Influence of Molecular Weight and Lithium Bis(trifluoromethanesulfonyl)imide on the Thermal Processability of Poly(ethylene oxide) for Solid-State Electrolytes.

New energy systems such as all-solid-state battery (ASSB) technology are becoming increasingly important today. Recently, researchers have been investigating the transition from the lab-scale production of ASSB components to a larger scale. Poly(ethylene oxide) (PEO) is a promising candidate for the large-scale production of polymer-based solid electrolytes (SPEs) because it offers many processing options. Hence, in this work, the thermal processing route for a PEO-Lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) SPE in the ratio of 20:1 (EO:Li) is investigated using kneading experiments. Here, we clearly show the sensitivity of PEO during thermal processing, especially for high-molecular-weight PEO (Mw = 600,000 g mol-1). LiTFSI acts as a plasticizer for low-molecular-weight PEO (Mw = 100,000 g mol-1), while it amplifies the degradation of high-molecular-weight PEO. Further, LiTFSI affects the thermal properties of PEO and its crystallinity. This leads to a higher chain mobility in the polymer matrix, which improves the flowability. In addition, the spherulite size of the produced PEO electrolytes differs from the molecular weight. This work demonstrates that low-molecular-weight PEO is more suitable for thermal processing as a solid electrolyte due to the process stability. High-molecular-weight PEO, especially, is strongly influenced by the process settings and LiTFSI.

Determination of Reaction Enthalpies of Synthesizing ß-Li3PS4 in Tetrahydrofuran.

While some promising materials for all-solid-state batteries are already extensively investigated in a lab scale, the transferability to mass production is still a limiting factor. ß-lithium thiophosphate (ß-Li3PS4) has good ionic conductivity and can be synthesized wet-chemically, which opens up the possibility for scale-up. For safe upscaling, the enthalpies of the synthesis steps need to be examined in order to handle exothermic and endothermic processes. Here, the reaction enthalpies of the wet-chemical synthesis of ß-Li3PS4 in tetrahydrofuran (THF) are determined. The synthesis routine is established in a lab scale, and the synthesis success is confirmed via X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). The reaction of the educts in THF is investigated using a reaction calorimeter and shows a strongly exothermic process. The subsequent processes are examined using differential scanning calorimetry with thermogravimetric analysis and show a strong endothermic process during solvent removal and a slightly exothermic process during crystallization.

Syntactic Iron Foams' Properties Tailored by Means of Case Hardening via Carburizing or Carbonitriding.

Metal foam inserts are known for their high potential for weight and vibration reduction in composite gear wheels. However, most metal foams do not meet the strength requirements mandatory for the transfer of sufficiently high levels of torque by the gears. Syntactic iron and steel foams offer higher strength levels than conventional two-phase metal foams, thus making them optimum candidates for such inserts. The present study investigates to what extent surface hardening treatments commonly applied to gear wheels can improve the mechanical properties of iron-based syntactic foams. Experiments performed thus focus on case hardening treatments based on carburizing and carbonitriding, with subsequent quenching and tempering to achieve surface hardening effects. Production of samples relied on the powder metallurgical metal injection molding (MIM) process. Syntactic iron foams containing 10 wt.% of S60HS hollow glass microspheres were compared to reference materials without such filler. Following heat treatments, the samples' microstructure was evaluated metallographically; mechanical properties were determined via hardness measurements on reference samples and 4-point bending tests, on both reference and syntactic foam materials. The data obtained show that case hardening can indeed improve the mechanical performance of syntactic iron foams by inducing the formation of a hardened surface layer. Moreover, the investigation indicates that the respective thermo-chemical treatments can be applied to composite gear wheels in exactly the same way as to monolithic ones. In the surface region modified by the treatment, martensitic microstructures were observed, and as consequence, the bending limits of syntactic foam samples were increased by a factor of three.

A Combined Thin Film/Thick Film Approach to Realize an Aluminum-Based Strain Gauge Sensor for Integration in Aluminum Castings.

There is currently a large demand for aluminum components to measure the mechanical and thermal loads to which they are subjected. With structural health monitoring, components in planes, vehicles, or bridges can monitor critical loads and potentially prevent an impending fatigue failure. Externally attached sensors need a structural model to obtain knowledge of the mechanical load at the point of interest, whereas embedded sensors can be used for direct measurement at the point of interest. To produce an embedded sensor, which is automatically encapsulated against environmental influence, the sensor must be able to withstand the boundary conditions of the host component's manufacturing process. This embedding process is particularly demanding in the case of casting. Previous work showed that silicon-based sensors have a high failure rate when embedded in cast aluminum parts and that using aluminum as a substrate is preferable under these circumstances. In the present paper, we present the fabrication process for the combination of a thick-film insulation and a thin-film strain gauge sensor, on such an aluminum substrate. The sensor is capable of withstanding high temperatures of at least 600 °C for over 20 min and a subsequent embedding in a gravity die casting process.

Structural and Computational Assessment of the Influence of Wet-Chemical Post-Processing of the Al-Substituted Cubic Li7La3Zr2O12.

Li7La3Zr2O12 (LLZO) and related compounds are considered as promising candidates for future all-solid-state Li-ion battery applications. Still, the processing of those materials into thin membranes with the right stoichiometry and crystal structure is difficult and laborious. The sensitivity of the Li-ion conductive garnets against moisture and the associated Li+/H+ cation exchange makes their processing even more difficult. Formulation of suitable polymer/ceramic hybrid solid state electrolytes could be a prosperous way to reach the future large scale production of solid state Li-ion batteries. In fact, solvent mediated and/or slurry based wet-processing of the LLZO, e.g., tape-casting, could result in irreversible Li-ion loss of the pristine material due to Li+/H+ cation exchange. The concomitant structural changes and loss in functionality in terms of Li-ion conductivity are the results of the above process. Therefore, in the present work a systematic study on the chemical stability and structural retention of Al-substituted LLZO in different solvents is reported. It was found that Li+/H+ exchange in LLZO occurs upon solvent immersion, and its magnitude is dependent on the availability of -OH functional groups of the solvent molecules. As a result, a larger degree of Li+/H+ exchange causes higher increase of the lattice parameter of the LLZO, determined by synchrotron diffraction analyses. The expansion of the cubic unit cell was ascertained, when Li+ was replaced by H+ in the host lattice, by ab initio computational studies. The application of the most common solvent as dispersion medium, i.e., high purity water, causes the most significant Li+/H+ exchange and, therefore, structural change, while acetonitrile was proven to be the best suitable solvent for wet postprocessing of LLZO. Finally, computational calculations suggested that the Li+/H+ exchange could result in diminished ionic, i.e., mixed Li+-H+, conductivity due to the insertion of protons with lower mobility than that of Li-ions.

Lithiation Behavior of Silicon Nanowire Anodes for Lithium-Ion Batteries: Impact of Functionalization and Porosity.

Metal-assisted chemical etching (MACE) provides a versatile way to synthesize silicon nanowires (SiNW) of different morphologies. MACE was used to synthesize oxide-free porous and nonporous SiNW for use as anodes for lithium-ion batteries. To improve their processing behavior, the SiNW were functionalized using acrylic acid. Differential capacity plots were used as a way to identify the degradation processes during cycling through tracking the formation of Li15 Si4 and changes in polarization. The cycling performance between porous and nonporous SiNW differed regarding Coulombic efficiency and cycling stability. The differences were attributed to the porous hull and its ability to reduce the volume expansion, although not through its porous nature but the reduced uptake of Li ions.

Cloud-Based Automated Design and Additive Manufacturing: A Usage Data-Enabled Paradigm Shift.

Integration of sensors into various kinds of products and machines provides access to in-depth usage information as basis for product optimization. Presently, this large potential for more user-friendly and efficient products is not being realized because (a) sensor integration and thus usage information is not available on a large scale and (b) product optimization requires considerable efforts in terms of manpower and adaptation of production equipment. However, with the advent of cloud-based services and highly flexible additive manufacturing techniques, these obstacles are currently crumbling away at rapid pace. The present study explores the state of the art in gathering and evaluating product usage and life cycle data, additive manufacturing and sensor integration, automated design and cloud-based services in manufacturing. By joining and extrapolating development trends in these areas, it delimits the foundations of a manufacturing concept that will allow continuous and economically viable product optimization on a general, user group or individual user level. This projection is checked against three different application scenarios, each of which stresses different aspects of the underlying holistic concept. The following discussion identifies critical issues and research needs by adopting the relevant stakeholder perspectives.

Hydrothermal synthesis and humidity sensing property of ZnO nanostructures and ZnO-In(OH)3 nanocomposites.

Prism- and raspberry-like ZnO nanoparticles and ZnO-In(OH)(3) nanocomposites were prepared by template free hydrothermal method. XRD investigations and microscopic studies showed that pill-like In(OH)(3) particles with body-centered cubic crystal structure formed on the surface of ZnO nanoparticles resulting in increased specific surface area. TEM-EDX mapping images demonstrated that not only nanocomposite formation took place in the course of the synthesis, but zinc ions were also built into the crystal lattice of the In(OH)(3). However, only undoped In(OH)(3) was found on the surface of the pill-like particle aggregates by XPS analyses. The raspberry- and prism-like ZnO particles exhibit strong visible emission with a maximum at 585 and 595 nm, respectively, whose intensity significantly increase due to nanocomposite formation. Photoelectric investigations revealed that photocurrent intensity decreased with increasing indium ion concentration during UV light excitation, which was explained by increase in visible fluorescence emission. QCM measurements showed that morphology of ZnO and concentration of In(OH)(3) had an influence on the water vapor sensing properties.

Surface biofunctionalization and production of miniaturized sensor structures using aerosol printing technologies.

The work described in this paper demonstrates that very small protein and DNA structures can be applied to various substrates without denaturation using aerosol printing technology. This technology allows high-resolution deposition of various nanoscaled metal and biological suspensions. Before printing, metal and biological suspensions were formulated and then nebulized to form an aerosol which is aerodynamically focused on the printing module of the system in order to achieve precise structuring of the nanoscale material on a substrate. In this way, it is possible to focus the aerosol stream at a distance of about 5 mm from the printhead to the surface. This technology is useful for printing fluorescence-marked proteins and printing enzymes without affecting their biological activity. Furthermore, higher molecular weight DNA can be printed without shearing. The advantages, such as printing on complex, non-planar 3D structured surfaces, and disadvantages of the aerosol printing technology are also discussed and are compared with other printing technologies. In addition, miniaturized sensor structures with line thicknesses in the range of a few micrometers are fabricated by applying a silver sensor structure to glass. After sintering using an integrated laser or in an oven process, electrical conductivity is achieved within the sensor structure. Finally, we printed BSA in small micrometre-sized areas within the sensor structure using the same deposition system. The aerosol printing technology combined with material development offers great advantages for future-oriented applications involving biological surface functionalization on small areas. This is important for innovative biomedical micro-device development and for production solutions which bridge the disciplines of biology and electronics.