Tailoring Ni and Sr2Mg0.25Ni0.75MoO6−δ Cermet Compositions for Designing the Fuel Electrodes of Solid Oxide Electrochemical Cells
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials Preparation
2.2. Materials Characterization
3. Results and Discussion
3.1. Phase Relation
3.2. Thermal Behaviour
- The molybdenum ions reduction, Mo6+ → Mo5+ (Equation (2)), results in a slight increase in the average ionic radii of elements occupied B-position of the A2BB’O6 structure, since r(Mo6+) = 0.59 Å and r(Mo5+) = 0.61 Å [45].
- Together with a minor strain in cationic sublattice, the dimension change (contraction) in the anionic sublattice is estimated to be more pronounced due to oxygen desorption ( = 1.40 Å, = 1.18 Å [46,47]) occurring as a compensation of the Mo-ions reduction process. Here, the ionic radii values are provided using the Shannon’s system [48].
- NiO undergoes a complete reduction in a hydrogen atmosphere until the formation of a Ni metallic phase. The volume changes during this reduction amount ~40% [49].
3.3. Conductivity Behaviour
3.4. Microstructural Features
4. Conclusions
- All the materials were stable in both oxidising and reducing atmospheres. The reduced samples were found to comprise dual-phase materials, while an impurity SrMoO4 phase was detected along with two target phases for the oxidised samples.
- Thermal expansion of the studied composite materials was linear over the entire temperature range (200–800 °C); the calculated TECs values remained more or less consistent with a variation in composition, decreasing from the oxidised to the reduced samples.
- The total conductivity of the reduced composites did not exceed 3 S cm−1 at 800 °C at 15 ≤ x, mol.% ≤ 70; whereas, it amounts to 450 S cm−1 for x = 85 mol.% at the same temperature.
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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x in (1−x)Sr2Mg0.25Ni0.75MoO6−δ + xNiO | αox·106, К−1 | x in (1−x)Sr2Mg0.25Ni0.75MoO6−δ + xNi | αred·106, К−1 |
---|---|---|---|
0 | 14.6 [34] | 0 | 14.0 [34] |
15 | 15.1 | 15 | 13.8 |
30 | 15.6 | 30 | 13.9 |
50 | 15.6 | 50 | 14.0 |
70 | 15.6 | 70 | 13.9 |
85 | 15.4 | 85 | 14.5 |
100 | 23.1 (200–235 °C) 16.6 (235–800 °C) | 100 | 17.0 (200–580 °C) 21.2 (580–800 °C) |
x, Ni content | σ, S cm−1 | Ea, eV |
---|---|---|
15 | 0.79 | 0.11 (500–650 °C), 0.23 (650–800 °C) |
30 | 1.18 | 0.18 (500–650 °C), 0.33 (650–800 °C) |
50 | 1.01 | 0.19 (500–650 °C), 0.30 (650–800 °C) |
70 | 2.66 | 0.23 (500–650 °C), 0.43 (650–800 °C) |
85 | 458 | – (500–600 °C), 0.21 (650–800 °C) |
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Skutina, L.S.; Vylkov, A.A.; Kuznetsov, D.K.; Medvedev, D.A.; Shur, V.Y. Tailoring Ni and Sr2Mg0.25Ni0.75MoO6−δ Cermet Compositions for Designing the Fuel Electrodes of Solid Oxide Electrochemical Cells. Energies 2019, 12, 2394. https://doi.org/10.3390/en12122394
Skutina LS, Vylkov AA, Kuznetsov DK, Medvedev DA, Shur VY. Tailoring Ni and Sr2Mg0.25Ni0.75MoO6−δ Cermet Compositions for Designing the Fuel Electrodes of Solid Oxide Electrochemical Cells. Energies. 2019; 12(12):2394. https://doi.org/10.3390/en12122394
Chicago/Turabian StyleSkutina, Lubov S., Aleksey A. Vylkov, Dmitry K. Kuznetsov, Dmitry A. Medvedev, and Vladimir Ya. Shur. 2019. "Tailoring Ni and Sr2Mg0.25Ni0.75MoO6−δ Cermet Compositions for Designing the Fuel Electrodes of Solid Oxide Electrochemical Cells" Energies 12, no. 12: 2394. https://doi.org/10.3390/en12122394