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Title: Electronic and protonic conduction in LaFeO 3

Abstract

Perovskite-type LaFeO3 has promising applications as a negative-electrode material for Ni/metal-hydride batteries. To further improve electrode performance, a thorough understanding of its charge-transport mechanisms is required. We use hybrid density functional theory to investigate the structural and electronic properties of bulk LaFeO3, as well as the effect of point defects and polarons on charge transport. Electronic charge localizes in the form of small hole and electron polarons; this self-trapping occurs in the bulk and also in the vicinity of point defects and impurities. We find that oxygen vacancies act as deep donors, while Fe and La vacancies are acceptors with the induced holes trapped as small polarons. Hydrogen interstitials and Ge and Ti impurities, on the other hand, act as donors that can trap small electron polarons. Hydrogen binds strongly to the La and Fe vacancies and hence these defects are detrimental to protonic conduction. We also elucidate how doping with Sr enhances the electrode performance of LaFeO3:Sr impurities substituting on La sites act as acceptors and enable electronic conductivity through hole polarons, with a hopping barrier of 0.39 eV. In addition, Sr impurities suppress the formation of cation vacancies, thereby enhancing proton conductivity.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States). Dept. of Materials
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1493609
DOE Contract Number:  
AC02-05CH11231; FG02-07ER46434
Resource Type:
Journal Article
Journal Name:
J. Mater. Chem. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 29; Journal ID: ISSN 2050-7488
Country of Publication:
United States
Language:
English

Citation Formats

Zhu, Zhen, Peelaers, Hartwin, and Van de Walle, Chris G. Electronic and protonic conduction in LaFeO 3. United States: N. p., 2017. Web. doi:10.1039/c7ta04330a.
Zhu, Zhen, Peelaers, Hartwin, & Van de Walle, Chris G. Electronic and protonic conduction in LaFeO 3. United States. doi:10.1039/c7ta04330a.
Zhu, Zhen, Peelaers, Hartwin, and Van de Walle, Chris G. Sun . "Electronic and protonic conduction in LaFeO 3". United States. doi:10.1039/c7ta04330a.
@article{osti_1493609,
title = {Electronic and protonic conduction in LaFeO 3},
author = {Zhu, Zhen and Peelaers, Hartwin and Van de Walle, Chris G.},
abstractNote = {Perovskite-type LaFeO3 has promising applications as a negative-electrode material for Ni/metal-hydride batteries. To further improve electrode performance, a thorough understanding of its charge-transport mechanisms is required. We use hybrid density functional theory to investigate the structural and electronic properties of bulk LaFeO3, as well as the effect of point defects and polarons on charge transport. Electronic charge localizes in the form of small hole and electron polarons; this self-trapping occurs in the bulk and also in the vicinity of point defects and impurities. We find that oxygen vacancies act as deep donors, while Fe and La vacancies are acceptors with the induced holes trapped as small polarons. Hydrogen interstitials and Ge and Ti impurities, on the other hand, act as donors that can trap small electron polarons. Hydrogen binds strongly to the La and Fe vacancies and hence these defects are detrimental to protonic conduction. We also elucidate how doping with Sr enhances the electrode performance of LaFeO3:Sr impurities substituting on La sites act as acceptors and enable electronic conductivity through hole polarons, with a hopping barrier of 0.39 eV. In addition, Sr impurities suppress the formation of cation vacancies, thereby enhancing proton conductivity.},
doi = {10.1039/c7ta04330a},
journal = {J. Mater. Chem. A},
issn = {2050-7488},
number = 29,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

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