An ab initio Study of Reduction of V2O5 through the Formation of Oxygen Vacancies and Li Intercalation

David O. Scanlon, Aron Walsh, Benjamin J. Morgan, Graeme W. Watson

Research output: Contribution to journalArticle

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Abstract

Two methods of reduction of V2O5 have been investigated: oxygen vacancy formation and lithium intercalation. The electronic structure, geometry, and energetics of these reduced systems are examined. Oxygen vacancies in bulk α-V2O5 have been investigated by using gradient-corrected density functional theory (GGA) and density functional theory corrected for on-site Coulomb interactions in strongly correlated systems (GGA+U). The GGA calculation predicts a delocalized defect electronic state. This disagrees with experimental evidence, which indicates that oxygen vacancies produce a localized reduced vanadium state in the band gap. The DFT+U results for U = 4.0 eV are consistent with available UPS and XPS data, indicating strong localization on the vanadium atoms nearest the vacancy, and showing reduced V(IV) species. Intercalation of Li in V2O5, which has important potential applications in energy storage devices, is also reported at the GGA+U level, using the value of U obtained from the oxygen-deficient calculation, and localized reduction is demonstrated. These results are again in agreement with available UPS data and crystallographic data, indicating good transferability of this value of U among the systems of interest. Calculated lithium intercalation energies for both the α- and γ-V2O5 phases are reported, and the structure and relative stability of the deintercalated γ-V2O5 phase are also examined.
Original languageEnglish
Pages (from-to)9903-9911
Number of pages9
JournalJournal of Physical Chemistry C
Volume112
Issue number26
DOIs
Publication statusPublished - 1 Jul 2008

Fingerprint

Oxygen vacancies
Intercalation
intercalation
Vanadium
Density functional theory
Lithium
oxygen
vanadium
lithium
Electronic states
density functional theory
Coulomb interactions
Discrete Fourier transforms
Energy storage
Vacancies
Electronic structure
Energy gap
energy storage
X ray photoelectron spectroscopy
Atoms

Keywords

  • band theory
  • ray-powder diffraction
  • density-functional theory
  • metal-oxides
  • oxidative dehydrogenation
  • thin-films
  • oxide surfaces
  • electronic-structure
  • vanadium pentoxide
  • low-index surfaces

Cite this

An ab initio Study of Reduction of V2O5 through the Formation of Oxygen Vacancies and Li Intercalation. / Scanlon, David O.; Walsh, Aron; Morgan, Benjamin J.; Watson, Graeme W.

In: Journal of Physical Chemistry C, Vol. 112, No. 26, 01.07.2008, p. 9903-9911.

Research output: Contribution to journalArticle

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