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Materials formulated as La(2-x)Sr(x)NiO(4+delta) (0

A novel perovskite oxide with the title composition has been prepared by soft-chemistry procedures followed by thermal treatments at 1000 °C. This polycrystalline sample has been characterized by temperature-dependent neutron powder diffraction (NPD), thermal analysis, electrical conductivity, and thermal expansion measurements, in order to evaluate its potential use as a mixed electronic-ionic conductor in intermediate-temperature solid oxide fuel cells (IT-SOFCs). At room temperature (RT), the sample adopts a tetragonal superstructure of perovskite with a ) a 0 , c ) 2a 0 (a 0 ≈ 3.9 Å) defined in the P4/mmm space group. Co and Sb are distributed at random over the octahedral positions of the perovskite; flattened and elongated (Co,Sb)O 6 octahedra alternate along the c axis, sharing corners in a three-dimensional array (3C-like structure). The refinement of the oxygen occupancy factors yields the crystallographic formula SrCo 0.9 Sb 0.1 O 2.73(4) ; the oxygen vacancies are located at the equatorial O2 and O3 atoms, in alternating layers with different occupancy. O3 atoms exhibit, at RT, large thermal factors of 5.3 Å 2 , suggesting a considerable mobility. This structure is stable up to 500 °C; between 500 and 700 °C, an order-disorder phase transition takes place to give a fully disordered simple-cubic perovskite with a ) a 0 (space group Pm3 j m); this structure is shown to be stable up to 940 °C from NPD data. This is a second-order nonreconstructive transition, which is not observed at the differential thermal analysis curves, although it is probably responsible for a subtle change of slope at 650 °C in the thermal expansion curve. The thermal evolution of the electrical conductivity exhibits a maximum of 300 S • cm -1 at 400 °C; above this electronic transition, the conductivity regularly decreases, but it is still well above the required 100 S • cm -1 in the temperature region 650-850 °C corresponding to the working regime of a IT-SOFC.

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