The room temperature cation occupancy in LiMgVO4 and LiZnVO4 crystallographic sites is obtained by means of the combined use of X-ray powder diffraction (XRPD), Li-7 and V-51 magic angle spinning nuclear magnetic resonance (MAS NMR), and micro-Raman measurements. In the LiMgVO4 Cmcm orthorhombic structure, the 4c (C-2v symmetry) tetrahedral vanadium site is fully ordered; on the contrary, the Li 4c tetrahedral site and the 4b (C-2h symmetry) Mg octahedral site display about 22% of reciprocal cationic exchange. Higher cationic disorder is observed in LiZnVO4: the three cations can distribute on the three tetrahedral and distinct sites of the R-3 structure. XRPD and MAS NMR analysis results highly agree for what concerns vanadium ion distribution on the three cationic sites (about 25, 26, and 47%). From the full profile fitting of XRPD patterns with the Rietveld method, it is also obtained that Li+ displays a slightly preferred occupation of the T1 position (similar to 55%) and Zn2+ of the T2 position (similar to 46%). The vibrational spectra of the two compounds are characterized by different peak positions and broadening of the Raman modes, reflecting the cation distribution and the local vibrational unit distortion. A comparison is also made with recent Raman results on Li3VO4. High temperature XRPD measurements rule out possible structural transitions up to 673 K for both compounds

Capsoni, D., Bini, M., Massarotti, V., Mustarelli, P., Belotti, F., Galinetto, P. (2006). Cation distribution in LiMgVO4 and LiZnVO4: structural and spectroscopic study. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, 110(11), 5409-5415 [10.1021/jp057088t].

Cation distribution in LiMgVO4 and LiZnVO4: structural and spectroscopic study

Mustarelli, P;
2006

Abstract

The room temperature cation occupancy in LiMgVO4 and LiZnVO4 crystallographic sites is obtained by means of the combined use of X-ray powder diffraction (XRPD), Li-7 and V-51 magic angle spinning nuclear magnetic resonance (MAS NMR), and micro-Raman measurements. In the LiMgVO4 Cmcm orthorhombic structure, the 4c (C-2v symmetry) tetrahedral vanadium site is fully ordered; on the contrary, the Li 4c tetrahedral site and the 4b (C-2h symmetry) Mg octahedral site display about 22% of reciprocal cationic exchange. Higher cationic disorder is observed in LiZnVO4: the three cations can distribute on the three tetrahedral and distinct sites of the R-3 structure. XRPD and MAS NMR analysis results highly agree for what concerns vanadium ion distribution on the three cationic sites (about 25, 26, and 47%). From the full profile fitting of XRPD patterns with the Rietveld method, it is also obtained that Li+ displays a slightly preferred occupation of the T1 position (similar to 55%) and Zn2+ of the T2 position (similar to 46%). The vibrational spectra of the two compounds are characterized by different peak positions and broadening of the Raman modes, reflecting the cation distribution and the local vibrational unit distortion. A comparison is also made with recent Raman results on Li3VO4. High temperature XRPD measurements rule out possible structural transitions up to 673 K for both compounds
Articolo in rivista - Articolo scientifico
Cathodes, NMR
English
2006
110
11
5409
5415
reserved
Capsoni, D., Bini, M., Massarotti, V., Mustarelli, P., Belotti, F., Galinetto, P. (2006). Cation distribution in LiMgVO4 and LiZnVO4: structural and spectroscopic study. JOURNAL OF PHYSICAL CHEMISTRY. B, CONDENSED MATTER, MATERIALS, SURFACES, INTERFACES & BIOPHYSICAL, 110(11), 5409-5415 [10.1021/jp057088t].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/257084
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