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Structural Modulation in the High Capacity Battery Cathode Material LiFeBO3.

Authors :
Janssen, Yuri
Middlemiss, Derek S.
Shou-Hang Bo
Grey, Clare P.
Khalifah, Peter G.
Source :
Journal of the American Chemical Society. 8/1/2012, Vol. 134 Issue 30, p12516-12527. 12p.
Publication Year :
2012

Abstract

The crystal structure of the promising Li-ion battery cathode material LiFeBO3 has been redetermined based on the results of single crystal X-ray diffraction data. A commensurate modulation that doubles the periodicity of the lattice in the a-axis direction is observed. When the structure of LiFeBO3 is refined in the 4-dimensional superspace group C2/ c(α0γ)00, with α = 1/2 and γ = 0 and with lattice parameters of a = 5.1681 Å, b = 8.8687 Å, c = 10.1656 Å, and β = 91.514°, all of the disorder present in the prior C2/c structural model is eliminated and a long-range ordering of 1D chains of corner-shared LiO4 is revealed to occur as a result of cooperative displacements of Li and 0 atoms in the c-axis direction. Solid-state hybrid density functional theory calculations find that the modulation stabilizes the LiFeBO3 structure by 1.2 kJ/mol (12 meV/f.u.), and that the modulation disappears after delithiation to form a structurally related FeBO3 phase. The band gaps of LiFeBO3 and FeBO3 are calculated to be 3.5 and 3.3 eV, respectively. Bond valence sum maps have been used to identify and characterize the important Li conduction pathways, and suggest that the activation energies for Li diffusion will be higher in the modulated structure of LiFeBO3 than in its unmodulated analogue. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00027863
Volume :
134
Issue :
30
Database :
Academic Search Index
Journal :
Journal of the American Chemical Society
Publication Type :
Academic Journal
Accession number :
78352652
Full Text :
https://doi.org/10.1021/ja301881c