Impact of Praseodymia Additions and Firing Conditions on Structural and Electrical Transport Properties of 5 mol.% Yttria Partially Stabilized Zirconia (5YSZ)

Ceramics samples with the nominal composition [(ZrO2)0.95(Y2O3)0.05]1-x[PrOy]x and praseodymia contents of x = 0.05–0.15 were prepared by the direct firing of compacted 5YSZ + PrOy mixtures at 1450–1550 °C for 1–9 h and characterized for prospective applicability in reversible solid oxide cells. XRD and SEM/EDS analysis revealed that the dissolution of praseodymium oxide in 5YSZ occurs via the formation of pyrochlore-type Pr2Zr2O7 intermediate. Increasing PrOy additions results in a larger fraction of low-conducting pyrochlore phase and larger porosity, which limit the total electrical conductivity to 2.0–4.6 S/m at 900 °C and 0.28–0.68 S/m at 700 °C in air. A longer time and higher temperature of firing promotes the phase and microstructural homogenization of the ceramics but with comparatively low effect on density and conductivity. High-temperature processing leads to the prevailing 3+ oxidation state of praseodymium cations in fluorite and pyrochlore structures. The fraction of Pr4+ at 600–1000 °C in air is ≤2% and is nearly independent of temperature. 5YSZ ceramics with praseodymia additions remain predominantly oxygen ionic conductors, with p-type electronic contribution increasing with Pr content but not exceeding 2% for x = 0.15 at 700–900 °C. The average thermal expansion coefficients of prepared ceramics are in the range of 10.4–10.7 ppm/K.

Phase Equilibrium in ZrO2-CeO2-Eu2O3 System at a Temperature of 1500 °C

The phase equilibria and structural transformations in the ternary ZrO2-CeO2-Eu2O3 system at 1500 °C were studied by X-ray diffraction and scanning electron microscopy in the overall concentration range. The system was found to constitute fields of solid solutions based on the tetragonal (Т) modification of ZrО2, cubic (С) and monoclinic (B) modifications of Eu2O3, cubic with a fluorite-type structure (F) modifications of СеО2 (ZrО2), and ordered intermediate phase with a pyrochlore-type structure of Eu2Zr2O7 (Py). The refined lattice parameters of the unit cells corresponding to the solid solutions and microstructures of the definite field of compositions for the systems were determined. The peculiarity of the isothermal section of the phase diagram in the ZrO2-СеO2-Eu2O3 system at 1500 °С is the formation of phase equilibria on the basis of the fluorite solid solutions of ZrO2(CeO2) along with other components. There are at least three homogeneous fields of cubic phases. The isothermal section of the ZrO2-CeO2-Eu2O3 system at 1500 °С was constituted of four three-phase regions (C-Eu2O3 + F-CeO2+Py, C-Eu2O3 + F-ZrO2+Py, Py + F-ZrO2 + T-ZrO2, Py + F-CeO2 + T-ZrO2).

Electrode and Electrolyte Materials From Atomistic Simulations: Properties of LixFEPO4 Electrode and Zircon-Based Ionic Conductors

LixFePO4 orthophosphates and fluorite- and pyrochlore-type zirconate materials are widely considered as functional compounds in energy storage devices, either as electrode or solid state electrolyte. These ceramic materials show enhanced cation exchange and anion conductivity properties that makes them attractive for various energy applications. In this contribution we discuss thermodynamic properties of LixFePO4 and yttria-stabilized zirconia compounds, including formation enthalpies, stability, and solubility limits. We found that at ambient conditions LixFePO4 has a large miscibility gap, which is consistent with existing experimental evidence. We show that cubic zirconia becomes stabilized with Y content of ~8%, which is in line with experimental observations. The computed activation energy of 0.92eV and ionic conductivity for oxygen diffusion in yttria-stabilized zirconia are also in line with the measured data, which shows that atomistic modeling can be applied for accurate prediction of key materials properties. We discuss these results with the existing simulation-based data on these materials produced by our group over the last decade. Last, but not least, we discuss similarities of the considered compounds in considering them as materials for energy storage and radiation damage resistant matrices for immobilization of radionuclides.