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A First-Principles Study of the Role of Na Vacancies in the Thermoelectricity of Na x CoO2

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An Erratum to this article was published on 26 March 2011

Abstract

First principles calculations using the generalized gradient approximation to density functional theory have been carried out to evaluate formation energies of defects and the resultant changes in electronic structure of NaCoO2 and Na0.5CoO2. The calculated formation energies confirm that Na vacancies form readily in this material, particularly through volatilization at elevated temperatures, consistent with experimentally observed behavior. Numerical analysis of the change in charge distribution upon Na vacancy formation shows that the vacancy plays a crucial role in modifying the electronic properties of the material. In these p-type thermoelectric materials, Na vacancies act as a reservoir for the minority carrier (electrons), removing them from the CoO2 layer while simultaneously increasing the concentration of majority carriers (holes) available for conduction in the CoO2 layer.

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Acknowledgements

This work was in part supported by a Grant- in-Aid for Scientific Research by the Ministry of Education, Science, Sports and Culture. The authors thank Dr T. Nagira for helpful discussions.

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Authors and Affiliations

  1. Department of Adaptive Machine Systems, Osaka University, 2-1 Yamadaoka, Suita, Osaka, 565-0871, Japan

    Masato Yoshiya, Takahiro Okabayashi & Masahiro Tada

  2. Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta, Nagoya, 456-8587, Japan

    Masato Yoshiya & Craig A. J. Fisher

Authors
  1. Masato Yoshiya
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  2. Takahiro Okabayashi
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  3. Masahiro Tada
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  4. Craig A. J. Fisher
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Correspondence to Masato Yoshiya.

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An erratum to this article can be found at http://dx.doi.org/10.1007/s11664-011-1628-7

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Yoshiya, M., Okabayashi, T., Tada, M. et al. A First-Principles Study of the Role of Na Vacancies in the Thermoelectricity of Na x CoO2 . J. Electron. Mater. 39, 1681–1686 (2010). https://doi.org/10.1007/s11664-010-1237-x

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  • DOI: https://doi.org/10.1007/s11664-010-1237-x

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