TY - JOUR

T1 - Influence of the substitution with rare earth elements on the properties of layered lanthanum nickelate – Part 1: Structure, oxygen transport and electrochemistry evaluation

AU - Pikalova, E.

AU - Eremeev, N.

AU - Sadovskaya, E.

AU - Sadykov, V.

AU - Tsvinkinberg, V.

AU - Pikalova, N.

AU - Kolchugin, A.

AU - Vylkov, A.

AU - Baynov, I.

AU - Filonova, E.

N1 - Funding Information: The electrodes preparation and characterization was partly supported by RFBR project № 20-03-00151 . Materials syntethis and characterization was made in the framework of the budget task UHTE UB RAS, project 122020100324-3 using the equipment of the shared access center “Composition of compounds”, IHTE UB RAS. BIC support of the isotope exchange study by the Ministry of Science and Higher Education of the Russian Federation projects AAAA-A21-121011390009-1 and AAAA-A21-121011390007-7 is acknowledged as well. Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/6

Y1 - 2022/6

N2 - This study is aimed at studying the properties of La2NiO4+δ (LNO) substituted with rare earth elements to increase its oxygen over-stoichiometry and enhance oxygen transport thus improving electrochemical properties of the related electrodes. Materials of the La1.6Ln0.4NiO4+δ series (where Ln = Pr (LPNO), Nd (LNNO), Sm (LSNO), Eu (LENO), Gd (LGNO)) are synthesized by a nitrate combustion technique and their structural features, oxygen over-stoichiometry, and oxygen transport properties are investigated by different methods such as X-ray diffraction, TGA, temperature programmed isotopic oxygen exchange with C18O2 (TPIE) in a flow reactor. The unit cell volume in the La1.6Ln0.4NiO4+δ series decreases from Pr (V = 188.3 Å3) to Gd (V = 186.7 Å3). According to the TGA data, the LNO value of oxygen over-stoichiometry, δ, is equal to 0.15, while all substituted materials, except LGNO, show higher values: 0.16 for LENO, 0.17 for LSNO and LNNO, and the highest value equal to 0.18 has been revealed for LPNO. Oxygen mobility and surface reactivity are studied by the temperature-programmed isotope exchange of oxygen with C18O2 in a flow reactor. All samples can be characterized by a fast oxygen diffusivity provided by cooperative mechanism of oxygen migration involving both regular and highly mobile interstitial oxygen. Variation of oxygen tracer diffusion coefficient with dopant cation nature is probably associated with interstitial oxygen content. The best characteristics have been acquired for Ln = Eu (D⁎ = 2.4∙10−9 cm2/s at 700 °C). Electrochemical properties of the related La1.6Ln0.4NiO4+δ electrodes are investigated in a contact with a Ce0.8Sm0.2O1.9 solid-state electrolyte. The influence of the temperature of the electrode formation and the effect of the collector layer on the electrode electrochemical activity are considered. The LENO, LPNO and LSNO-based electrodes demonstrate low polarization resistance related to the enhanced oxygen diffusion properties. Substitution with Gd, contrarily, significantly deteriorates electrochemical properties of LNO.

AB - This study is aimed at studying the properties of La2NiO4+δ (LNO) substituted with rare earth elements to increase its oxygen over-stoichiometry and enhance oxygen transport thus improving electrochemical properties of the related electrodes. Materials of the La1.6Ln0.4NiO4+δ series (where Ln = Pr (LPNO), Nd (LNNO), Sm (LSNO), Eu (LENO), Gd (LGNO)) are synthesized by a nitrate combustion technique and their structural features, oxygen over-stoichiometry, and oxygen transport properties are investigated by different methods such as X-ray diffraction, TGA, temperature programmed isotopic oxygen exchange with C18O2 (TPIE) in a flow reactor. The unit cell volume in the La1.6Ln0.4NiO4+δ series decreases from Pr (V = 188.3 Å3) to Gd (V = 186.7 Å3). According to the TGA data, the LNO value of oxygen over-stoichiometry, δ, is equal to 0.15, while all substituted materials, except LGNO, show higher values: 0.16 for LENO, 0.17 for LSNO and LNNO, and the highest value equal to 0.18 has been revealed for LPNO. Oxygen mobility and surface reactivity are studied by the temperature-programmed isotope exchange of oxygen with C18O2 in a flow reactor. All samples can be characterized by a fast oxygen diffusivity provided by cooperative mechanism of oxygen migration involving both regular and highly mobile interstitial oxygen. Variation of oxygen tracer diffusion coefficient with dopant cation nature is probably associated with interstitial oxygen content. The best characteristics have been acquired for Ln = Eu (D⁎ = 2.4∙10−9 cm2/s at 700 °C). Electrochemical properties of the related La1.6Ln0.4NiO4+δ electrodes are investigated in a contact with a Ce0.8Sm0.2O1.9 solid-state electrolyte. The influence of the temperature of the electrode formation and the effect of the collector layer on the electrode electrochemical activity are considered. The LENO, LPNO and LSNO-based electrodes demonstrate low polarization resistance related to the enhanced oxygen diffusion properties. Substitution with Gd, contrarily, significantly deteriorates electrochemical properties of LNO.

KW - Air electrode

KW - Isotope exchange

KW - LaNiO

KW - Oxygen over-stoichiometry

KW - Oxygen transport

KW - Polarization resistance

KW - Rare earth element

KW - SOFC

KW - La2NiO4+δ

UR - http://www.scopus.com/inward/record.url?scp=85127094575&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/4c2578ec-9a94-3da4-9700-6c86a0476d4d/

U2 - 10.1016/j.ssi.2022.115903

DO - 10.1016/j.ssi.2022.115903

M3 - Article

AN - SCOPUS:85127094575

VL - 379

JO - Solid State Ionics

JF - Solid State Ionics

SN - 0167-2738

M1 - 115903

ER -