Publikationen

In this study, carbide-derived carbon fibers from silicon oxycarbide precursor were synthesized by electrospinning of a commercially available silicone resin without adding a carrier polymer for the electrospinning process. The electrospun fibers were pyrolyzed yielding SiOC. Modifying the synthesis procedure, we were also able to obtain electrosprayed SiOC beads instead of fibers. After chlorine treatment, nanoporous carbon with a specific surface area of up to 2394 m2 g−1 was obtained (3089 m2 g−1 BET). Electrochemical characterization of the SiOC-CDC either as free-standing fiber mat electrodes or polymer-bound bead films was performed in 1 M tetraethylammonium tetrafluoroborate in acetonitrile (TEA-BF4 in ACN). The electrospun fibers presented a high gravimetric capacitance of 135 F g−1 at 10 mV s−1 and a very high power handling, maintaining 63% of the capacitance at 100 A g−1. Comparative data of SiOC-CDC beads and fibers show enhanced power handling for fiber mats only when the fiber network is intact, that is, a lowered performance was observed when using crushed mats that employ polymer binder.

Metallic lithium is the most widespread reference electrode in lithium ion battery research, but its high reactivity limits the usage primarily to conventional carbonate based electrolytes. Novel high power concepts, like hybrid supercapacitors, require lithium containing electrolytes with high ionic conductivity (e.g., acetonitrile), which are not always stable versus lithium. In the current work we face this issue by refining activated carbon as a quasi-reference electrode originally employed for conventional supercapacitors. Different commercially available carbon powders were examined as reference electrode materials and calibrated in lithium-salt containing acetonitrile versus Li+ intercalation/de-intercalation reaction of nanoparticulate Li4Ti5O12. The stability of the activated carbon reference electrode is highly affected by the salt employed and decreases in the following order: LiTFSI > LiClO4 > LiPF6 > LiBF4. Only a negligible impact of electrolyte solvent, pore size distribution and reference electrode binder was observed. Furthermore, activated carbon was functionalized (HNO3 treated) and de-functionalized (thermal annealing in vacuum or hydrogen) to investigate the impact of carbon functionalization on the reference electrode stability. Nitrogen and oxygen containing surface groups have been found to drastically improve long-term stability of activated carbon quasi-reference electrodes. Even after 15 days exposed to the electrolyte, the potential of HNO3 treated activated carbon is marginally altered by 10 mV.

A novel, two step synthesis is presented combining the formation of carbide-derived carbon (CDC) and redox-active vanadium pentoxide (V2O5) in a core-shell manner using solely vanadium carbide (VC) as the precursor. In a first step, the outer part of VC particles is transformed to nanoporous CDC owing to the in situ formation of chlorine gas from NiCl2 at 700 [degree]C. In a second step, the remaining VC core is calcined in synthetic air to obtain V2O5/CDC core-shell particles. Materials characterization by means of electron microscopy, Raman spectroscopy, and X-ray diffraction clearly demonstrates the partial transformation from VC to CDC, as well as the successive oxidation to V2O5/CDC core-shell particles. Electrochemical performance was tested in organic 1 M LiClO4 in acetonitrile using half- and asymmetric full-cell configuration. High specific capacities of 420 mA h g-1 (normalized to V2O5) and 310 mA h g-1 (normalized to V2O5/CDC) were achieved. The unique nanotextured core-shell architecture enables high power retention with ultrafast charging and discharging, achieving more than 100 mA h g-1 at 5 A g-1 (rate of 12C). Asymmetric cell design with CDC on the positive polarization side leads to a high specific energy of up to 80 W h kg-1 with a superior retention of more than 80% over 10 000 cycles and an overall energy efficiency of up to 80% at low rates.

Manganese oxide presents very promising electrochemical properties as an electrode material in supercapacitors, but there remain important open questions to guide further development of the complex manganese oxide/carbon/electrolyte system. Our work addresses specifically the influence of carbon ordering and the difference between outer and inner porosity of carbon particles for the application in aqueous 1 M Na2SO4 and 1 M LiClO4 in acetonitrile. Birnessite-type manganese oxide was hydrothermally hybridized on two kinds of carbon onions with only outer surface area and different electrical conductivity, and conventional activated carbon with a high inner porosity. Carbon onions with a high degree of carbon ordering, high conductivity, and high outer surface area were identified as the most promising material, yielding 179 F g-1. Pore blocking in activated carbon yields unfavorable electrochemical performances. The highest specific energy of 16.4 W h kg-1 was measured for a symmetric full-cell arrangement of manganese oxide coated high temperature carbon onions in the organic electrolyte. High stability during 10 000 cycles was achieved for asymmetric full-cells, which proved as a facile way to enhance the electrochemical performance stability.

Carbon onions are a relatively new member of the carbon nanomaterials family. They consist of multiple concentric fullerene-like carbon shells which are highly defective and disordered. Due to their small size of typically below 10 nm, the moderate surface area, and high conductivity they were used for supercapacitor applications. As electrode material, carbon onions provide fast charge/discharge rates resulting in high specific power but present comparable low specific energy. They improve the performance of activated carbon electrodes as conductive additive and show suitable properties as substrate for redox-active materials. This review provides a critical discussion of the electrochemical properties of different types of carbon onions as electrode material. It also compares general advantages and disadvantages of different carbon onion synthesis methods. The structure, physical and chemical properties of carbon onions, in particular nanodiamond-derived carbon onions, are described with emphasis on those parameters especially important for electrochemical energy storage systems, including among others structure, conductivity, and porosity. Although the primary focus of current research is on electrode materials for supercapacitors, the use of carbon onions as conductive additive for activated carbon and electro-active polymers, as well as substrate for redox-active species is also discussed.

We synthesized CuZr/Cu multilayers and performed nanoindentation testing to explore the dependence of plastic deformation modes on the thickness of CuZr layers. The Cu layers were 18 nm thick and the CuZr layers varied in thickness from 4 nm to 100 nm. We observed continuous plastic co-deformation in the 4 nm and 10 nm CuZr − 18 nm Cu multilayers and plastic-induced shear instability in thick CuZr layers (>20 nm). The plastic co-deformation is ascribed to the nucleation and interaction of shear transformation zones in CuZr layers at the adjacent interfaces, while the shear instability is associated with the nucleation and propagation of shear bands in CuZr layers. Shear bands are initialized in the CuZr layers due to the accumulated glide dislocations along CuZr-Cu interfaces, and propagate into adjacent Cu layers via slips on {111} plane non-parallel to the interface. Due to crystallographic constraint of the Cu layers, shear bands are approximately parallel to {111} plane in the Cu layer.

This study investigated the effect of temperature on indentation-induced one-way and two-way shape memory properties in Ti-50.3 at% Ni alloy. Indentation temperatures ranged from below the martensite finish temperature (Mf) to above the austenite finish temperature (Af) with the explicit intent of varying the indented phase. Samples used in the study were characterized by differential scanning calorimetry and transmission electron microscopy (TEM). The topographical behavior of the shape memory effect was investigated through Vickers indentation and laser scanning 3D confocal measurements. The magnitudes of deformation recovery associated with the one-way and two-way shape-memory effect (OWSME, TWSME) decreased with increasing indentation temperatures, which is a reflection of the decreasing volume of material experiencing martensitic reorientation during indentation. Indented and subsequently planarized samples exhibited TWSME protrusions when thermally cycled. Laser scanning measurements were used to characterize the height of the protrusions as increasing depths of material were polished away, which provided insight into the overall affected volume beneath the indent. As indentation temperatures increased, both the height of the protrusions, and consequently the polish depth necessary to completely remove the effect, decreased. TEM investigations revealed that directly underneath a nanoindent the microstructure was very fine due to the high-strain deformation; this was contrasted with a much coarser grain size in the undeformed bulk material. Overall these results strongly imply that the deformation recovery associated with the OWSME and TWSME can be maximized by indenting at temperatures at Mf or below because the volume of deformed microstructure beneath the indent is maximized. This finding has important practical value for any potential application that utilizes indentation-induced phase transformation deformation recovery in NiTi.

Aspherical optical lenses with spatially varying curvature are desired for capturing high quality, aberration free images in numerous optical applications. Conventionally such lenses are prepared by multistep top-down processes which are expensive, time-consuming, and prone to high failure rate. In this context, an alternate method is presented here based on arrested spreading of a sessile drop of a transparent, cross-linkable polymeric liquid on a solid substrate heated to an elevated temperature. Whereas surface tension driven flow tends to render it spherical, rapid cross-linking arrests such flow so that nonequilibrium aspherical shapes are attained. It is possible to tune also the initial state of the drop via delayed pinching of a liquid cylinder which precedes its release on the substrate. This method has led to the generation of a wide variety of optical lenses, ranging from spherical plano convex to superspherical solid immersion to exotic lenses not achieved via conventional methods.

Various local testing methods, namely, nanoindentation, compression and bending tests of micropillars were used to better understand the influence of ternary Cr atoms on the extrinsic and intrinsic mechanical properties of Fe3Al intermetallics with the D03 super lattice. Using such local techniques enables us to quantify the influence of Cr on the enhancement of the Young´s modulus. Furthermore, the effect of Cr on the yield stress, strain hardening and appearance of slip traces was studied based on the stress-strain curves and secondary electron micrographs of the bended and compressed pillars.

Omniphobic surfaces found in nature have great potential for enabling novel and emerging products and technologies to facilitate the daily life of human societies. One example is the water and even oil-repellent cuticle of springtails (Collembola). The wingless arthropods evolved a highly textured, hierarchically arranged surface pattern that affords mechanical robustness and wetting resistance even at elevated hydrostatic pressures. Springtail cuticle-derived surfaces therefore promise to overcome limitations of lotus-inspired surfaces (low durability, insufficient repellence of low surface tension liquids). In this review, we report on the liquid-repellent natural surfaces of arthropods living in aqueous or temporarily flooded habitats including water-walking insects or water spiders. In particular, we focus on springtails presenting an overview on the cuticular morphology and chemistry and their biological relevance. Based on the obtained liquid repellence of a variety of liquids with remarkable efficiency, the review provides general design criteria for robust omniphobic surfaces. In particular, the resistance against complete wetting and the mechanical stability strongly both depend on the topographical features of the nano- and micropatterned surface. The current understanding of the underlying principles and approaches to their technological implementation are summarized and discussed.