Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Predicting Oxygen Off-Stoichiometry and Hydrogen Incorporation in Complex Perovskite Oxides

Journal Article · · Chemistry of Materials

Chemically and structurally complex solid compounds, including those with significant off-stoichiometry, are rapidly extending new material functionality across a variety of applications. Accelerated development of these compounds requires accurate predictions of material defect properties including effective defect formation energies and equilibrium defect concentrations. Traditional first-principles approaches typically examine dilute defect concentrations and relatively ordered atomic structures to identify the lowest energy defect sites. These approaches are rarely suitable for describing the disorder present in these systems and its influence on defect formation, which can lead to unphysically large predictions for defect concentrations. Here, we demonstrate a new method to accurately predict the temperature and pressure dependence of oxygen vacancy concentrations and proton interstitial concentrations in complex oxides. This method extends standard dilute defect calculations to incorporate atomic and magnetic disorder, employs the ensemble descriptions of defect sites resulting in improved predictions of defect formation energies, and accounts for effects beyond the dilute defect limit. To demonstrate our method, we show that the predicted defect concentrations in perovskites used as ceramic fuel cell cathodes, including Ba0.5Sr0.5Fe0.8Zn0.2O3-d, Ba0.5Sr0.5Co0.8Fe0.2O3-d, and BaCo1-x-y-zFexZryYzO3-d, are in good agreement with experimental values, thereby opening the door for predictive design of complex oxides by these applications.

Research Organization:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (EE-3F); USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program
DOE Contract Number:
AC36-08GO28308
OSTI ID:
1843366
Report Number(s):
NREL/JA-5K00-81454; MainId:82227; UUID:ac741a23-8132-4e3b-a429-e7619a45c0ec; MainAdminID:63762
Journal Information:
Chemistry of Materials, Vol. 34, Issue 2
Country of Publication:
United States
Language:
English

References (37)

Recent Progress in the Development of Anode Materials for Solid Oxide Fuel Cells journal April 2011
Energy Conversion with Solid Oxide Fuel Cell Systems: A Review of Concepts and Outlooks for the Short- and Long-Term journal September 2012
Readily processed protonic ceramic fuel cells with high performance at low temperatures journal July 2015
Cathode materials for solid oxide fuel cells: a review journal October 2009
Novel materials for solid oxide fuel cell technologies: A literature review journal October 2017
Investigation of the permeation behavior and stability of a Ba0.5Sr0.5Co0.8Fe0.2O3−δ oxygen membrane journal July 2000
A high-performance cathode for the next generation of solid-oxide fuel cells journal September 2004
A Cobalt-Free Oxygen-Permeable Membrane Based on the Perovskite-Type Oxide Ba0.5Sr0.5Zn0.2Fe0.8O3-δ journal July 2005
Synthesis, electrical and electrochemical properties of Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite oxide for IT-SOFC cathode journal January 2008
High performance protonic ceramic membrane fuel cells (PCMFCs) with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode journal September 2008
Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs journal December 2008
Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations journal January 2009
Convergence of density and hybrid functional defect calculations for compound semiconductors journal September 2013
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation journal July 2013
Intrinsic Material Properties Dictating Oxygen Vacancy Formation Energetics in Metal Oxides journal May 2015
Composition Dependence of the Band Gap and Doping in Cu 2 O -Based Alloys as Predicted by an Extension of the Dilute-Defect Model journal October 2014
Monte Carlo simulations of disorder in ZnSn N 2 and the effects on the electronic structure journal August 2017
Accuracy of quantum Monte Carlo methods for point defects in solids journal August 2010
Thermodynamics of the Heusler alloy Co 2 − x Mn 1 + x Si : A combined density functional theory and cluster expansion study journal March 2009
Structural stability and defect energetics of ZnO from diffusion quantum Monte Carlo journal April 2015
Energetics of quaternary III-V alloys described by incorporation and clustering of impurities journal September 2009
Tunable Oxygen Vacancy Formation Energetics in the Complex Perovskite Oxide Sr x La 1– x Mn y Al 1– y O 3 journal November 2014
Proton conductivity in mixed-conducting BSFZ perovskite from thermogravimetric relaxation journal January 2014
Accurate prediction of defect properties in density functional supercell calculations journal November 2009
Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides journal January 2007
Origins of the doping asymmetry in oxides: Hole doping in NiO versus electron doping in ZnO journal June 2007
Special quasirandom structures journal July 1990
Efficient stochastic generation of special quasirandom structures journal September 2013
The alloy theoretic automated toolkit: A user guide journal December 2002
Magnetic Properties of the System SrCo 1- x Fe x O 3- y journal October 1972
Electric and Magnetic Properties of the Strontium Ferrates journal September 1965
Ferromagnetic Properties of SrFe1−xCoxO3Synthesized under High Pressure journal January 1996
Antiferromagnetic spin structure in below 15K determined by neutron and journal November 2007
Oxygen stoichiometry and expansion behavior of Ba0.5Sr0.5Co0.8Fe0.2O3−δ journal February 2010
Uncertainty of oxygen content in highly nonstoichiometric oxides from neutron diffraction data: example of perovskite-type Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3−δ journal January 2017
Phase Stability and Oxygen Nonstoichiometry of Highly Oxygen-Deficient Perovskite-Type Oxides: A Case Study of (Ba,Sr)(Co,Fe)O 3−δ journal December 2011
Publisher Correction: First-principles calculation of intrinsic defect chemistry and self-doping in PbTe journal November 2017