P. Mustarelli et al., TRANSFERRED HYPERFINE INTERACTION AND STRUCTURE IN LIMN2O4 AND LI2MNO3 COEXISTING PHASES - A XRD AND LI-7 NMR-MAS STUDY, Physical review. B, Condensed matter, 55(18), 1997, pp. 12018-12024
X-ray diffraction (XRD) and Li-7 MMR-MAS measurements have been perfor
med on LiMn2O4 (lithium cationic fraction, x = 0.333), Li2MnO3 (x = 0.
667), and the intermediate composition with x = 0.40. The use of magic
angle spinning produces complex manifolds of the spinning sidebands.
The predominant interaction affecting the NMR spectrum is the transfer
red hyperfine coupling (TFHI) between the Mn ions and the Li spins. TF
HI parameters are extracted from MAS-NMR spectra of oxides containing
a large quantity of manganese. We obtained a full spectral assignment
for the spinel LiMn2O4, for the rocksalt Li2MnO3, and for the x = 0.40
sample, which contains the rocksalt and both stoichiometric and nonst
oichiometric spinel phases. According to XRD data, the rocksalt phase
contains three nonequivalent lithium sites whose NMR peaks are shifted
upheld from x = 0.667 to 0.40 because of the cell volume expansion. T
he Li+ ions belonging to the two spinel phases of x = 0.40 are quite m
obile and give origin by motional narrowing to a single peak, which is
slightly shifted upheld with respect to that of LiMn2O4.