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The application of double perovskite cobaltites Ba Ln Co 2 O 6-δ ( Ln = lanthanide element) in electrochemical devices for energy conversion requires control of their properties at operating conditions. This work presents a study of a series of Ba Ln Co 2 O 6-δ ( Ln = La, Pr, Nd) with a focus on the evolution of structural and electrical properties with temperature. Symmetry, oxygen non-stoichiometry, and cobalt valence state have been examined by means of Synchrotron Radiation Powder X-ray Diffraction (SR-PXD), thermogravimetry (TG), and X-ray Absorption Spectroscopy (XAS). The results indicate that all three compositions maintain mainly orthorhombic structure from RT to 1000 °C. Chemical expansion from Co reduction and formation of oxygen vacancies is observed and characterized above 350 °C. Following XAS experiments, the high spin of Co was ascertained in the whole range of temperatures for BLC, BPC, and BNC.

High-Temperature Structural and Electrical Properties of BaLnCo2O6 Positrodes