Density functional theory + U analysis of the electronic structure and defect chemistry of LSCF (La0.5Sr0.5Co0.25Fe0.75O3-δ)

Andrew M Ritzmann; Johannes M Dieterich; Emily A Carter

doi:10.1039/c6cp01720g

Density functional theory + U analysis of the electronic structure and defect chemistry of LSCF (La0.5Sr0.5Co0.25Fe0.75O3-δ)

Phys Chem Chem Phys. 2016 Apr 28;18(17):12260-9. doi: 10.1039/c6cp01720g.

Authors

Andrew M Ritzmann¹, Johannes M Dieterich², Emily A Carter³

Affiliations

¹ Department of Chemical and Biological Engineering, Princeton University, Princeton, NJ 08544, USA.
² Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544, USA.
³ Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544, USA and Program in Applied and Computational Mathematics, Andlinger Center for Energy and the Environment, Princeton University, Princeton, NJ 08544, USA. eac@princeton.edu.

PMID: 27079696
DOI: 10.1039/c6cp01720g

Abstract

Reducing operating temperatures is a key step in making solid oxide fuel cell (SOFC) technology viable. A promising strategy for accomplishing this goal is employing mixed ion-electron conducting (MIEC) cathodes. La1-xSrxCo1-yFeyO3-δ (LSCF) is the most widely employed MIEC cathode material; however, rational optimization of the composition of LSCF requires fundamental insight linking its electronic structure to its defect chemistry. To provide the necessary insight, density functional theory plus U (DFT+U) calculations are used to investigate the electronic structure of LSCF (xSr = 0.50, yCo = 0.25). The DFT+U calculations show that LSCF has a significantly different electronic structure than La1-xSrxFeO3 because of the addition of cobalt, but that minimal electronic structure differences exist between La0.5Sr0.5Co0.25Fe0.75O3 and La0.5Sr0.5Co0.5Fe0.5O3. The oxygen vacancy formation energy (ΔEf,vac) is calculated for residing in different local environments within La0.5Sr0.5Co0.25Fe0.75O3. These results show that configurations have the highest ΔEf,vac, while have the lowest ΔEf,vac and may act as traps for . We conclude that compositions with more Fe than Co are preferred because the additional sites would lead to higher overall ΔEf,vac (and lower concentrations), while the trapping strength of the sites is relatively weak (∼0.3 eV).

Publication types

Research Support, U.S. Gov't, Non-P.H.S.