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Title: 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:
 [1]
  1. 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) (SC-22)
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. doi:10.1063/1.5022176.
Lany, Stephan. Wed . "Communication: The electronic entropy of charged defect formation and its impact on thermochemical redox cycles". United States. doi: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}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 3 works
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Figures / Tables:

Figure 1 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 » pH2O = 1 atm.« less

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