Wolfram Münchgesang

The anisotropy of oxygen vacancy migration in SrTiO3.

Oxygen migration in perovskites is well known to occur via vacancies along the TiO6 octahedron edges. Ionic conduction depends further on the orientation of the crystal in the electric field. To study the anisotropy in cubic SrTiO3 single crystals, temperature-dependent electroformation measurements ranging from 11 °C to 50 °C have been conducted for representative crystallographic directions within the crystal system. Electroformation of pure SrTiO3 follows an Arrhenius behavior, implying an ionic migration process of intrinsic oxygen defects. Activation energies E A for oxygen vacancy migration have been determined to 0.70 eV for [Formula: see text] and [Formula: see text] directions in contrast to 0.77 eV for [Formula: see text]. Mobility of oxygen vacancies is enhanced in [Formula: see text] compared to [Formula: see text] and [Formula: see text] by up to half an order of magnitude. A migration model based on atomistic migration paths and their multiplicities accounts for these experimental variations in mobility.

On the Way to New Possible Na-Ion Conductors: The Voronoi-Dirichlet Approach, Data Mining and Symmetry Considerations in Ternary Na Oxides.

With the constant growth of the lithium battery market and the introduction of electric vehicles and stationary energy storage solutions, the low abundance and high price of lithium will greatly impact its availability in the future. Thus, a diversification of electrochemical energy storage technologies based on other source materials is of great relevance. Sodium is energetically similar to lithium but cheaper and more abundant, which results in some already established stationary concepts, such as Na-S and ZEBRA cells. The most significant bottleneck for these technologies is to find effective solid ionic conductors. Thus, the goal of this work is to identify new ionic conductors for Na ions in ternary Na oxides. For this purpose, the Voronoi-Dirichlet approach has been applied to the Inorganic Crystal Structure Database and some new procedures are introduced to the algorithm implemented in the programme package ToposPro. The main new features are the use of data mined values, which are then used for the evaluation of void spaces, and a new method of channel size calculation. 52 compounds have been identified to be high-potential candidates for solid ionic conductors. The results were analysed from a crystallographic point of view in combination with phenomenological requirements for ionic conductors and intercalation hosts. Of the most promising candidates, previously reported compounds have also been successfully identified by using the employed algorithm, which shows the reliability of the method.

Energy Storage in crystalline Materials based on multivalent Ions

Energy conversion and storage has become the main challenge to satisfy the growing demand for renewable energy solutions as well as mobile applications. Nowadays, several technologies exist for the conversion of electric energy into e. g. heat, light and motion or vice versa. Among a large variety of storage concepts, the conversion of electrical in chemical energy is of great relevance in particular for location-independent use. Main factors that still limit the use of electrochemical cells are the volumetric and gravimetric energy density, cyclability as well as safety. The concept for a new thin-film rechargeable battery that possibly improves these properties is presented. In contrast to the widespread lithium-ion technology, the discussed battery is based on the redox reaction of multivalent Al-ions and their migration through solid electrolytes. The ion conduction and insertion processes in the crystalline materials of the suggested cell are discussed under a crystallographic point of view to identify suitable electrode and separator materials. A multilayer-stack of all-solid-state batteries is synthesized by pulsed laser deposition and investigated in situ, i. e. during charge and discharge, by X-ray reflection and diffraction methods. The correlation between crystal structure, morphology and electrical performance is investigated in order to characterize the ion diffusion and insertion process.

Categorization of electrochemical storage materials en route to new concepts

Because of their broad range of applications, electrochemical energy storage devices are the subject of a growing field of science and technology. Their unique features of high practical energy and power densities and low prices allow mobile and stationary applications. A large variety of electrochemical systems has been tailored for specific applications: Lithium-ion batteries for example have been optimized for mobile applications ranging from mobile phones to electric vehicles. On the other hand, sodium-sulphur accumulators – among others – have been developed for stationary applications to account for the capricious nature of renewable energies. Chemistry, physics and materials science have led to the optimization of existing cell-chemistries and the development of new concepts such as all-liquid or all-solid state batteries as well as high-energy density metal-air batteries. The aim of the BMBF (Federal Ministry of Education and Research, Germany)-financed project “CryPhysConcept” is to develop new concepts for electrochemical energy storage applying a crystallographic approach. First, a categorization of the main solid components of batteries based on their underlying working principles is suggested. Second, an algorithm for the identification of suitable new materials and material combinations, based on economical, ecological and material properties as well as crystallographic parameters, is presented. Based on these results, new concepts using multi-valent metal ions are proposed. Theoretical as well as experimental results including an iron-ion approach are presented.