Ni-doping effects on formation and migration of oxygen vacancies in SrFe1−xNixO3−δ oxygen carriers

Ni is a promising B-site doping element capable of improving the oxygen carrier performance of SrFeO3 perovskite. In this work, the effect of Ni doping on the formation and migration of oxygen vacancies in SrFe1-xNixO3-δ (x = 0, 0.0625, 0.125, 0.1875, and 0.25) is investigated using density functional theory calculations. Our results show that the oxygen vacancies formed from Ni-O-Fe chains exhibit lower formation energy (Ef) compared to those from Fe-O-Fe chains in each doping system. Additionally, Ef generally decreases with an increase of Ni content. This Ni-promoted formation of VO is attributed to three factors: weakened Ni-O bonding, the closure of O-2p states to the Fermi level by Ni-O hybridization, and Ni3+ decreasing the positive charges to be compensated by VO formation. Due to these multiple advantages, a modest Ni doping of x = 0.25 can induce a higher PO2 and a lower T comparted to the relatively larger Co doping of x = 0.5, thermodynamically. Kinetically, Ni-doping appears to be a disadvantage as it hinders oxygen migration, due to a higher oxygen migration barrier through SrSrNi compared to the SrSrFe pathway. However, the overall oxygen ion conduction would not be significantly influenced by hopping through a nearby pathway of SrSrFe with a low migration barrier in a system doped with a small amount of Ni. In a word, a small amount of Ni doping has an advantage over Co doping in terms of enhancing the oxygen carrier performance of the parent SrFeO3 system.