Density functional theory + U analysis of the electronic structure and defect chemistry of LSCF (La 0.5 Sr 0.5 Co 0.25 Fe 0.75 O 3-δ )

Ritzmann, Andrew M.; Dieterich, Johannes M.; Carter, Emily A.

doi:10.1039/c6cp01720g

Density functional theory + U analysis of the electronic structure and defect chemistry of LSCF (La _0.5 Sr _0.5 Co _0.25 Fe _0.75 O _3-δ )

Journal Article · Thu Dec 31 23:00:00 EST 2015 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/c6cp01720g· OSTI ID:1370135

Ritzmann, Andrew M.; Dieterich, Johannes M.; Carter, Emily A.

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. La_1-xSr_xCo_1-yFe_yO_3-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 La_1-xSr_xFeO₃ because of the addition of cobalt, but that minimal electronic structure differences exist between La_0.5Sr_0.5Co_0.25Fe_0.75O₃ and La_0.5Sr_0.5Co_0.5Fe_0.5O₃. The oxygen vacancy (V$$-\atop{o}$$) formation energy (ΔEf,vac) is calculated for V$$-\atop{o}$$ residing in different local environments within La_0.5Sr_0.5Co_0.25Fe_0.75O₃. These results show that Co-V$$-\atop{o}$$-Co configurations have the highest ΔEf,vac, while Co-V$$-\atop{o}$$-Fe have the lowest ΔEf,vac and may act as traps for V$$-\atop{o}$$. We conclude that compositions with more Fe than Co are preferred because the additional Co-V$$-\atop{o}$$-Co sites would lead to higher overall ΔEf,vac (and lower V$$-\atop{o}$$ concentrations), while the trapping strength of the Image Co-V$$-\atop{o}$$-Fe sites is relatively weak (~0.3 eV).

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Heterogeneous Functional Materials Center (HeteroFoaM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

DOE Contract Number:: SC0001061

OSTI ID:: 1370135

Journal Information:: Physical Chemistry Chemical Physics. PCCP (Print), Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Issue: 17 Vol. 18; ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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