Publikationen

The electrochemical flow capacitor (EFC) has been recently introduced as a new concept for rapid and capacitive energy storage using flowable carbon-electrolyte suspensions. In our study, we investigate the EFC under static and constant flow condition. Unlike static carbon suspensions where poor particle-particle-contact and particle settling yield a highly resistive and time-dependent behavior, we show that flow operation of carbon suspensions reach high Coulombic efficiency and stable energy density performance. Our results also indicate that the specific capacitance per total mass of carbon electrodes in flow operation is comparable to conventional binder-bound carbon film electrodes.

Capacitive technologies, such as capacitive deionization and energy harvesting based on mixing energy ("capmix" and "CO2 energy"), are characterized by intermittent operation: phases of ion electrosorption from the water are followed by system regeneration. From a system application point of view, continuous operation has many advantages, to optimize performance, to simplify system operation, and ultimately to lower costs. In our study, we investigate as a step towards second generation capacitive technologies the potential of continuous operation of capacitive deionization and energy harvesting devices, enabled by carbon flow electrodes using a suspension based on conventional activated carbon powders. We show how the water residence time and mass loading of carbon in the suspension influence system performance. The efficiency and kinetics of the continuous salt removal process can be improved by optimizing device operation, without using less common or highly elaborate novel materials. We demonstrate, for the first time, continuous energy generation via capacitive mixing technology using differences in water salinity, and differences in gas phase CO2 concentration. Using a novel design of cylindrical ion exchange membranes serving as flow channels, we continuously extract energy from available concentration differences that otherwise would remain unused. These results may contribute to establishing a sustainable energy strategy when implementing energy extraction for sources such as CO2-emissions from power plants based on fossil fuels.

Extracting electric energy from small temperature differences is an emerging field in response to the transition toward sustainable energy generation. We introduce a novel concept for producing electricity from small temperature differences by the use of an assembly combining ion exchange membranes and porous carbon electrodes immersed in aqueous electrolytes. Via the temperature differences, we generate a thermal membrane potential that acts as a driving force for ion adsorption/desorption cycles within an electrostatic double layer, thus converting heat into electric work. We report for a temperature difference of 30 °C a maximal energy harvest of ~2 mJ/m2, normalized to the surface area of all the membranes.

Electrochemical double layer capacitors (EDLCs) are inherently high power devices when compared to rechargeable batteries. While capacitance and energy storage ability are mainly increased by optimizing the electrode active material or the electrolyte, the power capability could be improved by including conductive additives in the electrode formulations. This publication deals with the use of four different carbon additives – two carbon blacks and two graphites – in standard activated carbon based EDLC electrodes. The investigations include: (i) physical characterization of carbon powder mixtures such as surface area, press density, and electrical resistivity measurements, and (ii), electrochemical characterization via impedance spectroscopy and cyclic voltammetry of full cells made with electrodes containing 5 wt.% of carbon additive and compared to cells made with pure activated carbon electrodes in organic electrolyte. Improved cell performance was observed in both impedance and cyclic voltammetry responses. The results are discussed considering the main characteristics of the different carbon additives, and important considerations about electrode structure and processability are drawn.

Most efforts to improve the energy density of supercapacitors are currently dedicated to optimized porosity or hybrid devices employing pseudocapacitive elements. Little attention has been given to the effects of the low charge carrier density of carbon on the total material capacitance. To study the effect of graphitization on the differential capacitance, carbon onion (also known as onion-like carbon) supercapacitors are chosen. The increase in density of states (DOS) related to the low density of charge carriers in carbon materials is an important effect that leads to a substantial increase in capacitance as the electrode potential is increased. Using carbon onions as a model, it is shown that this phenomenon cannot be related only to geometric aspects but must be the result of varying graphitization. This provides a new tool to significantly improve carbon supercapacitor performance, in addition to having significant consequences for the modeling community where carbons usually are approximated to be ideal metallic conductors. Data on the structure, composition, and phase content of carbon onions are presented and the correlation between electrochemical performance and electrical resistance and graphitization is shown. Highly graphitic carbons show a stronger degree of electrochemical doping, making them very attractive for enhancing the capacitance.

Hybrid materials represent one of the most growing new material classes at the edge of technological innovations. Unique possibilities to create novel material properties by synergetic combination of inorganic and organic components on the molecular scale makes this materials class interesting for application-oriented research of chemists, physicists, and materials scientists. The modular approach for combination of properties by the selection of the best suited components opens new options for the generation of materials that are able to solve many technological problems. This review will show in selected examples how science and technological driven approaches can help to design better materials for future applications.

Amphiphilic surface-functionalized titania nanoparticles were prepared in a Pickering emulsion applying hydrophobic or hydrophilic agents containing a phosphonate anchor group. The Pickering emulsion approach allows for the formation of anisotropic nanoparticles with a high degree of surface-functionalization that mimic the behavior of surfactants. Therefore, the efficiency of the formed particles in stabilizing emulsions was studied and it could be shown that the stability of emulsions substantially increases by addition of amphiphilic particles. Due to the photocatalytic activity of anatase nanoparticles the emulsions stability against creaming can be decreased by irradiation with UV light. The critical micelle concentration (CMC) of suspensions of amphiphilically modified nanoparticles was determined by conductivity measurements. The prepared surface-functionalized nanoparticles show similar characteristics as amphiphilic block copolymers.

A novel strategy for a directed nanoparticle coupling to isolated Stephanopyxis turris valves is presented. After pyrolysis, the valves exhibit incomplete wetting due to their characteristic T-shaped profiles as a prerequisite for a regioselective coupling reaction. A micromanipulation system allows for precise handling and their immobilization onto an adhesive substrate and manipulation into arrays.

The surface stability of yttria-doped tetragonal polycrystalline zirconia is critical for load-bearing biomedical applications. In this work, the small-scale mechanical behavior of this material is probed by employing the in situ micro-cantilever bending technique to near-surface regions. Micro-cantilevers are milled by the focused ion beam technique in the as-sintered condition as well as after hydrothermal degradation by water vapor and tested in order to investigate the effect of degradation on the local flexural response. Results demonstrate that the technique is reliable for assessing the mechanical properties of thin superficial layers and their dependence on orientation. In the non-degraded material, the flexural strength is surprisingly higher than in standard-size specimens and transformation-induced plasticity takes place during testing, inducing defects that become critical at the failure stress. The strength and stiffness of cantilevers obtained from the degraded surface are indeed much lower, and the magnitude of the effect clearly depends on their orientation with respect to the surface. These results are discussed in terms of the presence and spatial distribution of microcracks nucleated during hydrothermal degradation.

Measurement of surface tension (s.t.) and critical micelle concentration (c.m.c.) of a surfactant in dynamic condition is important for several engineering applications, for which, the interface between two or more different phases does not remain constant but alters and replenishes continuously with flow of the fluids so that equilibrium may not be reached between the bulk and the interface. There are however not many methods for measuring these quantities in dynamic experiments which mimics the real dynamic situations. In this report, we present a novel two-phase flow pattern inside a triple-helical micro-channel using which, we show that it may be possible to measure the dynamic s.t. of a liquid. When two immiscible liquids such as oil and water are pumped into it, at a certain range of flow rates, oil flows as the continuous phase, whereas water remains in it as a wavy filament, the wavelength of which varies with the flow rates of oil and water but also on the interfacial tension between these two liquids. We show that wavelength decreases with increase in concentration of a solute attaining a minima at the c.m.c. A simple scaling analysis captures most experimental observations.