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 Lab. (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 = {2018},
month = {2}
}
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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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