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

  • Samantha L. Millican
    Samantha L. Millican
    Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309, United States
  • Ann M. Deml
    Ann M. Deml
    Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
    Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
    More by Ann M. Deml
  • Meagan Papac
    Meagan Papac
    Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
    Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
    More by Meagan Papac
  • Andriy Zakutayev
    Andriy Zakutayev
    Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
    Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
  • Ryan O’Hayre
    Ryan O’Hayre
    Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
  • Aaron M. Holder
    Aaron M. Holder
    Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309, United States
    Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
  • Charles B. Musgrave*
    Charles B. Musgrave
    Department of Chemical and Biological Engineering, University of Colorado, Boulder, Colorado 80309, United States
    Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
    Department of Chemistry, University of Colorado, Boulder, Colorado 80309, United States
    Renewable and Sustainable Energy Institute, University of Colorado, Boulder, Colorado 80309, United States
    *Email: [email protected]
  • , and 
  • Vladan Stevanović*
    Vladan Stevanović
    Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401, United States
    Materials Science Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
    *Email: [email protected]
Cite this: Chem. Mater. 2022, 34, 2, 510–518
Publication Date (Web):January 3, 2022
https://doi.org/10.1021/acs.chemmater.0c04765
Copyright © 2022 American Chemical Society

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    Abstract

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    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−δ, Ba0.5Sr0.5Co0.8Fe0.2O3−δ, and BaCo1–xyzFexZryYzO3−δ, are in good agreement with experimental values, thereby opening the door for predictive design of complex oxides by these applications.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.0c04765.

    • Additional computational details for DFT + U calculations; (Figure S1) variation in the total energy of random magnetic configurations for BCFZY compounds; (Figure S2) comparison of calculated and experimental lattice parameters for all compounds; (Figure S3) distribution of oxygen vacancy formation energies for all compounds and proton interstitial formation energies of BCFZY compounds; (Figure S4) density of states for the host and oxygen deficient BCFZY4411 structures; (Figure S5) computationally determined equilibrium oxygen off-stoichiometry under dry conditions for all compounds; and (Figure S6) comparison of computationally determined and experimentally measured oxygen off-stoichiometry for BSCF5582 (PDF)

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    Cited By

    This article is cited by 4 publications.

    1. Muhammad Rizwan Khan, Harshan Reddy Gopidi, Mateusz Wlazło, Oleksandr I. Malyi. Fermi-Level Instability as a Way to Tailor the Properties of La3Te4. The Journal of Physical Chemistry Letters 2023, 14 (7) , 1962-1967. https://doi.org/10.1021/acs.jpclett.2c03701
    2. Jiyun Park, Boyuan Xu, Jie Pan, Dawei Zhang, Stephan Lany, Xingbo Liu, Jian Luo, Yue Qi. Accurate prediction of oxygen vacancy concentration with disordered A-site cations in high-entropy perovskite oxides. npj Computational Materials 2023, 9 (1) https://doi.org/10.1038/s41524-023-00981-1
    3. Wenwen Zhang, Hiroki Muroyama, Yuichi Mikami, Qingshi Liu, Xiaojuan Liu, Toshiaki Matsui, Koichi Eguchi. Effectively enhanced oxygen reduction activity and stability of triple-conducting composite cathodes by strongly interacting interfaces for protonic ceramic fuel cells. Chemical Engineering Journal 2023, 461 , 142056. https://doi.org/10.1016/j.cej.2023.142056
    4. Steven A. Wilson, Ellen B. Stechel, Christopher L. Muhich. Overcoming significant challenges in extracting off-stoichiometric thermodynamics using the compound energy formalism through complementary use of experimental and first principles data: A case study of Ba1-xSrxFeO3-δ. Solid State Ionics 2023, 390 , 116115. https://doi.org/10.1016/j.ssi.2022.116115

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