Papers by Author: Martin Wilkening

Abstract: 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.

Abstract: Materials with an average particle size of less than about 50 nm often show new or at least enhanced physical properties. In many cases nanocrystalline ionic conductors exhibit a high increase of cation, e. g. Li+, or anion, e. g. F−, diffusivity. In the present contribution we review recent studies on ion dynamics in nanocrystalline ion conductors, both single-phase systems and composites, being prepared by high-energy ball milling. These include, e.g., LiTaO3, Li2O:Al2O3, LiF:Al2O3, BaF2, CaF2, BaF2:CaF2 and (BaF2:CaF2):Al2O3. Dynamic properties were probed by 7Li and/or 19F NMR line shape and relaxation as well as ion conductivity measurements.

Abstract: Multiple-time spin-alignment echo (SAE) NMR spectroscopy of spin- 3 2 nuclei is used to study ultraslow diffusion in the hexagonal layered Li ion conductor LixTiS2 (x  1). Two-time correlation functions were monitored by recording (Jeener-Broekaert) echo amplitudes for constant evolution and variable mixing times. Echo decay rates t