, Pr) and their nanocomposites with Ce0.9Gd0.1O2−δ and Y2(Ti0.8Zr0.2)1.6Mn0.4O7−δ solid electrolytes. Russ J Electrochem 49:645–651. https://doi.org/10.1134/S1023193513070136 CrossRefGoogle Scholar
- 28.Sadykov V, Eremeev N, Sadovskaya E et al (2015) Oxygen mobility and surface reactivity of PrNi1−xCoxO3−δ perovskites and their nanocomposites with Ce0.9Y0.1O2−δ by temperature-programmed isotope exchange experiments. Solid State Ionics 273:35–40. https://doi.org/10.1016/j.ssi.2014.11.021 CrossRefGoogle Scholar
- 30.Pikalova EY, Kolchugin AA, Bogdanovich NM, Bronin DI (2014) Electrical and electrochemical properties of La2–xCaxNiO4+δ and La2–xCaxNiO4+δ-Ce0.8Sm0.2O1.9 cathode materials for intermediate temperature SOFCs. Adv Sci Technol 93:25–30. https://doi.org/10.4028/www.scientific.net/AST.93.25 CrossRefGoogle Scholar
- 37.Muzykantov V, Popovskii V, Boreskov G (1964) Kinetics of isotope exchange in a molecular oxygen––solid oxide system. Kinet Catal 5:624–629Google Scholar
- 39.Boehm E (2002) Les nickelates A2MO4+ð, nouveaux matériaux de cathode pour piles à combustible SOFC moyenne température. Université Sciences et Technologies - Bordeaux I, LilleGoogle Scholar
- 49.Sadykov VA, Pavlova SN, Kharlamova TS et al (2010) Perovskites and their nanocomposites with fluorite-like oxides as materials for solid oxide fuel cells cathodes and oxygen-conducting membranes: mobility and reactivity of the surface/bulk oxygen as a key factor of their performance. In: Borovski M (ed) Perovskites Struct. Prop. Uses. Nova Science Publishers, New York, pp 67–178Google Scholar