The application of double perovskite cobaltites BaLnCo₂O_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 BaLnCo₂O_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.

The cubic Ba_0.5La_0.5CoO_3‐δ was synthesized using solid state reaction. The structural properties were determined by the simultaneous refinement of Synchrotron Powder X‐ray Diffraction and Neutron Powder Diffraction data. Iodometric titration was used to examine the oxygen stoichiometry and average cobalt oxidation state. Low‐temperature magnetic studies show soft ferromagnetic character of fully oxidized material, with θ_P = 198(3) K and µ_eff = 2.11(2) µ_B. Electric measurements show the thermally activated nature of conductivity at low temperatures, whereas, due to the variable oxidation and spin state of cobalt, a single charge transport mechanism cannot be distinguished. Around room temperature, a wide transition from thermally activated conductivity to semi‐metallic behavior is observed. Under the inert atmosphere, the oxygen content lowers and the cation ordering takes place, leading to coexistence of two, ordered and disordered, phases. As a result of this change, thermally activated conductivity is observed also at high temperatures in inert atmosphere.

The modified DC Hebb–Wagner polarization method with an electron and oxygen-ion blocking electrode was for the first time applied to study partial protonic conductivity in triple-conducting oxides: BaZr_0.7Ce_0.2Y_0.1O_3−δ and BaGd_0.3La_0.7Co₂O_6−δ.

Mixed conducting perovskite BGLC82 undergoes an order–disorder transition upon hydration. Crystalline phases in BGLC have been identified and quantified with respect to volume percent and cation occupancy vs. La fraction.