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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