Insights into Oxygen Migration in LaBaCo2O6−δ Perovskites from In Situ Neutron Powder Diffraction and Bond Valence Site Energy Calculations

Fabian Hesse, Ivan Da Silva, Jan-Willem G. Bos

Research output: Contribution to journalArticlepeer-review

1 Downloads (Pure)

Abstract

Layered cobalt oxide perovskites are important mixed ionic and electronic conductors. Here, we investigate LaBaCo2O6−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 Eb ∼ 2.8 eV for the cubic perovskite to Eb ∼ 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 CoO2 and LaO planes. Vacancy ordering leads to the emergence of additional migration pathways with low-energy barriers, for example, 1D channels with Eb = 0.5 eV and 3D channels with Eb = 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 LnBaCo2O6−δ perovskites with reduced symmetry.
Original languageEnglish
Pages (from-to)1191-1202
Number of pages12
JournalChemistry of Materials
Volume34
Issue number3
Early online date27 Jan 2022
DOIs
Publication statusPublished - 8 Feb 2022

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Fingerprint

Dive into the research topics of 'Insights into Oxygen Migration in LaBaCo2O6−δ Perovskites from In Situ Neutron Powder Diffraction and Bond Valence Site Energy Calculations'. Together they form a unique fingerprint.

Cite this