Predicting Thermochemical Equilibria with Interacting Defects: Alloys for Water Splitting
Abstract
Solar thermochemical hydrogen is one of the few potential routes towards direct fuel production from renewable energy sources, but the thermodynamic boundary conditions for efficient and economic energy conversion are challenging. Success or failure of a given oxide working material depends on the subtle balance between enthalpy and entropy contributions in the redox processes. Developing a mechanistic understanding of the behavior of materials on the basis of atomistic models and first-principles calculations is an important part of advancing the technology. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox-active defects start to interact with each other, thereby impeding the formation of additional defects. This problem is of more general importance to applications that rely on high levels of off-stoichiometry or doping, including, for example, batteries, thermoelectrics, and ceramic fuel cells. To account for such repulsive defect interactions, we introduce a statistical mechanics approach, defining an expression for the free energy of defect interaction based on limited sampling of defect configurations in density functional theory supercell calculations. The parameterization of this energy contribution as a function of defect concentration and temperature allows on-the-fly simulation of thermochemical equilibria. The approach consistently incorporates finite temperature effects by includingmore »
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)
- OSTI Identifier:
- 2305765
- Alternate Identifier(s):
- OSTI ID: 2316013
- Report Number(s):
- NREL/JA-5K00-87302
Journal ID: ISSN 2768-5608; 013008
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Published Article
- Journal Name:
- PRX Energy
- Additional Journal Information:
- Journal Name: PRX Energy Journal Volume: 3 Journal Issue: 1; Journal ID: ISSN 2768-5608
- Publisher:
- American Physical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 08 HYDROGEN; defect equilibria; density functional theory; solar thermochemical hydrogen
Citation Formats
Goyal, Anuj, Sanders, Michael D., O’Hayre, Ryan P., and Lany, Stephan. Predicting Thermochemical Equilibria with Interacting Defects: Sr 1 − x Ce x Mn O 3 − δ Alloys for Water Splitting. United States: N. p., 2024.
Web. doi:10.1103/PRXEnergy.3.013008.
Goyal, Anuj, Sanders, Michael D., O’Hayre, Ryan P., & Lany, Stephan. Predicting Thermochemical Equilibria with Interacting Defects: Sr 1 − x Ce x Mn O 3 − δ Alloys for Water Splitting. United States. https://doi.org/10.1103/PRXEnergy.3.013008
Goyal, Anuj, Sanders, Michael D., O’Hayre, Ryan P., and Lany, Stephan. Fri .
"Predicting Thermochemical Equilibria with Interacting Defects: Sr 1 − x Ce x Mn O 3 − δ Alloys for Water Splitting". United States. https://doi.org/10.1103/PRXEnergy.3.013008.
@article{osti_2305765,
title = {Predicting Thermochemical Equilibria with Interacting Defects: Sr 1 − x Ce x Mn O 3 − δ Alloys for Water Splitting},
author = {Goyal, Anuj and Sanders, Michael D. and O’Hayre, Ryan P. and Lany, Stephan},
abstractNote = {Solar thermochemical hydrogen is one of the few potential routes towards direct fuel production from renewable energy sources, but the thermodynamic boundary conditions for efficient and economic energy conversion are challenging. Success or failure of a given oxide working material depends on the subtle balance between enthalpy and entropy contributions in the redox processes. Developing a mechanistic understanding of the behavior of materials on the basis of atomistic models and first-principles calculations is an important part of advancing the technology. One challenge is to quantitatively predict thermochemical equilibria at high concentrations when the redox-active defects start to interact with each other, thereby impeding the formation of additional defects. This problem is of more general importance to applications that rely on high levels of off-stoichiometry or doping, including, for example, batteries, thermoelectrics, and ceramic fuel cells. To account for such repulsive defect interactions, we introduce a statistical mechanics approach, defining an expression for the free energy of defect interaction based on limited sampling of defect configurations in density functional theory supercell calculations. The parameterization of this energy contribution as a function of defect concentration and temperature allows on-the-fly simulation of thermochemical equilibria. The approach consistently incorporates finite temperature effects by including the leading contributions to the temperature-dependent free energy for the case at hand, i.e., the ideal gas and configurational enthalpies and entropies. We demonstrate the capability and utility of the approach by simulating the water splitting redox processes for Sr1-xCexMnO3-δ alloys.},
doi = {10.1103/PRXEnergy.3.013008},
journal = {PRX Energy},
number = 1,
volume = 3,
place = {United States},
year = {Fri Feb 16 00:00:00 EST 2024},
month = {Fri Feb 16 00:00:00 EST 2024}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1103/PRXEnergy.3.013008
https://doi.org/10.1103/PRXEnergy.3.013008
Other availability
Search WorldCat to find libraries that may hold this journal
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Semiconducting transition metal oxides
journal, June 2015
- Lany, Stephan
- Journal of Physics: Condensed Matter, Vol. 27, Issue 28
Outstanding Properties and Performance of CaTi0.5Mn0.5O3–δ for Solar-Driven Thermochemical Hydrogen Production
journal, February 2021
- Qian, Xin; He, Jiangang; Mastronardo, Emanuela
- Matter, Vol. 4, Issue 2
Perfect short-range ordered alloy with line-compound-like properties in the ZnSnN2:ZnO system
journal, May 2020
- Pan, Jie; Cordell, Jacob J.; Tucker, Garritt J.
- npj Computational Materials, Vol. 6, Issue 1
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Polymorphic energy ordering of MgO, ZnO, GaN, and MnO within the random phase approximation
journal, May 2013
- Peng, Haowei; Lany, Stephan
- Physical Review B, Vol. 87, Issue 17
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
Insulating gap in the transition-metal oxides: A calculation using the local-spin-density approximation with the on-site Coulomb U correlation correction
journal, April 1994
- Wei, Pan; Qi, Zheng Qing
- Physical Review B, Vol. 49, Issue 16
Exploring Ca–Ce–M–O (M = 3d Transition Metal) Oxide Perovskites for Solar Thermochemical Applications
journal, November 2020
- Sai Gautam, Gopalakrishnan; Stechel, Ellen B.; Carter, Emily A.
- Chemistry of Materials, Vol. 32, Issue 23
Defect graph neural networks for materials discovery in high-temperature clean-energy applications
journal, August 2023
- Witman, Matthew D.; Goyal, Anuj; Ogitsu, Tadashi
- Nature Computational Science, Vol. 3, Issue 8
The system SrMnO3−x
journal, April 1970
- Negas, Taki; Roth, Robert S.
- Journal of Solid State Chemistry, Vol. 1, Issue 3-4
Computational Fermi level engineering and doping-type conversion of Mg:Ga 2 O 3 via three-step synthesis process
journal, June 2021
- Goyal, Anuj; Zakutayev, Andriy; Stevanović, Vladan
- Journal of Applied Physics, Vol. 129, Issue 24
Evaluating transition metal oxides within DFT-SCAN and frameworks for solar thermochemical applications
journal, September 2018
- Sai Gautam, Gopalakrishnan; Carter, Emily A.
- Physical Review Materials, Vol. 2, Issue 9
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998
- Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
- Physical Review B, Vol. 57, Issue 3, p. 1505-1509
High-throughput DFT calculations of formation energy, stability and oxygen vacancy formation energy of ABO3 perovskites
journal, October 2017
- Emery, Antoine A.; Wolverton, Chris
- Scientific Data, Vol. 4, Issue 1
Nature of the octahedral tilting phase transitions in perovskites: A case study of
journal, January 2018
- Klarbring, Johan; Simak, Sergei I.
- Physical Review B, Vol. 97, Issue 2
Predicting Oxygen Off-Stoichiometry and Hydrogen Incorporation in Complex Perovskite Oxides
journal, January 2022
- Millican, Samantha L.; Deml, Ann M.; Papac, Meagan
- Chemistry of Materials, Vol. 34, Issue 2
Intrinsic inhomogeneity in the electron-doped manganite Sr0.95Ce0.05MnO3
journal, January 2007
- Wu, H. Y.; Ruan, K. Q.; Huang, S. L.
- Solid State Communications, Vol. 141, Issue 4
Solar thermochemical fuels: Present status and future prospects
journal, May 2022
- Warren, Kent J.; Weimer, Alan W.
- Solar Compass, Vol. 1
Redox Defect Thermochemistry of FeAl 2 O 4 Hercynite in Water Splitting from First-Principles Methods
journal, January 2022
- Millican, Samantha L.; Clary, Jacob M.; Musgrave, Charles B.
- Chemistry of Materials, Vol. 34, Issue 2
A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 2
Relative energies and electronic structures of CoO polymorphs through ab initio diffusion quantum Monte Carlo
journal, October 2018
- Saritas, Kayahan; Krogel, Jaron T.; Reboredo, Fernando A.
- Physical Review B, Vol. 98, Issue 15
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 124, Issue 21
Phase Identification of the Layered Perovskite Ce x Sr 2– x MnO 4 and Application for Solar Thermochemical Water Splitting
journal, May 2019
- Barcellos, Debora R.; Coury, Francisco G.; Emery, Antoine
- Inorganic Chemistry, Vol. 58, Issue 12
Light- and bias-induced metastabilities in Cu(In,Ga)Se[sub 2] based solar cells caused by the (V[sub Se]-V[sub Cu]) vacancy complex
journal, January 2006
- Lany, Stephan; Zunger, Alex
- Journal of Applied Physics, Vol. 100, Issue 11
Giant onsite electronic entropy enhances the performance of ceria for water splitting
journal, August 2017
- Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A.
- Nature Communications, Vol. 8, Issue 1
Magnetic Structure of the Cubic Perovskite Type SrMnO 3
journal, July 1974
- Takeda, Takayoshi; Ōhara, Sōji
- Journal of the Physical Society of Japan, Vol. 37, Issue 1
Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides
journal, January 2007
- Lany, Stephan; Zunger, Alex
- Physical Review Letters, Vol. 98, Issue 4
Hybrid functionals applied to extended systems
journal, January 2008
- Marsman, M.; Paier, J.; Stroppa, A.
- Journal of Physics: Condensed Matter, Vol. 20, Issue 6
Multiple and nonlocal cation redox in Ca–Ce–Ti–Mn oxide perovskites for solar thermochemical applications
journal, January 2023
- Wexler, Robert B.; Sai Gautam, Gopalakrishnan; Bell, Robert T.
- Energy & Environmental Science, Vol. 16, Issue 6
Interplay between Composition, Electronic Structure, Disorder, and Doping due to Dual Sublattice Mixing in Nonequilibrium Synthesis of ZnSnN 2 :O
journal, January 2019
- Pan, Jie; Cordell, Jacob; Tucker, Garritt J.
- Advanced Materials, Vol. 31, Issue 11
Compositionally Complex Perovskite Oxides for Solar Thermochemical Water Splitting
journal, February 2023
- Zhang, Dawei; De Santiago, Héctor A.; Xu, Boyuan
- Chemistry of Materials
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies
journal, March 2012
- Stevanović, Vladan; Lany, Stephan; Zhang, Xiuwen
- Physical Review B, Vol. 85, Issue 11
BaCe 0.25 Mn 0.75 O 3−δ —a promising perovskite-type oxide for solar thermochemical hydrogen production
journal, January 2018
- R. Barcellos, Debora; Sanders, Michael D.; Tong, Jianhua
- Energy & Environmental Science, Vol. 11, Issue 11
Jahn-Teller distortion and magnetoresistance in electron doped Sr1-xCexMnO3 (x = 0.1, 0.2, 0.3 and 0.4)
journal, March 2000
- Sundaresan, A.; Tholence, J. L.; Maignan, A.
- The European Physical Journal B, Vol. 14, Issue 3
Composition, structure, and stability of as a function of oxygen pressure
journal, December 2001
- Reuter, Karsten; Scheffler, Matthias
- Physical Review B, Vol. 65, Issue 3
Energetics of quaternary III-V alloys described by incorporation and clustering of impurities
journal, September 2009
- Biswas, Koushik; Lany, Stephan
- Physical Review B, Vol. 80, Issue 11
The thermochemical properties of BaCeO3(s) and SrCeO3(s) fromT=(5 to 1500) K
journal, April 1998
- Cordfunke, E. H. P.; Booij, A. S.; Huntelaar, M. E.
- The Journal of Chemical Thermodynamics, Vol. 30, Issue 4
Energy materials screening with defect graph neural networks
journal, August 2023
- ,
- Nature Computational Science, Vol. 3, Issue 8, p. 671-672
A computational framework for automation of point defect calculations
journal, April 2017
- Goyal, Anuj; Gorai, Prashun; Peng, Haowei
- Computational Materials Science, Vol. 130
Convergence of density and hybrid functional defect calculations for compound semiconductors
journal, September 2013
- Peng, Haowei; Scanlon, David O.; Stevanovic, Vladan
- Physical Review B, Vol. 88, Issue 11
Experimental Vibrational Zero-Point Energies: Diatomic Molecules
journal, June 2007
- Irikura, Karl K.
- Journal of Physical and Chemical Reference Data, Vol. 36, Issue 2
Computational discovery of stable and metastable ternary oxynitrides
journal, June 2021
- Sharan, Abhishek; Lany, Stephan
- The Journal of Chemical Physics, Vol. 154, Issue 23
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles
journal, February 2018
- Lany, Stephan
- The Journal of Chemical Physics, Vol. 148, Issue 7
Structural, Thermal and Electrical Properties of Ce-Doped SrMnO3
journal, March 2000
- Hashimoto, S.; Iwahara, H.
- Journal of Electroceramics, Vol. 4, Issue 1, p. 225-231
A thermochemical study of ceria: exploiting an old material for new modes of energy conversion and CO 2 mitigation
journal, July 2010
- Chueh, William C.; Haile, Sossina M.
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 368, Issue 1923
First-principles thermodynamic modeling of atomic ordering in yttria-stabilized zirconia
journal, October 2010
- Dalach, P.; Ellis, D. E.; van de Walle, A.
- Physical Review B, Vol. 82, Issue 14
New Method for Calculating the One-Particle Green's Function with Application to the Electron-Gas Problem
journal, August 1965
- Hedin, Lars
- Physical Review, Vol. 139, Issue 3A
Renewable energy carriers derived from concentrating solar power and nonstoichiometric oxides
journal, April 2017
- McDaniel, Anthony H.
- Current Opinion in Green and Sustainable Chemistry, Vol. 4
Polaron size and shape effects on oxygen vacancy interactions in lanthanum strontium ferrite
journal, January 2017
- Das, Tridip; Nicholas, Jason D.; Qi, Yue
- Journal of Materials Chemistry A, Vol. 5, Issue 47
Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion
journal, October 1991
- Zhang, S.; Northrup, John
- Physical Review Letters, Vol. 67, Issue 17
A First‐Principles‐Based Sub‐Lattice Formalism for Predicting Off‐Stoichiometry in Materials for Solar Thermochemical Applications: The Example of Ceria
journal, August 2020
- Sai Gautam, Gopalakrishnan; Stechel, Ellen B.; Carter, Emily A.
- Advanced Theory and Simulations, Vol. 3, Issue 9
FINDSYM : program for identifying the space-group symmetry of a crystal
journal, January 2005
- Stokes, Harold T.; Hatch, Dorian M.
- Journal of Applied Crystallography, Vol. 38, Issue 1
A Computational Framework to Accelerate the Discovery of Perovskites for Solar Thermochemical Hydrogen Production: Identification of Gd Perovskite Oxide Redox Mediators
journal, March 2022
- Bare, Zachary J. L.; Morelock, Ryan J.; Musgrave, Charles B.
- Advanced Functional Materials, Vol. 32, Issue 25
Band theory and Mott insulators: Hubbard U instead of Stoner I
journal, July 1991
- Anisimov, Vladimir I.; Zaanen, Jan; Andersen, Ole K.
- Physical Review B, Vol. 44, Issue 3, p. 943-954
Band-structure calculations for the 3 transition metal oxides in
journal, February 2013
- Lany, Stephan
- Physical Review B, Vol. 87, Issue 8
The alloy theoretic automated toolkit: A user guide
journal, December 2002
- van de Walle, A.; Asta, M.; Ceder, G.
- Calphad, Vol. 26, Issue 4
Sr- and Mn-doped LaAlO3−δ for solar thermochemical H2 and CO production
journal, January 2013
- McDaniel, Anthony H.; Miller, Elizabeth C.; Arifin, Darwin
- Energy & Environmental Science, Vol. 6, Issue 8
Stabilization of Ternary Compounds via Ordered Arrays of Defect Pairs
journal, May 1997
- Zhang, S. B.; Wei, Su-Huai; Zunger, Alex
- Physical Review Letters, Vol. 78, Issue 21
Revisiting the Terawatt Challenge
journal, March 2020
- Kurtz, Sarah R.; Leilaeioun, Ashling (Mehdi); King, Richard R.
- MRS Bulletin, Vol. 45, Issue 3
Special quasirandom structures
journal, July 1990
- Zunger, Alex; Wei, S.-H.; Ferreira, L. G.
- Physical Review Letters, Vol. 65, Issue 3, p. 353-356
Factors Governing Oxygen Vacancy Formation in Oxide Perovskites
journal, August 2021
- Wexler, Robert B.; Gautam, Gopalakrishnan Sai; Stechel, Ellen B.
- Journal of the American Chemical Society, Vol. 143, Issue 33
Structural phase transition and magnetism in hexagonal by magnetization measurements and by electron, x-ray, and neutron diffraction studies
journal, March 2007
- Daoud-Aladine, A.; Martin, C.; Chapon, L. C.
- Physical Review B, Vol. 75, Issue 10
Large-Scale Benchmark of Exchange–Correlation Functionals for the Determination of Electronic Band Gaps of Solids
journal, July 2019
- Borlido, Pedro; Aull, Thorsten; Huran, Ahmad W.
- Journal of Chemical Theory and Computation, Vol. 15, Issue 9
The crystallography of correlated disorder
journal, May 2015
- Keen, David A.; Goodwin, Andrew L.
- Nature, Vol. 521, Issue 7552
Bowing of the defect formation energy in semiconductor alloys
journal, June 2013
- Ma, Jie; Wei, Su-Huai
- Physical Review B, Vol. 87, Issue 24
Accurate prediction of oxygen vacancy concentration with disordered A-site cations in high-entropy perovskite oxides
journal, February 2023
- Park, Jiyun; Xu, Boyuan; Pan, Jie
- npj Computational Materials, Vol. 9, Issue 1
Enthalpies of Oxidation of CaMnO 3-δ , Ca 2 MnO 4-δ and SrMnO 3-δ Deduced Redox Properties
journal, November 2001
- Rørmark, Lisbeth; Mørch, Anne Beate; Wiik, Kjell
- Chemistry of Materials, Vol. 13, Issue 11
The role of decomposition reactions in assessing first-principles predictions of solid stability
journal, January 2019
- Bartel, Christopher J.; Weimer, Alan W.; Lany, Stephan
- npj Computational Materials, Vol. 5, Issue 1
Formation of 6H-Ba3Ce0.75Mn2.25O9 during Thermochemical Reduction of 12R-Ba4CeMn3O12: Identification of a Polytype in the Ba(Ce,Mn)O3 Family
journal, April 2022
- Strange, Nicholas A.; Park, James Eujin; Goyal, Anuj
- Inorganic Chemistry, Vol. 61, Issue 16
Semiconductor thermochemistry in density functional calculations
journal, December 2008
- Lany, Stephan
- Physical Review B, Vol. 78, Issue 24
Reduction Thermodynamics of Sr 1− x Ce x MnO 3 and Ce x Sr 2− x MnO 4 Perovskites for Solar Thermochemical Hydrogen Production
journal, September 2021
- Bergeson-Keller, Anyka M.; Sanders, Michael D.; O’Hayre, Ryan P.
- Energy Technology, Vol. 10, Issue 1
Novel rare-earth-containing manganites Ba4REMn3O12 (RE=Ce, Pr) with 12R structure
journal, March 2004
- Fuentes, Antonio F.; Boulahya, Khalid; Amador, Ulises
- Journal of Solid State Chemistry, Vol. 177, Issue 3
The use of poly-cation oxides to lower the temperature of two-step thermochemical water splitting
journal, January 2018
- Zhai, Shang; Rojas, Jimmy; Ahlborg, Nadia
- Energy & Environmental Science, Vol. 11, Issue 8
Corner- versus face-sharing octahedra in perovskites ( , Sr, and Ba)
journal, May 2007
- Søndenå, Rune; Stølen, Svein; Ravindran, P.
- Physical Review B, Vol. 75, Issue 18
Implementation and performance of the frequency-dependent method within the PAW framework
journal, July 2006
- Shishkin, M.; Kresse, G.
- Physical Review B, Vol. 74, Issue 3