Jump to main content
Jump to site search

Issue 2, 2019
Previous Article Next Article

Re-evaluation of experimental measurements for the validation of electronic band structure calculations for LiFePO4 and FePO4

Author affiliations

Abstract

Experimental measurements used to validate previous electronic band structure calculations for olivine LiFePO4 and its delithiated phase, FePO4, have been re-investigated in this study. Experimental band gaps of LiFePO4 and FePO4 have been determined to be 6.34 eV and 3.2 eV by electron energy loss spectroscopy (EELS) and UV-Vis-NIR diffusion reflectance spectroscopy, respectively. X-ray photoemission (XPS) and Raman spectroscopy show that the surfaces of very carefully synthesized LiFePO4 display Li-depletion, which affects optical reflectance determinations. Based on these experimental measurements, functionals for density functional theory (DFT) calculations of the electronic properties have been revisited. Overall, electronic structures of LiFePO4 and FePO4 calculated using sX-LDA show the best self-consistent match to combined experimentally determined parameters. Furthermore, the open-circuit voltages of the LiFePO4 half-cell have been interpreted in terms of both Fermi levels and Gibbs free energies, which provides additional support for the electronic band structures determined by this research.

Graphical abstract: Re-evaluation of experimental measurements for the validation of electronic band structure calculations for LiFePO4 and FePO4

Back to tab navigation

Supplementary files

Article information


Submitted
05 Nov 2018
Accepted
25 Dec 2018
First published
09 Jan 2019

This article is Open Access

RSC Adv., 2019,9, 1134-1146
Article type
Paper

Re-evaluation of experimental measurements for the validation of electronic band structure calculations for LiFePO4 and FePO4

Y. Zhang, J. A. Alarco, A. S. Best, G. A. Snook, P. C. Talbot and J. Y. Nerkar, RSC Adv., 2019, 9, 1134
DOI: 10.1039/C8RA09154D

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material and it is not used for commercial purposes.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements