7Li NMR measurements were performed to study milling effects on ionic diffusion
in lithium cobalt oxide, LiCoO2 and piezoelectric compound, LiNbO3 prepared by
mechanical milling method. The milling process gives quite different effects on
NMR spectra of these compounds. Both 7Li MAS and static NMR spectra of the
milled LiCoO2 showed the line broadening with increasing milling time. 59Co static
spectra also showed specific changes in the line shape with increasing milling time.
These results would be attributed to the change in an electronic state of Co 3d
orbitals because of charge compensation associated with oxygen vacancies and/or
defects. 7Li static NMR spectrum of milled LiNbO3 exhibited complicated line
shape with increasing milling time. It was explained by superposition of two
spectra arising from mobile Li+ ions and non-mobile ones settled on the fixed site.
It was shown that the ratio of mobile Li+ ions increased up to a maximum of 9.4%
with increasing milling time. Milling effects on the Li+ ionic diffusion in LiCoO2
and LiNbO3 were discussed in connection with changes in local structure.
Ionic Diffusion and Structural Changes in Lithium Compounds. K.Nakamura,
H.Hirano, D.Nishioka, S.Endou, K.Itsuki, Y.Michihiro, T.Moriga, N.Kuwata,
J.Kawamura: Solid State Ionics, 2009, 180[6-8], 621-5