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Local structure and lithium mobility in intercalated Li3Al(x)Ti(2-x)(PO4)3 NASICON type materials: a combined neutron diffraction and NMR study.

Authors
  • Arbi, K
  • Hoelzel, M
  • Kuhn, A
  • García-Alvarado, F
  • Sanz, J
Type
Published Article
Journal
Physical Chemistry Chemical Physics
Publisher
The Royal Society of Chemistry
Publication Date
Sep 14, 2014
Volume
16
Issue
34
Pages
18397–18405
Identifiers
DOI: 10.1039/c4cp02938k
PMID: 25070935
Source
Medline
License
Unknown

Abstract

The structural features of intercalated Li3AlxTi2-x(PO4)3 compounds, with x = 0 and 0.2, have been deduced by Rietveld analysis of neutron diffraction (ND) patterns recorded between 100 and 500 K. The Li insertion decreases the symmetry from R3̄c to R3̄ in analyzed compounds. In pristine Li1+xAlxTi2-x(PO4)3 samples, Li occupies mainly six-fold M1 sites at ternary axes; but in lithiated Li3AlxTi2-x(PO4)3 samples, Li is located near M2 positions at M3/M3' four-fold coordinated sites. In both cases, Li arrangement minimizes electrostatic Li-Li repulsions. The insertion of lithium resulted in the reduction of Ti(4+) to Ti(3+) that shifts (7)Li, (27)Al and (31)P MAS-NMR resonances towards more positive chemical shifts, improving the resolution of different sites. The detection of twelve components in (7)Li MAS-NMR spectra recorded at room temperature suggests the location of Li(+) ions at three-oxygen faces that define M2 cavities. From (7)Li MAS-NMR spectra, the occupancy of sites and mobility of lithium were investigated in the temperature range 100-500 K. The correlation between structural information, deduced by neutron diffraction, and lithium mobility, deduced by NMR spectroscopy, provides new insights into structural factors that affect lithium mobility in materials with NASICON structure.

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