Using synchrotron-based luminescence excitation spectroscopy in the energy range 4-20 eV at 8 K, the indirect-X optical band-gap transition in cubic boron nitride is determined as 6.36 ± 0.03 eV, and the quasi-direct band-gap energy of hexagonal boron nitride is determined as 5.96 ± 0.04 eV. The composition and structure of the materials are self-consistently established by optically detected x-ray absorption spectroscopy, and both x-ray diffraction and Raman measurements on the same samples give independent confirmation of their chemical and structural purity: together, the results are therefore considered as providing definitive measurements of the optical band-gap energies of the two materials.
-012Li + Diffusion and Its Structural Basis in the Nanocrystalline and Amorphous Forms of Two-Dimensionally Ion-Conducting LixTiS 2 .-The Li diffusion in the nanocrystalline and amorphous forms of LixTiS 2 is compared by measuring the temperature and frequency dependencies of the spin-lattice relaxation rate of 7 Li. A schematic model for the ionic conduction process in two-dimensional nanocrystalline fast ionic conductors is proposed, introducing grain surface pathways as the dominant track for mobile ions.
Spinel-type structured Li4+xTi5O12 (0 6 x 6 3 ) is actually one of the most promising
anode materials for Li ion batteries. In its nanostructured form it is already used in some commercially
available Li ion batteries. As was recently shown by our group (Wilkening et al., Phys. Chem.
Chem. Phys. 9 (2007) 1239), Li diffusivity in microcrystalline Li4+xTi5O12 with x = 0 is rather slow.
In the present contribution the Li conductivity in nanocrystalline samples of the electronic insulator
Li4Ti5O12 prepared by different routes is investigated using impedance spectroscopy. The mean
crystallite size of the samples is about 20 nm. The ionic conductivity of nanocrystalline Li4Ti5O12
obtained by mechanical treatment is higher by about two orders of magnitude compared to that found
for a material which was prepared following a sol-gel method. The latter resembles the behaviour of
the microcrystalline sample with an average particle size in the μm range rather than that of a nanocrystalline
ball milled one with a mean crystallite size of about than 20 nm. The larger conductivity
of the ball milled sample is ascribed to a much higher defect density generated when the particle size
is reduced mechanically.
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