Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles
Abstract
The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.
- Authors:
-
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Program (EE-3F); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1424583
- Alternate Identifier(s):
- OSTI ID: 1421582
- Report Number(s):
- NREL/JA-5K00-70968
Journal ID: ISSN 0021-9606; TRN: US1801926
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 148; Journal Issue: 7; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 36 MATERIALS SCIENCE; solar thermochemical; water splitting; redox cycles; defect equilibria
Citation Formats
Lany, Stephan. Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles. United States: N. p., 2018.
Web. doi:10.1063/1.5022176.
Lany, Stephan. Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles. United States. https://doi.org/10.1063/1.5022176
Lany, Stephan. Wed .
"Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles". United States. https://doi.org/10.1063/1.5022176. https://www.osti.gov/servlets/purl/1424583.
@article{osti_1424583,
title = {Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles},
author = {Lany, Stephan},
abstractNote = {The ideal material for solar thermochemical water splitting, which has yet to be discovered, must satisfy stringent conditions for the free energy of reduction, including, in particular, a sufficiently large positive contribution from the solid-state entropy. By inverting the commonly used relationship between defect formation energy and defect concentration, it is shown here that charged defect formation causes a large electronic entropy contribution manifesting itself as the temperature dependence of the Fermi level. This result is a general feature of charged defect formation and motivates new materials design principles for solar thermochemical hydrogen production.},
doi = {10.1063/1.5022176},
journal = {Journal of Chemical Physics},
number = 7,
volume = 148,
place = {United States},
year = {Wed Feb 21 00:00:00 EST 2018},
month = {Wed Feb 21 00:00:00 EST 2018}
}
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Cited by: 17 works
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Figures / Tables:
Figure 1: Ideal gas law calculation of pO2 and pH2 vs temperature for two values of the O chemical potential, ΔμO,TR = ‐2.46 eV and ΔμO,GS = ‐2.94 eV, corresponding to desirable conditions for the TR and GS steps (dots), respectively. pH2 is determined from the H2+$\frac{1}{2}$O2↔H2O H2O equilibrium withmore »
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Works referenced in this record:
Native defects and self-compensation in ZnSe
journal, May 1992
- Laks, D. B.; Van de Walle, C. G.; Neumark, G. F.
- Physical Review B, Vol. 45, Issue 19
Semiconducting transition metal oxides
journal, June 2015
- Lany, Stephan
- Journal of Physics: Condensed Matter, Vol. 27, Issue 28
A thermodynamic study of nonstoichiometric cerium dioxide
journal, November 1975
- Panlener, R. J.; Blumenthal, R. N.; Garnier, J. E.
- Journal of Physics and Chemistry of Solids, Vol. 36, Issue 11, p. 1213-1222
Pressure dependence of deep levels in GaAs
journal, June 1982
- Ren, Shang Yuan; Dow, John D.; Wolford, D. J.
- Physical Review B, Vol. 25, Issue 12
Disentangling the role of small polarons and oxygen vacancies in
journal, June 2017
- Sun, Lu; Huang, Xiaowei; Wang, Ligen
- Physical Review B, Vol. 95, Issue 24
Considerations in the Design of Materials for Solar-Driven Fuel Production Using Metal-Oxide Thermochemical Cycles
journal, October 2013
- Miller, James E.; McDaniel, Anthony H.; Allendorf, Mark D.
- Advanced Energy Materials, Vol. 4, Issue 2, Article No. 1300469
Ab initio thermodynamics of intrinsic oxygen vacancies in ceria
journal, October 2012
- Gopal, Chirranjeevi Balaji; van de Walle, Axel
- Physical Review B, Vol. 86, Issue 13
Implications of the band gap problem on oxidation and hydration in acceptor-doped barium zirconate
journal, June 2015
- Lindman, Anders; Erhart, Paul; Wahnström, Göran
- Physical Review B, Vol. 91, Issue 24
Anion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors
journal, July 2005
- Lany, Stephan; Zunger, Alex
- Physical Review B, Vol. 72, Issue 3
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
First-principles calculations of the temperature dependence of the band gap of Si nanocrystals
journal, October 2007
- Franceschetti, A.
- Physical Review B, Vol. 76, Issue 16
Practical doping principles
journal, July 2003
- Zunger, Alex
- Applied Physics Letters, Vol. 83, Issue 1
High-Throughput Computational Screening of Perovskites for Thermochemical Water Splitting Applications
journal, July 2016
- Emery, Antoine A.; Saal, James E.; Kirklin, Scott
- Chemistry of Materials, Vol. 28, Issue 16
Effect of isotopic mass on the photoluminescence spectra of zinc oxide
journal, October 2003
- Manjón, F. J.; Mollar, M.; Hernández-Fenollosa, M. A.
- Solid State Communications, Vol. 128, Issue 1
First-principles thermodynamic framework for the evaluation of thermochemical - or -splitting materials
journal, December 2009
- Meredig, B.; Wolverton, C.
- Physical Review B, Vol. 80, Issue 24
Hybrid functionals applied to rare-earth oxides: The example of ceria
journal, January 2007
- Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim
- Physical Review B, Vol. 75, Issue 4
Advances and trends in redox materials for solar thermochemical fuel production
journal, November 2017
- Carrillo, Richard J.; Scheffe, Jonathan R.
- Solar Energy, Vol. 156
Magnetism without Magnetic Ions: Percolation, Exchange, and Formation Energies of Magnetism-Promoting Intrinsic Defects in CaO
journal, March 2006
- Osorio-Guillén, J.; Lany, S.; Barabash, S. V.
- Physical Review Letters, Vol. 96, Issue 10
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
Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides
journal, January 2007
- Lany, Stephan; Zunger, Alex
- Physical Review Letters, Vol. 98, Issue 4
Factors Affecting the Efficiency of Solar Driven Metal Oxide Thermochemical Cycles
journal, February 2013
- Siegel, Nathan P.; Miller, James E.; Ermanoski, Ivan
- Industrial & Engineering Chemistry Research, Vol. 52, Issue 9, p. 3276-3286
Oxide enthalpy of formation and band gap energy as accurate descriptors of oxygen vacancy formation energetics
journal, January 2014
- Deml, Ann M.; Stevanović, Vladan; Muhich, Christopher L.
- Energy & Environmental Science, Vol. 7, Issue 6
Implications of the band gap problem on oxidation and hydration in acceptor-doped barium zirconate
text, January 2015
- Lindman, Anders; Erhart, Paul; Wahnström, Göran
- arXiv
Anion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors
text, January 2005
- Lany, S.; Zunger, A.
- arXiv
Works referencing / citing this record:
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
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
Defect phase diagram for doping of Ga 2 O 3
journal, April 2018
- Lany, Stephan
- APL Materials, Vol. 6, Issue 4
Computational Fermi level engineering and doping-type conversion of Ga2O3 via three-step synthesis process
text, January 2021
- Goyal, Anuj; Zakutayev, Andriy; Stevanović, Vladan
- arXiv
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