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- Polymer-Elektrolytmembran-Brennstoffzelle (3)
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- hydraulic compression (2)
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Bereits im April 2012 wurde im HZwei Magazin ein Stackkonzept für PEM-Brennstoffzellen vorgestellt, bei dem im Gegensatz zu der heute üblichen bipolaren Zellenanordnung mit mechanischer Verpressung Einzelzellen über ein Hydraulikmedium verpresst werden. Die Vorteile der homogenen Verpressung und Temperierung der Zellen wurden hierbei herausgestellt. Zwischenzeitlich ist basierend auf diesem Ansatz das Labormuster eines PEM-Elektrolyseurs entwickelt worden, bei dem der produzierte Wasserstoff oder auch der Sauerstoff mit hohen Ausgangsdrücken, z.B. auf einem für Power-2-Gas-Anlagen günstigem Druckniveau, direkt bereitgestellt werden kann.
Brennstoffzellen gelten in der Forschung als eine der saubersten Technologien zur Stromerzeu-gung. In den Zellen, die meist z.B. so groß sind wie ein Taschenbuch, werden Wasserstoff und Sauerstoff in einer kontrollierten chemischen Reaktion in Wasserdampf umgewandelt. Dabei entstehen elektrische Energie und Wasser. Im Gegensatz zu den meisten anderen Formen der Stromproduktion wird kein Kohlendioxid freigesetzt. Das macht den Wandlungsprozess der Brennstoffzelle sehr umweltfreundlich.
Der Elektroingenieur Prof. Dr. Michael Brodmann von der Westfälischen Hochschule sieht in dieser Technologie die Zukunft mobiler wie stationärer Energieversorgung. Autos mit Elektro-motoren könnten mit Wasserstofftechnik angetrieben, portable Elektrogeräte oder auch ganze Gebäude umweltfreundlich mit Strom versorgt werden. Jedoch ist die Herstellung und Wartung der Brennstoffzellen derzeit sehr teuer, weshalb am Markt Energiewandler auf Basis fossiler Rohstoffe weiterhin dominieren. An diesem Problem arbeitet Brodmann gemeinsam mit Dr. Ulrich Rost. Im Labor des Westfälischen Energieinstituts haben die beiden Forscher eine neue Zelle entwickelt, die effektiver und günstiger ist – und dabei auf ein bewährtes Patent und neue Materialien gesetzt.
Due to high power density and superior efficiency, polymer electrolyte membrane fuel cells (PEMFC) are believed to play a significant role for carbon dioxide emissions free electrical energy systems in the future. Unlike in Carnot processes, chemical energy in the form of hydrogen and oxygen is converted directly into electrical energy without a further process step. One issue in the development of PEMFCs for mobile or stationary applications is the utilization of rare and expensive catalyst material like platinum within the membrane electrode assembly (MEA) see figure 1. In addition, the objective is to reduce production costs and to increase the lifetime of PEMFC. One approach to improve PEMFCs is the development of intelligent electrode architectures. However, cost effective high performance materials are necessary to reach the development targets.
Membrane electrode assemblies (MEA) developed at the Westphalian Energy Institute for polymer electrolyte membrane fuel cells (PEMFC) are high tech systems containing various materials structured in nanoscale, at which electrochemical reactions occur on catalyst nano particle surfaces. For low reactance homogeneous compression of the MEA’s layers is necessary. A novel stack architecture for electrochemical cells, especially PEMFC as well as PEM electrolysers, has been developed according to achieve ideal cell operation conditions. Single cells of such a stack are inserted into flexible slots that are surrounded by hydraulic media. While operation the hydraulic media is pressurised which leads to an even compression and cooling of the stack’s cells. With this stack design it has been possible to construct a test facility for simultaneous characterisation of several MEA samples. As compression and temperature conditions of every single sample are equal, with the novel test system the effect of e.g. different electrode configurations can be investigated. Furthermore, the modular stack design leads to the development of hybrid energy applications combining fuel cells, electrolysers, batteries as well as metal hydride tanks in one system.
Various aqueous citrate electrolyte compositions for the Ni-Mo electrodeposition are explored in order to deposit Ni-Mo alloys with Mo-content ranging from 40 wt% to 65 wt% to find an alloy composition with superior catalytic activity towards the hydrogen evolution reaction (HER). The depositions were performed on copper substrates mounted onto a rotating disc electrode (RDE) and were investigated via scanning electron microscopy (SEM), X-ray fluorescence (XRF) and X-ray diffraction (XRD) methods as well as linear sweep voltammetry (LSV) and impedance spectroscopy. Kinetic parameters were calculated via Tafel analysis. Partial deposition current densities and current efficiencies were determined by correlating XRF measurements with gravimetric results. The variation of the electrolyte composition and deposition parameters enabled the deposition of alloys with Mo-content over the range of 40-65 wt%. An increase in Mo-content in deposited alloys was recorded with an increase in rotation speed of the RDE. Current efficiency of the deposition was in the magnitude of <1%, which is characteristic for the deposition of alloys with high Mo-content. The calculated kinetic parameters were used to determine the Mo-content with the highest catalytic activity for use in the HER.
The present paper presents one- and two-step approaches for electrochemical Pt and Ir deposition on a porous Ti-substrate to obtain a bifunctional oxygen electrode. Surface pre-treatment of the fiber-based Ti-substrate with oxalic acid provides an alternative to plasma treatment for partially stripping TiO2 from the electrode surface and roughening the topography. Electrochemical catalyst deposition performed directly onto the pretreated Ti-substrates bypasses unnecessary preparation and processing of catalyst support structures. A single Pt constant potential deposition (CPD), directly followed by pulsed electrodeposition (PED), created nanosized noble agglomerates. Subsequently, Ir was deposited via PED onto the Pt sub-structure to obtain a successively deposited PtIr catalyst layer. For the co-deposition of PtIr, a binary PtIr-alloy electrolyte was used applying PED. Micrographically, areal micro- and nano-scaled Pt sub-structure were observed, supplemented by homogenously distributed, nanosized Ir agglomerates for the successive PtIr deposition. In contrast, the PtIr co-deposition led to spherical, nanosized PtIr agglomerates. The electrochemical ORR and OER activity showed increased hydrogen desorption peaks for the Pt-deposited substrate, as well as broadening and flattening of the hydrogen desorption peaks for PtIr deposited substrates. The anodic kinetic parameters for the prepared electrodes were found to be higher than those of a polished Ir-disc.
For proton exchange membrane water electrolysis (PEMWE) to become competitive, the cost of stack components, such as bipolar plates (BPP), needs to be reduced. This can be achieved by using coated low-cost materials, such as copper as alternative to titanium. Herein we report on highly corrosion-resistant copper BPP coated with niobium. All investigated samples showed excellent corrosion resistance properties, with corrosion currents lower than 0.1 µA cm−2 in a simulated PEM electrolyzer environment at two different pH values. The physico-chemical properties of the Nb coatings are thoroughly characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). A 30 µm thick Nb coating fully protects the Cu against corrosion due to the formation of a passive oxide layer on its surface, predominantly composed of Nb2O5. The thickness of the passive oxide layer determined by both EIS and XPS is in the range of 10 nm. The results reported here demonstrate the effectiveness of Nb for protecting Cu against corrosion, opening the possibility to use it for the manufacturing of BPP for PEMWE. The latter was confirmed by its successful implementation in a single cell PEMWE based on hydraulic compression technology.
Hochdruck PEM-Elektrolyse
(2017)
A systematic method for obtaining a novel electrode structure based on PtCoMn ternary alloy catalyst supported on graphitic carbon nanofibers (CNF) for hydrogen evolution reaction (HER) in acidic media is proposed. Ternary alloy nanoparticles (Co0.6Mn0.4 Pt), with a mean crystallite diameter under 10 nm, were electrodeposited onto a graphitic support material using a two-step pulsed deposition technique. Initially, a surface functionalisation of the carbon nanofibers is performed with the aid of oxygen plasma. Subsequently, a short galvanostatic pulse electrodeposition technique is applied. It has been demonstrated that, if pulsing current is employed, compositionally controlled PtCoMn catalysts can be achieved. Variations of metal concentration ratios in the electrolyte and main deposition parameters, such as current density and pulse shape, led to electrodes with relevant catalytic activity towards HER. The samples were further characterised using several physico-chemical methods to reveal their morphology, structure, chemical and electrochemical properties. X-ray diffraction confirms the PtCoMn alloy formation on the graphitic support and energy dispersive X-ray spectroscopy highlights the presence of the three metallic components from the alloy structure. The preliminary tests regarding the electrocatalytic activity of the developed electrodes display promising results compared to commercial Pt/C catalysts. The PtCoMn/CNF electrode exhibits a decrease in hydrogen evolution overpotential of about 250 mV at 40 mA cm−2 in acidic solution (0.5 M H2SO4) when compared to similar platinum based electrodes (Pt/CNF) and a Tafel slope of around 120 mV dec−1, indicating that HER takes place under the Volmer-Heyrovsky mechanism.
Platinum is one of the most effective electro catalysts for PEMFCs (proton exchange membrane fuel cells), but because of its prohibitive price, the use of this metal in industrial purposes is limited. As a consequence, during last years, several materials have been investigated, in order to obtain an efficient catalyst for both ORR (oxygen reduction reaction) and HOR (hydrogen oxidation reaction), which can replace the expensive platinum but preserving the same properties: high electrical conductivity, structural stability and good corrosion resistance. Moreover, one of the most important parameters for catalyst materials is the electrochemical surface area (real surface area), which has a strong influence on the reaction rate and also on the current density.
CNFs (carbon nanofibers) are considered to be a promising catalyst support material due to their unique characteristics, excellent mechanical, electrical and structural properties, high surface area and nevertheless, good interaction with platinum particles.
The possibility of preparing CNFs decorated with platinum by electrochemical methods was tested, using a hexachloroplatinic solution bath. The experiments were carried out with the aid of a Potentiostat/Galvanostat MMate 510, in a three – electrode cell.
The aim of the present work was to determine the electrochemical surface area of the CNFs – Pt catalysts, using an electrochemical method. The obtained results correlate very well with the particles size and distribution of platinum, analyzed by SEM (scanning electron microscopy) respectively with the quantity of deposited platinum determined by TG (thermo gravimetrical analyses). Cyclic voltammetry is a suitable method for estimation of the real surface area for catalyst particles.
Platinum nanoparticles electrodeposition on carbon nanofibers (CNF) support has been performed with the purpose to obtain electrodes that can be further used especially in a polymer electrolyte membrane fuel cell (PEMFC). A pretreatment of CNF is required in order to enhance the surface energy, which simultaneously improves handling and wettability as well as interaction with the platinum cations. This step was performed using oxygen plasma functionalization. To produce CNF supported Pt catalysts, an electrochemical method was applied and the deposition parameters were adjusted to obtain nanosized platinum particles with a good distribution onto the graphitic surface. The morphology and structure of the obtained particles were investigated by scanning electron microscopy combined with energy dispersive X-Ray spectroscopy. The amount of deposited platinum was established using thermogravimetrical measurements. Cyclic voltammetry performed in 0.5 M H2SO4 solution was applied for determining the electrochemical surface area (ECSA) of the obtained electrodes.The functionalization degree of the CNF outer surface has a strong influence on the structure, distribution and amount of platinum particles. Moreover, the current densities, which were set for the deposition process influenced not only the particles size but also the platinum amount. Applying an oxygen plasma treatment of 80 W for 1800 s, the necessary degree of surface functionalization is achieved in order to deposit the catalyst particles. The best electrodes were prepared using a current density of 50 mA cm-2 during the deposition process that leads to a homogenous platinum distribution with particles size under 80 nm and ECSA over 6 cm2