Refine
Year of publication
Document Type
- Conference Proceeding (27)
- Article (18)
- Part of a Book (3)
- Doctoral Thesis (1)
- Report (1)
Keywords
- Polymer-Elektrolytmembran-Brennstoffzelle (4)
- hydraulic compression (2)
- modular stack design (2)
- carbon nanofibers, platinum electrodeposition, ele ctrochemical surface area (1)
- Elektrodenvorbereitung (1)
- Elektrolyseure (1)
- Erneuerbare Energien (1)
- Homogene Kühlung (1)
- Hydraulic cell compression (1)
- Hydraulic compression, Carbon Nano Fibers, PEM Fuel Cells, Catalyst utilization (1)
Institute
For this experimental work gas diffusion electrodes (GDE) with low platinum loading are prepared for the application as anodes in polymer electrolyte membrane fuel cells. As catalyst support material, carbon nano fibres (CNF) are investigated due to high specific surface area as well as high graphitisation degree. Optimisation is achieved by an economic and environmental friendly pre-treatment process in oxygen plasma. For electrode preparation an ink is used containing oxygen plasma activated CNFs as well as hydrophilic polymer. After spray coating of this CNF ink on a graphitic substrate, platinum is deposited by pulse plating method. Preliminary results established that the plasma activation improves considerably CNF dispersibility as well as the amount, respectively, the morphology of the deposited platinum. Morphology and microstructure are observed by electron microscopy. Platinum loading is determined by thermogravimetric analysis to be in the range of 0.010 to 0.016 mg cm-2. Furthermore, MEAs are prepared from these GDEs and testing is performed in a novel modular test stack based on hydraulic compression. Technical information about the test stack design and functions are given in this work. In this test environment maximum specific power output of 182 mW cm-2 has been obtained under robust operation conditions.
Um die Wasserstofftechnik in Zukunft wirtschaftlich und damit kommerziell am Markt verfügbar werden zu lassen, sind heute noch immer große Forschungs- und Entwicklungsanstrengungen notwendig. Dabei erfordert die Entwicklung von optimierten Komponenten wie beispielsweise der Membran-Elektroden-Einheit (MEA – engl. Membrane Electrode Assembly) für Brennstoffzellen sowie Elektrolyseure reproduzierbare und homogene Prüfbedingungen. Für diesen Zweck ist ein Prüfsystem auf Basis eines von der Westfälischen Hochschule (WHS) patentierten modularen Stackkonzepts mit hydraulischer Verpressung entworfen und realisiert worden. Mit dem hier vorgestellten System ist es möglich, auf Einzelzellenbasis mehrere Proben zum gleichen Zeitpunkt unter identischen Umgebungsbedingungen auf ihre Charakteristik hin zu untersuchen.
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.
To further increase platinum utilisation in PEM fuel cells CNFs are investigated as catalyst support material due to the CNF’s high specific surface area. Furthermore, CNFs provide suitable properties concerning corrosion resistance as well as electrical conductivity in contrast to conventional carbon supports.
This work presents the results of an electrode preparation procedure based on O2 plasma activated CNFs. The plasma treatment leads to CNF dispersibility in alcohol/water for a spray coating process. Furthermore, O2 plasma activation enhances metal deposition on the CNF’s surface. Pulse plating procedure as well as wet chemical metal synthesis have been used for particle deposition. For pulse plating a potentiostat/galvanostat type MMates 510 AC from Materials Mates, Italy has been used. Electrode morphology has been determined in SEM type XL 30 ESEM from Philips, The Netherlands.
This report gives a brief overview to the state of the art of PEM fuel cell technology and a description of a newly developed fuel cell stack concept. One main research activity at the Westphalian Energy Institute of the Westphalian University of Applied Sciences is the development of PEM fuel cells, for which a range of different materials have been investigated for fuel cell pole plate construction. Whereas graphite is a material which has suitable properties concerning conductivity as well as manufacturing e.g. for milling, stainless steel foils are suitable for economical hydroforming processes. However, with steel coating is necessary to increase corrosion resistance as well as electrical conductivity. A new fuel cell stack design is currently under development using separated single fuel cells with hydraulic cell compression. The advantages of this stack concept are modularity, effective heat exchanging and constant, uniform cell compression which are further described in this work.
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.
Since the 1980’s, against the backdrop of global warming and the decline of conventional energy resources, low emission and renewable energy systems have gotten into the focus of politics as well as research and development. In order to decrease the emission of greenhouse gases Germany intents to generate 80% of its electrical energy from renewable and low emission sources by 2050. For low emission electricity generation hydrogen operated fuel cells are a potential solution. However, although fuel cell technology has been well known since the 19th century cost effective materials are needed to achieve a breakthrough in the market.
Proton Exchange Membrane Fuel Cells with Carbon Nanotubes as Electrode Material
At the Westphalian Energy Institute of the Wesphalian University of Applied Sciences one main focus is on the research of proton exchange membrane fuel cells (PEMFC). PEMFC membrane electrode assemblies (MEA) consist of a polymer membrane with electrolytic properties covered on both sides by a catalyst layer (CL) as well as a porous and electrical conductive gas diffusion layer (GDL).
For PEMFC carbon nanotubes (CNT) have ideal properties as electrode material concerning electrical conductivity, oxidation resistance and media transport. CNTs are suitable for the use as catalyst support material within the CL due to their large surface in comparison to conventional carbon supports. Furthermore, oxygen plasma treated CNTs show electrochemical activity referred to hydrogen adsorption and desorption, which has been shown by cyclic voltammetry in 0.5 M sulfuric acid solution. According to the PEMFCs anode a GDL coated with oxygen plasma activated CNTs has promising properties to significantly reduce catalyst content (e.g. platinum) of the anodic CL.
In this experimental work we present a novel electrolyzer system for the production of hydrogen and oxygen at high pressure levels without an additional mechanical compressor. Due to its control strategies, the operation conditions for this electrolyzer can be kept optimal for each load situation of the system. Furthermore, the novel system design allows for dynamic long-term operation as well as for easy maintainability. Therefore, the device meets the requirements for prospective power-to-gas applications, especially, in order to store excess energy from renewable sources. A laboratory scale device has been developed and high-pressure operation was validated. We also studied the long-term stability of the system by applying dynamic load cycles with load changes every 30 sec. After 80 h of operation the used membrane electrode assembly (MEA) was investigated by means of SEM, EDX and XRD analysis.
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.
This experimental work deals with the preparation and investigation of PEM fuel cell electrodes, which are obtained using Graphene Related Material (GRM) serving as catalyst support material for platinum nanoparticles. The applied GRM belong to the group of carbon nanofibers and exhibits a helical-ribbon structure with dimensions of 50 nm in diameter and an average length up to a few µm. Furthermore, utilized GRM provide a superior graphitisation degree of about 100 %, which leads to both high corrosion resistance and low ohmic resistance. Material stability plays one of the main roles for long term fuel cell operation, whereby a great electrical catalyst contact combined with high specific surface area yields in high fuel cell performances.
Prior to GRM dispersion and deposition onto a gas diffusion layer, the graphene structures are functionalized by oxygen plasma treatment. Through this step, functional oxygen groups are generated onto the GRM outer surface providing an improved hydrophilic behaviour and facilitating the GRM suspension preparation. In addition, the oxygen groups act as anchors for platinum nanoparticles which are subsequently deposited onto the GRM surface through a pulse electrodeposition process.
Membrane electrode assemblies produced with the prepared electrodes are investigated in-situ in a PEM fuel cell test bench.
In this study, a novel design concept for PEMFC (polymer electrolytemembrane fuel cell) stacks is presented with singlecells inserted in pockets surrounded by a hydraulic medium. Thehydraulic pressure introduces necessary compression forces to themembrane electrode assembly of each cell within a stack. Moreover, homogeneous cell cooling is achieved by this medium. First,prototypes presented in this work indicate that, upscaling of cells for the novelstack design is possible without significantperformancelosses. Due to its modularity and scalability, this stackdesign meets the requirements for large PEMFC units.
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.
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.
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.
Carbon Nanofibers (CNF) 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 metallic catalyst particles. The possibility of preparing CNF decorated with platinum by an electrochemical method was tested, using a hexachloroplatinic bath solution. The experiments were carried out with the aid of a Potentiostat/Galvanostat Ivium Technologies Vertex, in a three – electrode cell. The aim of the present work was to determine the electrochemical surface area (ECSA) of the CNF-Pt catalysts in relation to the functionalization treatment of fibers, using an electrochemical method. ECSA for different functionalized CNF-Pt catalysts was determined by cyclic voltammetry in 0.5 M H2SO4 solution. The highest active surface of platinum was obtained for the samples with CNF functionalized by plasma treatment using 80 W for 1800 s. The obtained results correlate very well with the particles size and distribution of platinum, revealed by scanning electron microscopy (SEM) and the quantity of deposited platinum determined by thermo gravimetrical analysis (TGA) respectively. Cyclic voltammetry (CV) has been proven to be a suitable method for estimation of the ECSA of the electrocatalysts.
This experimental work deals with the preparation and investigation of PEM fuel cell electrodes, which are obtained using Graphene Related Material (GRM) serving as catalyst support material for platinum nanoparticles. The applied GRM belong to the group of carbon nanofibers and exhibits a helical-ribbon structure with dimensions of 50 nm in diameter and an average length up to a few µm. Furthermore, utilized GRM provide a superior graphitisation degree of about 100 %, which leads to both high corrosion resistance and low ohmic resistance. Material stability plays one of the main roles for long term fuel cell operation, whereby a great electrical catalyst contact combined with high specific surface area yields in high fuel cell performances.
Prior to GRM dispersion and deposition onto a gas diffusion layer, the graphene structures are functionalized by oxygen plasma treatment. Through this step, functional oxygen groups are generated onto the GRM outer surface providing an improved hydrophilic behaviour and facilitating the GRM suspension preparation. In addition, the oxygen groups act as anchors for platinum nanoparticles which are subsequently deposited onto the GRM surface through a pulse electrodeposition process.
Membrane electrode assemblies produced with the prepared electrodes are investigated in-situ in a PEM fuel cell test bench.
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.
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.