Oxygen-ion and proton transport in Y3+-doped hexagonal perovskite Ba7In6Al2O19

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In this work, the thermal and electrical properties of the Y3+-doped Ba7In5.9Y0.1Al2O19 phase, characterized by a hexagonal perovskite structure (a = 5.935(7) Å, c = 37.736(8) Å), were studied. It has been established that the phase is capable of incorporating protons and exhibiting proton conductivity. The introduction of an isovalent dopant, yttrium, led to an increase in the concentration of protons (up to the limiting values of Ba7In5.9Y0.1Al2O19 ·0.55H2O), as a result of an increase in the unit cell volume and, accordingly, the free space for the placement of OH–-groups in an oxygen-deficient block containing coordination-unsaturated polyhedra [BaO9]. Isovalent doping led to an increase in the oxygen-ion conductivity, which is due to an increase in interatomic distances and a decrease in the migration activation energy. In a humid atmosphere (pH2O = = 1.92·10–2 atm), the Ba7In5.9Y0.1Al2O19 phase exhibited higher values of proton conductivity compared to the matrix compound Ba7In6Al2O19 and below 500°C it was characterized by dominant proton transport both in air and in a wide range of pO2 (10–18–0.21 atm).

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I. Animitsa

Ural Federal University named after the First President of Russia B. N. Yeltsin

编辑信件的主要联系方式.
Email: Irina.аnimitsa@urfu.ru
俄罗斯联邦, Yekaterinburg

R. Andreev

Ural Federal University named after the First President of Russia B. N. Yeltsin

Email: Irina.аnimitsa@urfu.ru
俄罗斯联邦, Yekaterinburg

D. Korona

Ural Federal University named after the First President of Russia B. N. Yeltsin

Email: Irina.аnimitsa@urfu.ru
俄罗斯联邦, Yekaterinburg

A. Gilev

Ural Federal University named after the First President of Russia B. N. Yeltsin

Email: Irina.аnimitsa@urfu.ru
俄罗斯联邦, Yekaterinburg

S. Nokhrin

Ural Federal University named after the First President of Russia B. N. Yeltsin

Email: Irina.аnimitsa@urfu.ru
俄罗斯联邦, Yekaterinburg

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2. Fig. 1. Experimental, calculated and difference X-ray diffraction patterns, as well as angular locations of reflections of the Ba7In5.9Y0.1Al2O19 sample.

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3. Fig. 2. SEM images of the cleavage surface of a ceramic (a) and powder (b) sample of Ba7In5.9Y0.1Al2O19.

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4. Fig. 3. TG curves of hydrated samples of Ba7In6Al2O19 xH2O and Ba7In5.9Y0.1Al2O19 xH2O.

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5. Fig. 4. Evolution of impedance hodographs with varying temperature in dry (a) and humid (b) air for Ba7In5.9Y0.1Al2O19.

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6. Fig. 5. Dependences of electrical conductivity on the partial pressure of oxygen of the Ba7In5.9Y0.1Al2O19 phase in dry (pH2O = 3.5 10–5 atm) (a) and wet (pH2O = 1.92 10–2 atm) (b) atmospheres, as well as a comparison of isotherms in dry and wet atmospheres (c) and a comparison with the undoped Ba7In6Al2O19 phase at 500°C (d).

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7. Fig. 6. Temperature dependences of oxygen-ion conductivity (a) and oxygen-ion transport numbers (b) for Ba7In6Al2O19 and Ba7In5.9Y0.1Al2O19 in a dry air atmosphere (pH2O = 3.5×10–5 atm).

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8. Fig. 7. Temperature dependences of proton and oxygen-ion conductivities of Ba7In5.9Y0.1Al2O19 and Ba5In1.9Y0.1Al2ZrO13.

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9. Fig. 8. Temperature dependences of proton conductivity and proton transport numbers for the Ba7In6Al2O19 and Ba7In5.9Y0.1Al2O19 phases.

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注意

2 Based on the materials of the lecture at the 17th International Meeting “Fundamental and Applied Problems of Solid State Ionics”, Chernogolovka, June 16–23, 2024.


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