Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

Lany, Stephan

doi:10.1063/1.5022176

Title: Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

Journal Article · Wed Feb 21 04:00:00 UTC 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5022176 · OSTI ID:1424583

Lany, Stephan ^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: 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 Organization:: 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) (SC-22)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1424583

Report Number(s):: NREL/JA--5K00-70968

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 7 Vol. 148; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (25)

Considerations in the Design of Materials for Solar-Driven Fuel Production Using Metal-Oxide Thermochemical Cycles Miller, James E.; McDaniel, Anthony H.; Allendorf, Mark D. Advanced Energy Materials, Vol. 4, Issue 2, Article No. 1300469 https://doi.org/10.1002/aenm.201300469	journal	October 2013
A thermodynamic study of nonstoichiometric cerium dioxide Panlener, R. J.; Blumenthal, R. N.; Garnier, J. E. Journal of Physics and Chemistry of Solids, Vol. 36, Issue 11, p. 1213-1222 https://doi.org/10.1016/0022-3697(75)90192-4	journal	November 1975
Advances and trends in redox materials for solar thermochemical fuel production Carrillo, Richard J.; Scheffe, Jonathan R. Solar Energy, Vol. 156 https://doi.org/10.1016/j.solener.2017.05.032	journal	November 2017
Effect of isotopic mass on the photoluminescence spectra of zinc oxide Manjón, F. J.; Mollar, M.; Hernández-Fenollosa, M. A. Solid State Communications, Vol. 128, Issue 1 https://doi.org/10.1016/s0038-1098(03)00616-1	journal	October 2003
High-Throughput Computational Screening of Perovskites for Thermochemical Water Splitting Applications Emery, Antoine A.; Saal, James E.; Kirklin, Scott Chemistry of Materials, Vol. 28, Issue 16 https://doi.org/10.1021/acs.chemmater.6b01182	journal	July 2016
Factors Affecting the Efficiency of Solar Driven Metal Oxide Thermochemical Cycles Siegel, Nathan P.; Miller, James E.; Ermanoski, Ivan Industrial & Engineering Chemistry Research, Vol. 52, Issue 9, p. 3276-3286 https://doi.org/10.1021/ie400193q	journal	February 2013
Giant onsite electronic entropy enhances the performance of ceria for water splitting Naghavi, S. Shahab; Emery, Antoine A.; Hansen, Heine A. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00381-2	journal	August 2017
Oxide enthalpy of formation and band gap energy as accurate descriptors of oxygen vacancy formation energetics Deml, Ann M.; Stevanović, Vladan; Muhich, Christopher L. Energy & Environmental Science, Vol. 7, Issue 6 https://doi.org/10.1039/c3ee43874k	journal	January 2014
Practical doping principles Zunger, Alex Applied Physics Letters, Vol. 83, Issue 1 https://doi.org/10.1063/1.1584074	journal	July 2003
Semiconducting transition metal oxides Lany, Stephan Journal of Physics: Condensed Matter, Vol. 27, Issue 28 https://doi.org/10.1088/0953-8984/27/28/283203	journal	June 2015
Pressure dependence of deep levels in GaAs Ren, Shang Yuan; Dow, John D.; Wolford, D. J. Physical Review B, Vol. 25, Issue 12 https://doi.org/10.1103/physrevb.25.7661	journal	June 1982
Native defects and self-compensation in ZnSe Laks, D. B.; Van de Walle, C. G.; Neumark, G. F. Physical Review B, Vol. 45, Issue 19 https://doi.org/10.1103/physrevb.45.10965	journal	May 1992
Anion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors Lany, Stephan; Zunger, Alex Physical Review B, Vol. 72, Issue 3 https://doi.org/10.1103/physrevb.72.035215	journal	July 2005
Hybrid functionals applied to rare-earth oxides: The example of ceria Da Silva, Juarez L. F.; Ganduglia-Pirovano, M. Verónica; Sauer, Joachim Physical Review B, Vol. 75, Issue 4 https://doi.org/10.1103/physrevb.75.045121	journal	January 2007
First-principles calculations of the temperature dependence of the band gap of Si nanocrystals Franceschetti, A. Physical Review B, Vol. 76, Issue 16 https://doi.org/10.1103/physrevb.76.161301	journal	October 2007
First-principles thermodynamic framework for the evaluation of thermochemical H 2 O - or CO 2 -splitting materials Meredig, B.; Wolverton, C. Physical Review B, Vol. 80, Issue 24 https://doi.org/10.1103/physrevb.80.245119	journal	December 2009
Ab initio thermodynamics of intrinsic oxygen vacancies in ceria Gopal, Chirranjeevi Balaji; van de Walle, Axel Physical Review B, Vol. 86, Issue 13 https://doi.org/10.1103/physrevb.86.134117	journal	October 2012
Convergence of density and hybrid functional defect calculations for compound semiconductors Peng, Haowei; Scanlon, David O.; Stevanovic, Vladan Physical Review B, Vol. 88, Issue 11 https://doi.org/10.1103/physrevb.88.115201	journal	September 2013
Implications of the band gap problem on oxidation and hydration in acceptor-doped barium zirconate Lindman, Anders; Erhart, Paul; Wahnström, Göran Physical Review B, Vol. 91, Issue 24 https://doi.org/10.1103/physrevb.91.245114	journal	June 2015
Disentangling the role of small polarons and oxygen vacancies in Ce O 2 Sun, Lu; Huang, Xiaowei; Wang, Ligen Physical Review B, Vol. 95, Issue 24 https://doi.org/10.1103/physrevb.95.245101	journal	June 2017
Chemical potential dependence of defect formation energies in GaAs: Application to Ga self-diffusion Zhang, S.; Northrup, John Physical Review Letters, Vol. 67, Issue 17 https://doi.org/10.1103/physrevlett.67.2339	journal	October 1991
Magnetism without Magnetic Ions: Percolation, Exchange, and Formation Energies of Magnetism-Promoting Intrinsic Defects in CaO Osorio-Guillén, J.; Lany, S.; Barabash, S. V. Physical Review Letters, Vol. 96, Issue 10 https://doi.org/10.1103/physrevlett.96.107203	journal	March 2006
Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides Lany, Stephan; Zunger, Alex Physical Review Letters, Vol. 98, Issue 4 https://doi.org/10.1103/physrevlett.98.045501	journal	January 2007
Implications of the band gap problem on oxidation and hydration in acceptor-doped barium zirconate Lindman, Anders; Erhart, Paul; Wahnström, Göran arXiv https://doi.org/10.48550/arxiv.1503.06612	text	January 2015
Anion vacancies as a source of persistent photoconductivity in II-VI and chalcopyrite semiconductors Lany, S.; Zunger, A. arXiv https://doi.org/10.48550/arxiv.cond-mat/0503018	text	January 2005

Cited By (4)

Computational Fermi level engineering and doping-type conversion of Ga2O3 via three-step synthesis process Goyal, Anuj; Zakutayev, Andriy; Stevanović, Vladan arXiv https://doi.org/10.48550/arxiv.2103.16639	text	January 2021
Interplay between Composition, Electronic Structure, Disorder, and Doping due to Dual Sublattice Mixing in Nonequilibrium Synthesis of ZnSnN ₂ :O Pan, Jie; Cordell, Jacob; Tucker, Garritt J. Advanced Materials, Vol. 31, Issue 11 https://doi.org/10.1002/adma.201807406	journal	January 2019
BaCe 0.25 Mn 0.75 O 3−δ —a promising perovskite-type oxide for solar thermochemical hydrogen production R. Barcellos, Debora; Sanders, Michael D.; Tong, Jianhua Energy & Environmental Science, Vol. 11, Issue 11 https://doi.org/10.1039/c8ee01989d	journal	January 2018
Defect phase diagram for doping of Ga ₂ O ₃ Lany, Stephan APL Materials, Vol. 6, Issue 4 https://doi.org/10.1063/1.5019938	journal	April 2018

Similar Records

Redox Defect Thermochemistry of FeAl₂O₄ Hercynite in Water Splitting from First-Principles Methods

Journal Article · Mon Jan 10 04:00:00 UTC 2022 · Chemistry of Materials · OSTI ID:1840916

Millican, Samantha L.; Clary, Jacob M.; Musgrave, Charles B.; +1 more

Alternate thermochemical cycles for advanced hydrogen production

Conference · Mon Mar 01 04:00:00 UTC 1982 · Am. Chem. Soc., Div. Pet. Chem., Prepr.; (United States) · OSTI ID:6432487

Bowman, M G; Hollabaugh, C M; Jones, W M; +1 more

Operational Limits of Redox Metal Oxides Performing Thermochemical Water Splitting

Journal Article · Wed May 26 04:00:00 UTC 2021 · Energy Technology · OSTI ID:1976328

Bayon, Alicia; de la Calle, Alberto; Stechel, Ellen B.; +1 more

Related Subjects

14 SOLAR ENERGY
36 MATERIALS SCIENCE
defect equilibria
redox cycles
solar thermochemical
water splitting

Title: Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles

Citation Formats

References (25)

Cited By (4)

Similar Records

Related Subjects