Insights into Oxygen Migration in LaBaCo(2)O(6−δ) Perovskites from In Situ Neutron Powder Diffraction and Bond Valence Site Energy Calculations

[Image: see text] Layered cobalt oxide perovskites are important mixed ionic and electronic conductors. Here, we investigate LaBaCo(2)O(6−δ) using in situ neutron powder diffraction. This composition is unique because it can be prepared in cubic, layered, and vacancy-ordered forms. Thermogravimetric analysis and diffraction reveal that layered and disordered samples have near-identical oxygen cycling capacities. Migration barriers for oxide ion conduction calculated using the bond valence site energy approach vary from E(b) ∼ 2.8 eV for the cubic perovskite to E(b) ∼ 1.5 eV for 2D transport in the layered system. Vacancy-ordered superstructures were observed at low temperatures, 350–400 °C for δ = 0.25 and δ = 0.5. The vacancy ordering at δ = 0.5 is different from the widely reported structure and involves oxygen sites in both CoO(2) and LaO planes. Vacancy ordering leads to the emergence of additional migration pathways with low-energy barriers, for example, 1D channels with E(b) = 0.5 eV and 3D channels with E(b) = 2.2 eV. The emergence of these channels is caused by the strong orthorhombic distortion of the crystal structure. These results demonstrate that there is potential scope to manipulate ionic transport in vacancy-ordered LnBaCo(2)O(6−δ) perovskites with reduced symmetry.