Oxide ion transport in Sr2Fe1.5Mo0.5O6-δ, a mixed ion-electron conductor: new insights from first principles modeling

Muñoz-García, Ana B.; Pavone, Michele; Ritzmann, Andrew M.; Carter, Emily A.

doi:10.1039/c3cp50995h

Title: Oxide ion transport in Sr₂Fe_1.5Mo_0.5O_6-δ, a mixed ion-electron conductor: new insights from first principles modeling

Journal Article · Tue Jan 01 00:00:00 EST 2013 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/c3cp50995h· OSTI ID:1381925

Muñoz-García, Ana B.; Pavone, Michele; Ritzmann, Andrew M.; Carter, Emily A.

We use ab initio density functional theory + U calculations to characterize the oxide ion diffusion process in bulk Sr2Fe1.5Mo0.5O6-δ (SFMO) by analyzing the formation and migration of oxygen vacancies. We show that SFMO's remarkable ionic conductivity arises from its intrinsic content of oxygen vacancies and a predicted very low migration barrier of such vacancies. Theoretical analysis of the electronic structure reveals a crucial role played by strongly hybridized Fe 3d/O 2p states to achieve the attendant mixed ion-electron conductor character so important for intermediate temperature fuel cell operation. We predict a next-nearest-neighbor-type migration pathway for the O2- ion should dominate. The low energy barrier of this pathway is mainly related to electrostatic interactions with homogeneously distributed Mo in the SFMO sublattice. We identify the reasons why Fe-rich perovskites, with the key addition of a certain concentration of Mo, produce excellent electronic and ionic transport properties so crucial for efficient operation of intermediate temperature solid oxide fuel cells.

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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)

DOE Contract Number:: SC0001061

OSTI ID:: 1381925

Journal Information:: Physical Chemistry Chemical Physics. PCCP (Print), Vol. 15, Issue 17; Related Information: HeteroFoaM partners with University of South Carolina (lead); University of California, Santa Barbara; University of Connecticut; Georgia Institute of Technology; Princeton University; Rochester Institute of Technology; Savannah River National Laboratory; University of South Carolina; University of Utah; ISSN 1463-9076

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

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Title: Oxide ion transport in Sr2Fe1.5Mo0.5O6-δ, a mixed ion-electron conductor: new insights from first principles modeling

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Title: Oxide ion transport in Sr₂Fe_1.5Mo_0.5O_6-δ, a mixed ion-electron conductor: new insights from first principles modeling