Rationally designed free-standing and binder-free Raney-type nickel–molybdenum (Ni–Mo) electrodes produced via atmospheric plasma spraying (APS) are developed by correlating APS process parameters with the microstructure of electrodes and their electrochemical performance in alkaline media. The results revealed that the electrode morphology and elemental composition are highly affected by the plasma parameters during the electrode fabrication. It is found that increasing plasma gas flow rate and input plasma power resulted in higher in-flight particle velocities and shorter dwell time, which in result delivered electrodes with much finer structure exhibiting homogeneous distribution of phases, larger quantity of micro pores and suitable content of Ni and Mo. Tafel slope of electrodes decreased with increasing the in-flight particles velocities from 71 to 33 mV dec−1in 30 wt.% KOH. However, beyond a critical threshold in-flight velocity and temperature of particles, electrodes started to exhibit larger globular pores and consequently reduced catalytic performance and higher Tafel slop of 36 mV dec−1in 30 wt.% KOH. Despite slightly lower electrochemical performance, the electrodes produced with highest plasma gas flow and energy showed most inter-particle bonded structure as well as highest stability with no measurable degradation over 47 days in operation as HER electrode in 30 wt.% KOH. The Raney-type Ni–Mo electrode fabricated at highest plasma gas flow rate and input plasma power has been tested as HER electrode in alkaline water electrolyzer, which delivered high current densities of 0.72 and 2 A cm−2at 1.8 and 2.2 V, respectively, representing a novel prime example of HER electrode, which can synergistically catalyze the HER in alkaline electrolyzer. This study shows that sluggish alkaline HER can be circumvented by rational electrode composition and interface engineering.
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.
25 October 2009 in International Journal of Energy Research
A higher density of large-angle grain boundaries in palladium membranes promotes hydrogen diffusion whereas small-angle grain boundaries suppress it. In this paper, the microstructure formation in 10 µm thick palladium membranes is tuned to achieve a submicronic grain size above 100 nm with a high density of large-angle grain boundaries. Moreover, changes in the grain boundaries’ structure is investigated after exposure to hydrogen at 300 and 500 °C. To attain large-angle grain boundaries in Pd, the coating was performed on yttria-stabilized zirconia/porous Crofer 22 APU substrates (intended for use later in an ultracompact membrane reactor). Two techniques of plasma sprayings were used: suspension plasma spraying using liquid nano-sized powder suspension and vacuum plasma spraying using microsized powder as feedstock. By controlling the process parameters in these two techniques, membranes with a comparable density of large-angle grain boundaries could be developed despite the differences in the fabrication methods and feedstocks. Analyses showed that a randomly oriented submicronic structure could be attained with a very similar grain sizes between 100 and 500 nm which could enhance hydrogen permeation. Exposure to hydrogen for 72 h at high temperatures revealed that the samples maintained their large-angle grain boundaries despite the increase in average grain size to around 536 and 720 nm for vacuum plasma spraying and suspension plasma spraying, respectively.
The consortium of the NAUTILUS project is developing a pilot marine genset, consisting of a Solid Oxide Fuel Cell (SOFC) coupled with a battery and to be hybridized with the existing LNG fueled Internal Combustion Engine (ICE) generators. The concept enables a step wise scale-up and integration through mild hybridization, balanced hybridization and full replacement of the ICEs. A demonstrator of the genset of 60 kW is being developed which will be validated at DLR. The project is aiming a technology that has the potential to reduce CO2 emissions by at least 40% and particulate emissions by 99% in a vessel meeting the targets of the IMO of 2030. For emission targets beyond 2030, the potential of NAUTILUS genset with synthetic fuels is evaluated. To enable such transition, the reformer unit is conceived to be separated from SOFC power blocks.