Papers by Author: Paul Heitjans

Abstract: The diffusion of lithium in amorphous lithium niobate layers is studied as a function of temperature between 293 and 423 K. About 800 nm thick amorphous ⁷LiNbO₃ layers were deposited on sapphire substrates by ion-beam sputtering. As a tracer source about 20 nm thin ⁶LiNbO₃ layers were sputtered on top. Isotope depth profile analysis is done by secondary ion mass spectrometry. Compared are amorphous samples which show a ratio of Li : Nb < 1 (Li-poor) and of Li : Nb > 1 (Li-rich) close to the stoichiometric composition of Li : Nb = 1 for crystalline LiNbO₃. The results reveal that the diffusivities of both types of samples obey the Arrhenius law with an activation enthalpy of 0.70 eV and 0.83 eV, respectively. The diffusivities of the sample containing a higher amount of Li are lower by a factor of about two to ten. This demonstrates that variation of the Li content in amorphous samples over the stability range of the crystalline LiNbO₃ phase has only a modest influence on diffusivities and activation enthalpies.

Abstract: Li diffusion is investigated in Li₂O-deficient, (110) oriented LiNbO₃ single crystals in the temperature range between 523 and 673 K by secondary ion mass spectrometry. A thin layer of ion-beam sputtered isotope enriched ⁶LiNbO₃ was used as a tracer source, which allows one to study pure isotope interdiffusion. The diffusivities coincide with those of (001) oriented single crystals and follow the Arrhenius law with an activation enthalpy of 1.33 eV. The results prove the existence of a three-dimensional diffusion mechanism.

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