Analysis of the physical and photoelectrochemical properties of c-Si(p)/a-SiC:H(p) photocathodes for solar water splitting. - In: Journal of physics, ISSN 1361-6463, Bd. 54 (2021), 19, 195101, S. 1-12
The photoelectrochemical (PEC) properties of sputtered aluminum doped hydrogenated amorphous silicon carbide thin films grown on p-type crystalline silicon substrates were investigated in 1 M solution under chopped light illumination. Optical and structural properties of the top absorber layer were systematically assessed after post-deposition isochronical annealing treatments. Samples exhibited a noticeable improvement of the opto-electronic properties after thermal treatments. In addition, an abrupt enhancement of the photocurrent was observed reaching a saturation value of 17 mA cm^-2 at -1.75 V vs. Ag/AgCl (3.5 M KCl). In this research we propose that this enhancement effect is associated to a charge transfer kinetic mechanism influenced by surface states and the p-type substrate. The latter most likely due to the space charge region extending beyond the absorber layer reaching the substrate. Current density-potential and electrochemical impedance spectroscopy measurements in dark revealed a reduction of the native layer at cathodic potentials higher than -1 V vs. Ag/AgCl (3.5 M KCl), which contributes to the high charge transfer kinetic of the system. We believe that these results will contribute to understand the substrate influence in the PEC performance of top absorber layers in multilayer structures for solar water splitting.
https://doi.org/10.1088/1361-6463/abdb69
Anti-corrosive siloxane coatings for improved long-term performance of supercapacitors with an aqueous electrolyte. - In: Electrochimica acta, ISSN 1873-3859, Bd. 372 (2021), 137840, S. 1-15
This paper reports on the impact that the corrosion of the stainless steel current collectors has on the performance fade of a symmetric, carbon/carbon electrochemical capacitor, operating with an aqueous electrolyte (1M Na2SO4). The results obtained by applying electrochemical ageing protocols (voltage-holding tests) confirm that the current collector of the positive electrode undergoes tremendous degradation during 200 h in the charged state. To prevent the detrimental impact of the corrosion, a hydrophobic siloxane coating has been successfully applied. In the case of siloxane-protected current collectors that are subjected to identical ageing protocols, no significant deterioration in the electrochemical capacitor performance was observed. The siloxane coating reduces the electrochemical corrosion rate of 316L stainless steel significantly, as the potentiodynamic polarization tests and the electrochemical impedance spectroscopy results show. The presence of the coating is demonstrated by the water contact angle measurements, atomic force microscopy and energy-dispersive X-ray spectroscopy analysis.
https://doi.org/10.1016/j.electacta.2021.137840
Layer-by-layer polyelectrolyte assembly for the protection of GaP surfaces from photocorrosion. - In: ACS applied nano materials, ISSN 2574-0970, Bd. 4 (2021), 1, S. 425-431
Polyelectrolyte layer-by-layer assemblies are known as protective coatings for corrosion inhibition. Here, we demonstrate that polyelectrolyte multilayers of poly(ethyleneimine) (PEI) and poly(styrene sulfonate) (PSS)-(PEI/PSS)x-adsorbed at the GaP(100) photocathode surface remarkably mitigate the photocorrosion of GaP without decreasing its photoconversion efficiency. The activity of the polybase-polyacid complex is based on buffering pH changes at the solid-liquid interface. We carried out ab initio molecular dynamics-based simulations of the GaP(100) surface in contact with liquid water and demonstrated that an increase in the proton concentration enhances GaP dissolution. We used the scanning vibrating electrode technique (SVET) to characterize the distribution of photocorrosion activity areas over bare and polyelectrolyte-coated GaP surfaces and we showed that a polyelectrolyte coating impedes the dissolution kinetics. Data obtained using the SVET were compared to photoetched pores on the semiconductor surface. Voltammetric and chronoamperometric measurements were also performed to evaluate photoconversion efficiencies before and after the application of the protective coatings.
https://doi.org/10.1021/acsanm.0c02768
Electrocatalysis of lithium (poly-) sulfides in organic ether-based electrolytes. - In: Journal of the Electrochemical Society, ISSN 1945-7111, Bd. 167 (2021), 16, 166520, insges. 9 S.
https://doi.org/10.1149/1945-7111/abd60c
Electrocodeposition of Ni composites and surface treatment of SiC nano-particles. - In: Surface and coatings technology, ISSN 1879-3347, Bd. 406 (2021), 126663, insges. 8 S.
https://doi.org/10.1016/j.surfcoat.2020.126663
Determination of transport parameters in [EMIm]Cl-based ionic liquids - diffusion and electrical conductivity. - In: Electrochimica acta, ISSN 1873-3859, Bd. 366 (2021), 137370
The density, electrical conductivity and diffusion coefficients of anions and cations in the ionic liquid AlCl3/1-ethyl-3-methylimidazolium chloride, [EMIm]Cl, were determined to study physical correlations of these important parameters. The density was measured for different molar ratios of AlCl3:[EMIm]Cl from 0.5:1 to 2.0:1 at ambient temperature. The diffusion coefficient of the electrochemically active heptachloroaluminate complex, Al2Cl7-, was measured for a molar ratio of 2:1 in the range of 25˚C to 100˚C. The corresponding current density and potential transients were discussed regarding the decomposition of the [EMIm]+ cation and deviation from the theoretical Cottrell behavior. The electrical conductivity was measured for molar ratios of 1.5:1 and 2:1 in the range of 25˚C to 100˚C. Both the diffusion coefficient and electrical conductivity can be described well by an Arrhenius law. The diffusion coefficients of AlCl4-, Al2Cl7- and [EMIm]+ were estimated from the Nernst-Einstein and Stokes-Einstein relation. The results indicate a strong impact of ion pairing in these electrolytes.
https://doi.org/10.1016/j.electacta.2020.137370
Development of the phase composition and the properties of Ti2AlC and Ti3AlC2 MAX-phase thin films - A multilayer approach towards high phase purity. - In: Applied surface science, Bd. 537 (2021), 147864
MAX phase thin films have been synthesized by thermal treatment of a Ti-Al-C multilayer system. The preparation of the multilayer system was carried out via magnetron sputtering. Based on the thickness ratio among the individual nanoscale monolayers (Ti, Al, C), the resulting MAX phase stoichiometry can be controlled. This paper describes the synthesis of both Ti2AlC and Ti3AlC2 MAX phases from the same precursor multilayer system which is composed of a sequence of Ti/Al/C pure elemental single layers with thicknesses of 14, 6, and 3.5 nm, respectively. This sequence is repeated 22 times with a total thickness of around 500 nm. Rapid thermal treatment tests were performed to study the phase development. The Ti2AlC MAX phase forms in a temperature range below 850 ˚C, whereas the Ti3AlC2 MAX phase starts to form at temperatures above 850 ˚C and reaches its highest phase purity at 950 ˚C. The thin film structures were studied by X-ray diffraction and Raman spectroscopy. Furthermore, the electrical and mechanical properties were investigated to gain more insights regarding the phase transformation and their influence on the thin film properties.
https://doi.org/10.1016/j.apsusc.2020.147864
Nanoparticle gas phase electrodeposition: fundamentals, fluid dynamics, and deposition kinetics. - In: Journal of aerosol science, ISSN 1879-1964, Bd. 151 (2021), 105652, S. 1-15
This communication uncovers missing fundamental elements and an expanded model of gas phase electrodeposition; a relatively new and in large parts unexplored process, which combines particle generation, transport zone and deposition zone in an interacting setup. The process enables selected area deposition of charged nanoparticles that are dispersed and transported by a carrier gas at atmospheric pressure conditions. Two key parameters have been identified: carrier gas flow rate and spark discharge power. Both parameters affect electrical current carried by charged species, nanoparticle mass, particle size and film morphology. In combination, these values enable to provide an estimate of the gas flow dependent Debye length. Together with Langmuir probe measurements of electric potential and field distribution, the transport can be described and understood. First, the transport of the charged species is dominated by the carrier gas flow. In close proximity, the transport is electric field driven. The transition region is not fixed and correlates with the electric potential profile, which is strongly dependent on the deposition rate. Considering the film morphology, the power of the discharge turns out to be the most relevant parameter. Low spark power combined with low gas flow leads to dendritic film growth. In contrast, higher spark power combined with higher gas flow produces compact layers.
https://doi.org/10.1016/j.jaerosci.2020.105652
Anwendungen der Schwingquarzmethode in der Galvanotechnik. - In: ZVO-Report, (2020), 2, S. 42
Abscheidung von dekorativen Chromschichten mittels niederfrequenter Pulsabscheidung zur Anpassung des optischen Erscheinungsbilds. - In: WOMag, ISSN 2195-5905, Bd. 9 (2020), 6, S. 1-8
Das optische Erscheinungsbild von galvanisch abgeschiedenen Chromschichten ist eines der wichtigsten Kriterien für deren dekorative Anwendung. Für die dekorative Verchromung werden zunehmend Elektrolyte auf Basis von dreiwertigem Chrom als Ersatz für die bisher verwendeten Elektrolyte auf Basis von sechswertigem Chrom eingesetzt. Chrom aus Elektrolyten mit dreiwertigen Chromverbindungen neigt jedoch dazu, bei Dicken über 100 nm einen gelblichen Farbton zu haben, was für die meisten Anwendungen unerwünscht ist. Die Farbverschiebung hängt mit einer Änderung der Oberflächenmorphologie aufgrund des Wachstums der Chromkeime zusammen. Durch die Verwendung von gepulstem Strom mit Einschaltzeiten im Bereich von Sekunden wird das unerwünschte Kornwachstum unterdrückt und die Bildung frischer Kerne begünstigt. Dadurch bilden sich kompakte Chromschichten mit feinerem Gefüge und verbesserten Farbwerten. Ein bläuliches Aussehen und ein hoher Glanz werden bis zu einer Dicke von mehr als 200 nm beibehalten. Basierend auf den Ergebnissen wird eine Kombination aus konstantem und gepulstem Strom vorgeschlagen, die ein ähnliches visuelles Erscheinungsbild ergibt wie nur bei gepulstem Strom, jedoch die angestrebte Schichtdicke in deutlich kürzerer Zeit erreicht.
https://dx.doi.org/10.7395/2020/Leimbach1