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Institut
In polymer electrolyte membrane fuel cells (PEMFC) noble metal nano particles are deposited on graphitic supports serving as electrocatalysts for devices with high power density. In this study anodes are analysed with low platinum loading of about 0.1 mg cm-2. These electrodes are prepared by carbon nano fibres (CNF) decorated with platinum nano particles. For electrode manufacturing two sorts of fibres, which are produced in an industrial scale, are used with different graphitisation degree and surface area. CNF layers are applied on commercially available graphitic substrate by spray coating which leads to a porous structure with high surface area. Subsequently, platinum deposition is achieved by pulsed electroplating for an improved platinum utilisation in PEMFC electrodes. Spray coating and platinum deposition are assisted by a previous oxygen plasma activation process. Prepared anode material is characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), X-ray fluorescence spectroscopy (XRF) and thermogravimetry (TGA). Electrochemical analyses (cyclic voltammetry and corrosion test) are carried out in 0.5 M sulphuric acid. The effect of graphitisation degree of carbon nano fibres on the performance of prepared electrodes is investigated in-situ in a PEM fuel cell test bench.
In this experimental work polymer electrolyte membrane fuel cell (PEMFC) electrodes are analysed, which are prepared by the use of two sorts of carbon nano fibres (CNF) serving as support material for platinum nano particles. Those CNFs, which are heat treated subsequently to their production, have a higher graphitisation degree than fibres as produced. The improved graphitisation degree leads to higher electrical conductivity, which is favourably for the use in PEMFC electrodes. Samples have been analysed, in order to determine graphitisation degree, electrical conductivity, as well as morphology and loading of the prepared electro catalyst. Membrane electrode assemblies manufactured from prepared electrodes are analysed in-situ in a PEM fuel cell test environment. It has been determined that power output for samples containing CNFs with higher graphitisation degree is increased by about 13.5%.
This work deals with the preparation and investigation of PEM fuel cell electrodes, which are obtained using graphene related material (GRM) serving as catalyst support for platinum nanoparticles. Applied GRM are used for the preparation of suspensions in four distinct mixing ratios. Two sorts of GRM have been investigated: carbon nanofibers (CNF) and graphene oxide (GO). Utilized CNFs provide a superior graphitization degree of about 100%, which leads to both high corrosion resistance and low ohmic resistance in PEM fuel cells.
For electrode preparation a GRM containing layer serving as catalyst support is applied onto a gas diffusion layer (GDL). Prior to GRM suspension and deposition onto a GDL, the graphene structures are functionalized by plasma treatment. Due to this step, an improved hydrophilic behavior for facilitating suspension preparation is achieved. In addition, a subsequent platinum nanoparticle deposition by pulsed electrodeposition process is optimized.
The technology of polymer electrolyte membrane (PEM) electrolysis provides an efficient way to produce hydrogen. In combination with renewable energy sources, it promises to be one of the key factors towards a carbon-free energy infrastructure in the future. Today, PEM electrolyzers with a power consumption higher than 1 MW and a gas output pressure of 30 bar (or even higher) are already commercially available. Nevertheless, fundamental research and development for an improved efficiency is far from being finally accomplished, and mostly takes place on a laboratory scale. Upscaling the laboratory prototypes to an industrial size usually cannot be achieved without facing further problems and/or losing efficiency. With our novel system design based on hydraulic cell compression, a lot of the commonly occurring problems like inhomogeneous temperature and current distribution can be avoided. In this study we present first results of an upscaling by a factor of 30 in active cell area.
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.
Hochdruck PEM-Elektrolyse
(2017)
Im Rahmen eines gemeinsamen Forschungsprojekts mit dem Titel „Energieautarke Bohrlochsensorik mittels Brennstoffzellen – GeoFuelCells“ wurde vom Geothermie-Zentrum Bochum und dem Westfälischen Energieinstitut, unterstützt aus dem Förderprogramm Ziel 2 (2007-2013 EFRE) des Landes NRW, ein brennstoffzellenbasiertes Energieversorgungssystem für Bohrloch-Anwendungen entwickelt.
Im Rahmen der Energiewende ist eine Erweiterung der in das Verbund-netz integrierten Energiespeicher notwendig, um zukünftig die heute gewohnte Versorgungssicherheit trotz eines sehr hohen Anteils volatiler regenerativer Energieerzeugungsanlagen zu ermöglichen. Eine geeignete elektrochemische Methode zur umweltfreundlichen Zwischenspeicherung großer Energiemengen stellt die Wasserelektrolyse mit bedarfsorientierter Rückverstromung dar. Dabei können die dynamischen Einspeise- und Laständerungen im elektrischen Verbundnetz im besonderen Maße von Elektrolyseur- und Brennstoffzellen-systemen auf Basis von Polymer-Elektrolyt-Membranen (PEM) aufgefangen werden.
Bestehende PEM-Systeme sind vor allem in ihrer konstruktiven Zellgröße und ihrer maximalen Leistung bei der Wasserstoffproduktion bzw. der Stromerzeugung stark begrenzt. Vor allem inhomogene Verpressungen großflächiger planarer Zellen in einem klassischen, mechanisch verspannten Stack führen zu hohen Leistungseinbußen. Zudem ergeben sich bei kleinen Stacks aufgrund der geringen Zellspannung ungünstige Wandlungsverhältnisse zwischen Strom und Spannung für eine vor- bzw. nachgeschaltete Leistungselektronik. Ein neuartiges Stackkonzept mit segmentierten Polplatten bietet eine konstruktive Lösung für das Problem größerer aktiver Zellflächen und leistet einen Beitrag zur Entwicklung industriell einsetzbarer Hochdruckelektrolyseure und Brennstoffzellen.
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.
Für einen Energiesektor, der zukünftig im hohen Maße auf erneuerbaren Quellen beruht, sind Energiespeicher unverzichtbar, um die heute gewohnte Versorgungssicherheit auch in Zeiten geringer Einspeisung aus Wasser, PV- und/oder Windkraftanlagen garantieren zu können. Da konventionelle Speichertechnologien wie beispielsweise Pumpspeicherkraftwerke durch fehlende mögliche Standorte in Deutschland nicht weiter ausgebaut werden, sind Alternativen notwendig. Es ist Konsens, hierfür emissionsarme Strategien zu entwickeln, um die gesetzten Ziele zur Reduktion von CO2 Emissionen zu erreichen. Neben Batterien, die vorzugsweise für Kurzzeitspeicher einzusetzen sind, bietet sich Wasserstoff als umweltfreundlicher Sekundärenergieträger an, der in großen Mengen gespeichert und in Brennstoffzellen mit hohem Wirkungsgrad emissionsfrei in elektrische Energie umgewandelt werden kann. Da elementarer Wasserstoff nicht natürlich vorkommt, ist dieser zuvor zu generieren. Überschüsse aus regenerativen Energiequellen können hierfür ideal genutzt werden. In diesem Beitrag wird ein aussichtsreiches Konzept für einen modularen Hochdruckelektrolyseur vorgestellt, welcher erlaubt, Wasserstoff bei einem hohen Ausgangsdruck bereitzustellen. Durch den prinzipiellen Aufbau, ist ein beliebiges Druckniveau am Ausgang nur von der mechanischen Stabilität der verwendeten Bauteile abhängig. Hierdurch ist es möglich, Wasserstoff direkt in einen Druckgasspeicher oder eine Pipeline zu produzieren, ohne einen zusätzlichen Verdichter nutzen zu müssen. Dies resultiert in signifikanten Kosteneinsparungen und verbessert den Systemwirkungsgrad zukünftiger Anlagen entscheidend.
In state of the art polymer electrolyte membrane fuel cells (PEMFC) rare and expensive platinum group metals (PGM) are used as catalyst material. Reduction of PGM in PEMFC electrodes is strongly required to reach cost targets for this technology. An optimal catalyst utilisation is achieved in the case of nano-structured particles supported on carbon material with a large specific surface area. In this study, graphitic material in form of carbon nanofibres (CNFs) is decorated with platinum (Pt) particles serving as catalyst material for PEMFC electrodes with low Pt loading. For electrode preparation CNFs have been previously activated by means of radio frequency induced oxygen plasma. This kind of treatment results in formation of functional groups on the CNF’s surface which directly influences the characteristics of subsequent Pt particle deposition. Different plasma parameters (plasma power, gas flow or exposure time) have to be set in order to achieve formation of oxygen containing functional groups (hydroxylic, carboxylic or carbonylic) on the CNF’s surface. In the frame of this experimental work, electrodes are investigated in respect of optimal morphology, microstructure as well as electrochemical properties. Therefore, samples were characterised by means of scanning electron microscopy combined with energy dispersive X-ray analysis, transmission electron microscopy, thermogravimetry, X-ray diffraction, X-ray fluorescence as well as polarisation measurements.
In the polymer electrolyte membrane fuel cells (PEMFC) state of the art, rare and expensive platinum group metals (PGM) or PGM alloys are used as catalyst material. Reduction of PGMs in PEMFC electrodes is strongly required to reach cost targets for this technology. An optimal catalyst utilization is achieved in case of nano-structured particles supported on carbon material with a large specific surface area. In this study, graphitic material, in form of carbon nanofibers (CNF), is decorated with Pt particles, serving as catalyst material for PEMFC electrodes with low Pt loading. As a novelty, the effect of oxygen plasma treatment of CNFs previously to platinum particle deposition has been studied. Electrodes are investigated in respect of the optimal morphology, microstructure as well as electrochemical properties. Therefore, samples are characterized by means of scanning electron microscopy combined with energy dispersive X-ray analysis, transmission electron microscopy, thermogravimetry, X-ray diffraction as well as X-ray fluorescence analysis. In order to determine the electrochemical active surface area of catalyst particles, cyclic voltammetry has been performed in 0.5 M sulphuric acid. Selected samples have been investigated in a PEMFC test bench according to their polarization behavior.
The membrane electrode assemblies (MEA) for polymer electrolyte membrane fuel cells (PEMFC) developed at the Westphalian Energy Institute are based on oxygen plasma activated carbon nanotubes (CNT) doped with platinum particles. For electrode preparation an ink is used containing the activated CNTs as well as hydrophobic and hydrophilic material in solved form. After this ink is sprayed onto a graphitic substrate platinum particles are deposited by pulse plating method, where the plasma activation enhances CNT dispersibility as well as platinum deposition. This materials mixture is structured in nanoscale with the aim to increase the catalyst particles’ specific surface. For low reactance at operation, homogeneous compression of the MEA’s layers is necessary within a PEMFC. A novel stack architecture for electrochemical cells, especially PEMFC as well as PEM electrolysers, has been developed in order to achieve ideal cell operation conditions. Single cells of such a stack are inserted into flexible slots that are surrounded by a hydraulic medium which is pressurised during operation in order to achieve 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 the same, the effects of e.g. different electrode configurations can be investigated with the novel test system.
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.