Title: Critical Assessment of the Thermodynamics of Vacancy Formation in Fe2O3 Using Hybrid Density Functional Theory

Journal Article · · Journal of Physical Chemistry. C
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
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Fe2O3 hematite is a technologically important material with applications in energy storage as well as being the key phase formed in the rust of iron-based materials. Despite this central importance, there is much that is still unknown regarding the properties of defects in Fe2O3 and consequently oxide growth. In this work, using screened hybrid density functional theory (HSE06), we consider the thermodynamics of vacancies in Fe2O3, considering the effects of ionic and electronic chemical potentials on both iron and oxygen vacancy formation. We find that, in the oxygen-rich limit, iron vacancies are easier to form, though the difference in formation energy between the two vacancies is only about 1 eV. In contrast, in the Fe-rich limit, oxygen vacancies have an extremely low formation energy, only 0.07 eV at mid-gap, and would spontaneously form as the Fermi level is reduced, while Fe vacancies require over 5 eV to form. Consistent with experiment, this indicates that Fe2O3 is relatively easily reduced but not oxidized. However, the theoretical picture is very different when considering other exchange–correlation functionals (GGA + U or SCAN), emphasizing the critical role of the exchange–correlation functional in describing this system accurately.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Fundamental Understanding of Transport Under Reactor Extremes (FUTURE); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
89233218CNA000001
OSTI ID:
1760602
Report Number(s):
LA-UR-20-24936
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 43 Vol. 124; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Iron
defects
defects in solids
electrical energy
energy