Ionic conduction mechanism in Ca-doped lanthanum oxychloride

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 5; no. 1; pp. 151 - 156
• Main Authors: Shitara, Kazuki, Kuwabara, Akihide, Hibino, Keisuke, Fujii, Kotaro, Yashima, Masatomo, Hester, James R, Umeda, Masanori, Nunotani, Naoyoshi, Imanaka, Nobuhito
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 07.01.2021
• Subjects: Calcium ions; Density functional theory; First principles; Free energy; Heat of formation; Lanthanum; Mathematical analysis; Point defects; Vacancies
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d0dt02502j

The mechanism of ionic conduction in Ca-doped lanthanum oxychloride (LaOCl) was investigated using first-principles calculations based on density functional theory. The calculations of the point defect formation energies suggest that Cl − ion vacancies and substituted Ca 2+ ions at La sites were dominant point defects. Although the migration energy of an O 2− ion is 0.95 eV, the migration energy of a Cl − ion was calculated to be 0.44 eV, which is consistent with the reported experimental value. These results imply that the main carrier in Ca-doped LaOCl is Cl − ions and ionic conduction occurs by a Cl − ion vacancy mechanism. The mechanism of ionic conduction in Ca-doped lanthanum oxychloride (LaOCl) was investigated using first-principles calculations based on density functional theory.