A Combined Variable-Temperature Neutron Diffraction and Thermogravimetric Analysis Study on a Promising Oxygen...

The present study investigates the temperature-structure-stoichiometry relationship of a promising oxygen electrode SrCo_0.9Nb_0.1O_3-δ over a temperature (T) range from room temperature (RT) to 900 °C. The techniques employed are variable-temperature neutron diffraction (VTND) and thermogravimetric analysis (TGA). At T < 75 °C, VTND reveals a tetragonal (P4/mmm) structure with a G-type magnetic ordering. Above 75 °C, the nucleus structure remains the same, while the magnetic ordering disappears. A phase transition from tetragonal (P4/mmm) to cubic (Pm3̅m) is observed at 412 °C, where the two Co sites and three O sites in the P4/mmm phase converge to one equivalent site, respectively. The phase transition temperature coincides with the peak temperature of oxygen uptake obtained by TGA. It is also observed that the Nb dopant has no preferred Co site to occupy. The oxygen vacancies are mostly located at the O3 site surrounding the Co2 site in the P4/mmm structure. The intermediate-spin state of Co³⁺ at the Co2 site is responsible for the observed distortions of CoO₆ octahedra, i.e., elongation of Co2O₆ octahedra and shortening of Co1O₆ octahedra along the c-axis, which is a phenomenon known as Jahn-Teller distortion. At high temperatures, large thermal displacement factor for O^2- is observed with high concentration of oxygen vacancies, providing a structural environment favorable to high O^2- conductivity in Nb-doped SrCoO₃-based oxygen electrode materials.