Electrochemically structured copper current collectors for application in energy conversion and storage: a review. - In: Energies, ISSN 1996-1073, Bd. 16 (2023), 13, 4933, S. 1-33
Copper current collectors (Cu CCs) impact the production technology and performance of many electrochemical devices by their unique properties and reliable operation. The efficiency of the related processes and the operation of the electrochemical devices could be significantly improved by optimization of the Cu CCs. Metallic Cu plays an important role in electrochemical energy storage and electrocatalysis, primarily as a conducting substrate on which the chemical processes take place. Li nucleation and growth can be influenced by the current collector by modulating the local current density and Li ion transport. For example, the commonly used planar Cu CC does not perform satisfactorily; therefore, a high number of different modifications of Cu CCs have been proposed and reported in the literature for minimizing the local current density, hindering Li dendrite formation, and improving the Coulombic efficiency. Here, we provide an updated critical overview of the basic strategies of 3D Cu CC structuring, methodologies for analyzing these structures, and approaches for effective control over their most relevant properties. These methods are described in the context of their practical usefulness and applicability in an effort to aid in their easy implementation by research groups and private companies with established traditions in electrochemistry and plating technology. Furthermore, the current overview could be helpful for specialists with experience in associated fields of knowledge such as materials engineering and surface finishing, where electrochemical methods are frequently applied. Motivated by the importance of the final application of Cu CCs in energy storage devices, this review additionally discusses the relationship between CC properties and the functional parameters of the already-implemented electrodes.
https://doi.org/10.3390/en16134933
Investigation on the influence of process parameters on the mechanical properties of extruded bio-based and biodegradable continuous fiber-reinforced thermoplastic sheets. - In: Polymers, ISSN 2073-4360, Bd. 15 (2023), 18, 3830, S. 1-14
The use of bio-based and biodegradable matrix materials in fiber-reinforced polymers (FRPs) is an approach to reduce the consumption of fossil resources and the amount of polymer waste. This study aims to assess the influence of the process parameters on the resulting mechanical properties of extruded bio-based and biodegradable continuous fiber-reinforced thermoplastics (CFRTPs) in the form of sheets. Therefore, the impregnation temperature during the production of PLA/flax fiber composites is varied between 220 ˚C and 280 ˚C, and the consolidation pressure, between 50 bar and 90 bar. A design of experiments approach is used. Fiber contents of 28.8% to 34.8% and void contents of 6.8% to 15.5% are determined for the composites by optical measurements. To assess the mechanical properties, tensile tests are performed. Using the evaluation software Minitab, a strong negative influence of the consolidation pressure on the tensile modulus and the tensile strength is observed. Increasing the pressure from 50 bar to 90 bar results in a reduction in the tensile modulus of 50.7% and a reduction in the tensile strength of 54.8%, respectively. It is assumed that this is due to fibers being damaged by the external force exerted onto the materials during the consolidation process in the calender. The influence of the impregnation temperature on the mechanical properties cannot be verified.
https://doi.org/10.3390/polym15183830
Ultrathin hematite-hercynite films for future unassisted solar water splitting. - In: Advanced Materials Technologies, ISSN 2365-709X, Bd. 8 (2023), 22, 2300655, S. 1-10
Photoelectrochemical (PEC) water splitting requires stable, efficient, and cost-effective photoelectrodes to enable future large-scale solar hydrogen production. Ultrathin hematite-hercynite photoanodes that meet all these criteria in an excellent way is presented here. Hematite-hercynite photoelectrodes are synthesized in a self-forming manner by thermal oxidation of iron-aluminum alloy films and characterized with regard to water splitting applications. Photoanodes fabricated from 17 wt.% Al at 493 ˚C for 8 h and 685 ˚C for 5 min exhibit, for instance, a photocurrent density of 1.24 and 1.53 mA cm−2 at 1.23 V versus RHE, respectively, as well as superior light absorption in the visible range of the solar spectrum. The PEC performance improvement in comparison to pure hematite thin film electrodes is first achieved by adjusting the aluminum concentration with an optimum range of 12-17 wt.% and second by optimizing the annealing conditions. The resulting photocurrent densities are about a factor of three higher than those obtained from electrodes synthesized from pure iron thin films using the same synthesis conditions. Finally, it is shown that ultrathin hematite-hercynite photoelectrodes enable even unassisted solar water splitting in a NaOH (1 m) electrolyte with a maximum solar-to-hydrogen conversion efficiency of 0.78%.
https://doi.org/10.1002/admt.202300655
Ni/Al multilayer reactions on nanostructured silicon substrates. - In: Journal of materials science, ISSN 1573-4803, Bd. 58 (2023), 31, S. 12811-12826
Fast energy release, which is a fundamental property of reactive multilayer systems, can be used in a wide field of applications. For most applications, a self-propagating reaction and adhesion between the multilayers and substrate are necessary. In this work, a distinct approach for achieving self-propagating reactions and adhesion between deposited Ni/Al reactive multilayers and silicon substrate is demonstrated. The silicon surface consists of random structures, referred to as silicon grass, which were created by deep reactive ion etching. Using the etching process, structure units of heights between 8 and 13 µm and density between 0.5 and 3.5 structures per µm^2 were formed. Ni and Al layers were alternatingly deposited in the stoichiometric ratio of 1:1 using sputtering, to achieve a total thickness of 5 µm. The analysis of the reaction and phase transformation was done with high-speed camera, high-speed pyrometer, and X-ray diffractometer. Cross-sectional analysis showed that the multilayers grew only on top of the silicon grass in the form of inversed cones, which enabled adhesion between the silicon grass and the reacted multilayers. A self-propagating reaction on silicon grass was achieved, due to the thermally isolating air pockets present around these multilayer cones. The velocity and temperature of the reaction varied according to the structure morphology. The reaction parameters decreased with increasing height and decreasing density of the structures. To analyze the exact influence of the morphology, further investigations are needed.
https://doi.org/10.1007/s10853-023-08794-9
3D passive microfluidic valves in silicon and glass using grayscale lithography and reactive ion etching transfer. - In: Microfluidics and nanofluidics, ISSN 1613-4990, Bd. 27 (2023), 8, 55, S. 1-12
A fabrication strategy for high-efficiency passive three-dimensional microfluidic valves with no mechanical parts fabricated in silicon and glass substrates is presented. 3D diffuser-nozzle valve structures were produced and characterized in their added value in comparison to conventional diffuser-nozzle valve designs with rectangular cross sections. A grayscale lithography approach for 3D photoresist structuring combined with a proportional transfer by reactive ion etching allowed to transfer 3D resist valve designs with high precision into the targeted substrate material. The efficiency with respect to the rectification characteristics or so-called diodicity of the studied valve designs is defined as the ratio of the pressure drops in backward and forward flow directions. The studied valve designs were characterized experimentally as well as numerically based on finite element simulations with overall matching results that demonstrate a significantly improved flow rectification of the 3D valves compared to the corresponding conventional structure. Our novel 3D valve structures show, for instance, even without systematic optimization a measured diodicity of up to 1.5 at low flow rates of only about 10 μl/s.
https://doi.org/10.1007/s10404-023-02663-2
Ultrafast coupling of optical near fields to low-energy electrons probed in a point-projection microscope. - In: Nano letters, ISSN 1530-6992, Bd. 23 (2023), 12, S. 5528-5534
We report the first observation of the coupling of strong optical near fields to wavepackets of free, 100 eV electrons with <50 fs temporal resolution in an ultrafast point-projection microscope. Optical near fields are created by excitation of a thin, nanometer-sized Yagi-Uda antenna, with 20 fs near-infrared laser pulses. Phase matching between electrons and near fields is achieved due to strong spatial confinement of the antenna near field. Energy-resolved projection images of the antenna are recorded in an optical pump-electron probe scheme. We show that the phase modulation of the electron by transverse-field components results in a transient electron deflection while longitudinal near-field components broaden the kinetic energy distribution. This low-energy electron near-field coupling is used here to characterize the chirp of the ultrafast electron wavepackets, acquired upon propagation from the electron emitter to the sample. Our results bring direct mapping of different vectorial components of highly localized optical near fields into reach.
https://doi.org/10.1021/acs.nanolett.3c00738
Influence of extrinsic induced tensile stress on the self-propagating high-temperature synthesis of nanosized Al/Ni multilayers. - In: Journal of materials science, ISSN 1573-4803, Bd. 58 (2023), 24, S. 10085-10095
Reactive multilayer systems consisting of alternating nanoscale Al and Ni layers are applicable in joining, various pyrotechnic applications and thermal batteries. Since diffusion based high-temperature synthesis occurs without the presence of air, efforts have focused on investigating the understanding of the fundamental reaction processes and characteristics. The aim of this study is to expose the reactive multilayers to extrinsic induced tensile stress so that the self-propagating synthesis can proceed under these conditions. Further, the properties during and after the reaction will be investigated. Multilayers deposited by sputtering on Kapton® substrates with different bilayer- and total thicknesses as well as commercial Nanofoils® with thicknesses of 40 µm and 60 µm were used as samples. The investigations focused on the propagation velocity measured with a high-speed camera, the temperature regime determined with a high-speed pyrometer, and the formed phases after the synthesis examined via X-ray diffraction. The gained results of this study reveal important insights for the application of the reactive Al/Ni multilayer system in terms of stability or reliability related to propagation front velocity, maximum temperature and formed phases under induced external tensile stresses.
https://doi.org/10.1007/s10853-023-08618-w
Novel gas phase route toward patterned deposition of sputter-free Pt/Al nanofoils. - In: Advanced Materials Technologies, ISSN 2365-709X, Bd. 8 (2023), 18, 2300448, S. 1-8
This article reports a new approach toward fabrication and directed assembly of nanoparticulate reactive system (Nanofoils) on patterned substrates. Different from current state-of-the-art, gas phase electrodeposition uses nanoparticles instead of atoms to form densely packed multilayered thin films at room temperature-pressure. On ignition, the multilayer system undergoes an exothermic self-propagating reaction. The numerous contact points between two metallic nanoparticulate layers aid in high heat release. Sub-10-nm Platinum (Pt) and Aluminum (Al) particles are synthesized through cathode erosion of metal electrodes in a flow of pure nitrogen gas (spark ablation). Pt/Al bilayer stacks with total thickness of 3–8 µm undergo self-propagating reaction with a 10.3 mm s−1 wavefront velocity on local ignition. The reaction wavefront is captured using high speed videography. Calorimetry studies reveal two exothermic peaks suggesting Pt/Al alloy formation. The peak at 135 ˚C has a higher calorific value of 150 mW g−1 while the peak at 400 ˚C has a 12 mW g−1 exothermic peak. X-ray diffraction study shows reaction-products are cubic Al2Pt with small quantities of orthorhombic Al6Pt and orthorhombic AlPt2. Electron microscopy studies help draw a correlation between film morphology, bimetallic interface, nanoparticle oxidation, and self-propagating reaction kinetics that is significant in broadening our understanding towards nanoparticulate reactive systems.
https://doi.org/10.1002/admt.202300448
Temperature dependence of the hyperfine magnetic field at Fe sites in Ba-doped BiFeO3 thin films studied by emission Mössbauer spectroscopy. - In: Crystals, ISSN 2073-4352, Bd. 13 (2023), 5, 724, S. 1-13
Emission 57Fe Mössbauer spectroscopy (eMS), following the implantation of radioactive 57Mn+ ions, has been used to study the temperature dependence of the hyperfine magnetic field at Fe sites in Ba-doped BiFeO3 (BFO) thin films. 57Mn β decays (t1/2 = 90 s) to the 14.4 keV Mössbauer state of 57Fe, thus allowing online eMS measurements at a selection of sample temperatures during Mn implantation. The eMS measurements were performed on two thin film BFO samples, 88 nm and 300 nm thick, and doped to 15% with Ba ions. The samples were prepared by pulsed laser deposition on SrTiO3 substrates. X-ray diffraction analyses of the samples showed that the films grew in a tetragonal distorted structure. The Mössbauer spectra of the two films, measured at absorber temperatures in the range 301 K-700 K, comprised a central pair of paramagnetic doublets and a magnetic sextet feature in the wings. The magnetic component was resolved into (i) a component attributed to hyperfine interactions at Fe3+ ions located in octahedral sites (Bhf); and (ii) to Fe3+ ions in implantation induced lattice defects, which were characterized by a distribution of the magnetic field BDistr. The hyperfine magnetic field at the Fe probes in the octahedral site has a room temperature value of Bhf = 44.5(9) T. At higher sample temperatures, the Bhf becomes much weaker, with the Fe3+ hyperfine magnetic contribution disappearing above 700 K. Simultaneous analysis of the Ba-BFO eMS spectra shows that the variation of the hyperfine field with temperature follows the Brillouin curve for S = 5/2.
https://doi.org/10.3390/cryst13050724
Solid-state dewetting of Ag/Ni bi-layers: accelerated void formation by the stress gradient in the bottom Ni layer. - In: Journal of alloys and compounds, ISSN 1873-4669, Bd. 960 (2023), 170735
Solid-state dewetting (SSD) of the immiscible Ag/Ni bi-layers was studied. After annealing at 400 ˚C for 1 min, the Ag film was dewetted on the Ni film, and this is the first observation about the SSD of one metal film on another metal film. The easier dewetting of Ag than Ni was attributed to its lower melting point, faster grain boundary self-diffusion and poor wettability between them. At 500 ˚C, the void formation in the bottom Ni layer was highlighted and compared to Ni single layer: many voids in the former while no visible voids in the latter, indicating that the presence of Ag accelerated the SSD of Ni. It was attributed to the vertical stress gradient in the bottom Ni film of Ag/Ni bi-layers, which accelerated the Ni diffusion and formation of the voids in the underlying Ni film around and below the Ag particles. Besides, voids were more easily formed below the Ag particles than between them due to the large lattice mismatch at the Ag/Ni interface and the possible formation of Ag-Ni alloys. The destabilization of the Ag on the Ni film contributes to the understanding of dewetting kinetics, which is beneficial to realize the controllable nanofabrication.
https://doi.org/10.1016/j.jallcom.2023.170735