PEM electrolyzer characterization with carbon-based hardware and material sets

Abstract The research and development of proton exchange membrane water electrolysis (PEMWE) is an upcoming and growing area due to a rising interest in hydrogen as an energy carrier. Operating conditions are harsher than in a fuel cell system, particularly because the potentials required for the oxygen evolution reaction are significantly higher. In commercial water electrolysis systems, this is compensated by typically using titanium material sets that are often protected against oxidation through coating processes. Such material choices make small scale research hardware and porous transport layers expensive and difficult to source. In this work, we show that the stability of traditional, carbon-based fuel cell materials such as porous transport layers and graphite flow fields can be sufficient for electrolyzer initial performance characterization procedures such as cell conditioning, a limited number of polarization curve measurements, and electrochemical impedance spectroscopy. We identify and quantify the onset of carbon degradation in porous transport layers with regards to operating length and define a strategy that enables the utilization of standard fuel cell hardware for short-term PEMWE experiments. With the knowledge that existing fuel cell material sets can be applied to conduct electrolyzer research when adhering to such limitations, fuel cell research hardware and experience can be more readily transferred to the younger and rapidly growing electrolysis research field

Nanostructured electrochemical devices for sensing, energy conversion and storage

Nanostructured materials are attracting growing interest for improving performance of devices and systems of large technological interest. In this work, the principal results about the use of nanostructured materials in the field of electrochemical energy storage, electrochemical water splitting, and electrochemical sensing are presented. Nanostructures were fabricated with two different techniques. One of these was the electrodeposition of the desired material inside the channels of a porous support acting as template. The other one was based on displacement reaction induced by galvanic contact between metals with different electrochemical nobility. In the present work, a commercial polycarbonate membrane was used as template. In the field of the electrochemical energy storage, the attention was focused on lead-acid battery, and it has been found that nanostructured morphology enhances the active mass utilization up to about 80%, with consequent increase of specific energy and cycling rates to unattainable values for the commercial battery. Nanostructured Ni-IrO2 composite electrodes showed valuable catalytic activity for water oxidation. By comparison with other Ni-based electrocatalyst, this electrode appears as the most promising anode for electrochemical water splitting in alkaline cells. Also in the field of sensing, the nanostructured materials fabricated by displacement reaction showed performance of high interest. Some new results about the use of copper nanowires for H2O22 sensing will be showed, evidencing better performance in comparison with copper thin film. In this work, we will show that nanostructured electrodes are very promising candidate to form different electrochemical setups that operate more efficiently comparing to device with flat electrode materials

Flexible electrode based on gold nanoparticles and reduced graphene oxide for uric acid detection using linear sweep voltammetry

In this work, an electrochemical sensor for uric acid determination is shown with a preliminary study for its validation in real samples (milk and urine). Uric acid can be electrochemically oxidized in aqueous solutions and thus it is possible to obtain electrochemical sensors for this chemical by means of this electrooxidation reaction. Indium tin oxide coated on flexible polyethylene terephthalate substrate, modified with reduced graphene oxide and gold nanoparticles by co-electrodeposition, was used. Electrodeposition was performed at -0.8V vs SCE for 200 s. All samples were characterized by electron scan microscopy and electron diffraction spectroscopy. A careful investigation on the effect of pH was performed to understand its influence on uric acid oxidation. The detection of uric acid was using the linear sweep voltammetry. Results show that the peak current increases linearly with uric acid concentration from 10 to 1000 μM with a limit of detection of about 7.1 μM. The sensor shows high selectivity towards different interferents that can be found in the milk and urine matrix, such as chloride, calcium, sodium and ammonium ions. To prove the applicability of the proposed sensor, uric acid was quantified in real milk and urine samples with excellent results comparable to those of conventional techniques

The Impact of Dynamic Emissivity−Temperature Trends on Spaceborne Data: Applications to the 2001 Mount Etna Eruption

Spaceborne detection and measurements of high-temperature thermal anomalies enable monitoring and forecasts of lava flow propagation. The accuracy of such thermal estimates relies on the knowledge of input parameters, such as emissivity, which notably affects computation of temperature, radiant heat flux, and subsequent analyses (e.g., effusion rate and lava flow distance to run) that rely on the accuracy of observations. To address the deficit of field and laboratory-based emissivity data for inverse and forward modelling, we measured the emissivity of ‘a’a lava samples from the 2001 Mt. Etna eruption, over the wide range of temperatures (773 to 1373 K) and wavelengths (2.17 to 21.0 µm). The results show that emissivity is not only wavelength dependent, but it also increases non-linearly with cooling, revealing considerably lower values than those typically assumed for basalts. This new evidence showed the largest and smallest increase in average emissivity during cooling in the MIR and TIR regions (~30% and ~8% respectively), whereas the shorter wavelengths of the SWIR region showed a moderate increase (~15%). These results applied to spaceborne data confirm that the variable emissivity-derived radiant heat flux is greater than the constant emissivity assumption. For the differences between the radiant heat flux in the case of variable and constant emissivity, we found the median value is 0.06, whereas the 25th and the 75th percentiles are 0.014 and 0.161, respectively. This new evidence has significant impacts on the modelling of lava flow simulations, causing a dissimilarity between the two emissivity approaches of ~16% in the final area and ~7% in the maximum thickness. The multicomponent emissivity input provides means for ‘best practice’ scenario when accurate data required. The novel approach developed here can be used to test an improved version of existing multi-platform, multi-payload volcano monitoring systems

Spaceborne EO and a Combination of Inverse and Forward Modelling for Monitoring Lava Flow Advance

We aim here to improve the understanding of the relationship between emissivity of the lava and temperature by carrying out a multi-stage experiment for the 2017 Mt Etna (Italy) eruption. We combine laboratory, spaceborne, and numerical modelling data, to quantify the emissivity–temperature relationship. Our laboratory-based Fourier-transform infrared (FTIR) results indicate that emissivity and temperature are inversely correlated, which supports the argument that emissivity of molten material is significantly lower than that of the same material in its solid state. Our forward-modelling tests using MAGFLOW Cellular Automata suggest that a 35% emissivity variation (0.95 to 0.60) can produce up to 46% overestimation (for constant emissivity 0.60) in simulated/forecasted lava flow lengths (compared to actual observed). In comparison, our simulation using a ‘two-component’ emissivity approach (i.e., different emissivity values for melt and cooled lava) and constant emissivity 0.95 compares well (≤10% overestimation) with the actual 2017 lava flow lengths. We evaluated the influence of variable emissivity on lava surface temperatures using spaceborne data by performing several parametrically controlled assessments, using both constant (‘uniform’) and a ‘two-component’ emissivity approach. Computed total radiant fluxes, using the same spaceborne scene (Landsat 8 Operational Land Imager (OLI)), differ ≤15% depending on emissivity endmembers (i.e., 0.95 and 0.60). These results further suggest that computed radiant flux using high-spatial resolution data is bordering at lower boundary (range) values of the moderate-to-high temporal resolution spaceborne data (i.e., Moderate Resolution Imaging Spectroradiometer (MODIS) and Spinning Enhanced Visible and Infrared Imager (SEVIRI)), acquired for the same target area (and the same time interval). These findings may have considerable impact on civil protection decisions made during volcanic crisis involving lava flows as they approach protected or populated areas. Nonetheless, the laboratory work, reported here, should be extended to include higher volcanic eruptive temperatures (up to 1350 K)

Nanostructured electrodes for hydrogen production in alkaline electrolyzer

Ever-widespread employment of renewable energy sources, such as wind and sun, request the simultaneous use of effective energy storage systems owing to the intermittent and unpredictable energy generation by these sources. The most reliable storage systems currently under investigation are batteries and electrochemical cells for hydrogen production from water splitting. Both systems store chemical energy which can be converted on demand. The low power density is the weakness of the batteries while the high production cost limits currently the wide use of hydrogen from electrochemical water splitting. In this work, attention was focused on the use of nanostructured Ni as a cathode for electrochemical production of hydrogen from alkaline solution. The work is aimed at analysing the energy dissipation at 0.5 Acm\ue2\u88\u922, which is a value of applicative interest, for detecting one of the cause determining the high production cost. The development of electrochemical cells employing alkaline solution is currently the most promising approach in comparison with electrolysers using acidic solution which are expensive, because require precious metals as electrodes and high cost cation-selective membrane for efficiently conducting water splitting. Nanostructured Ni electrodes were fabricated through a cheap and easily scalable process, based on the Ni electrodeposition inside the pores of a commercial polycarbonate membrane acting as a template. On the contrary, a galvanic connection driving a spontaneous displacement reaction was employed for synthesising Pd nanostructured electrode which was tested for comparison purposes. Once the membrane is dissolved in an organic solution, the electrodes were initially characterized by SEM, EDS and XRD analysis. Then, electrochemical tests were performed to evaluate electrocatalytic properties of the electrodes. The tests were conducted through either cyclic or linear sweep voltammetry in 30% w/w KOH aqueous solution. Then, the nanostructured electrodes were tested under constant current density of 0.5 Acm\ue2\u88\u922. In comparison with nanostructured Pd, Ni electrodes with the same morphology and in otherwise identical conditions show a better response in terms of electrocatalytic activity. In addition, these electrodes showed satisfying stability over time through tests longer than 60 h. The analysis of energy dissipation revealed that the prevalent contribution was due to the ohmic drop)which can be reduced through a properly cell design) based on the accurate control of the parameters determining ohmic drop inside the cell

Ni and Ni-Pd nanostructures electrodes for water-alkaline electrolyses

Hydrogen production by water electrolysis (WE) is a very promising technology because it is a pollution free-process specially if renewable energy are employed. Up to day, the cost of hydrogen production by WE is higher than other available technologies, making WE not competitive. Many efforts have been made to improve WE performance, through the use of electrodes made of transition metal alloys (Pt2Mo, TiPt) as a cathode or pyrochlore type oxide (Tl2RuxIr2-xO7) as an anode [1]. In the field of water-alkaline electrolyzer, the development of cheap nanoporous nickel electrodes with high electrocatalytic features is one of the potential approaches to increase the WE performance [2]., A facile method for obtaining nanostructured electrodes is template electrosynthesis. Through this method, we have fabricated electrodes formed of Ni nanowires that have a very high surface area. In a preliminary work, we have shown that alkaline electrolyzer assembled with IrO2 nanoparticles covering Ni nanowires, acting as an anode, and a Ni sheet, acting as cathode, shows very good and stable performance also at room temperature [3]. In this work, the attention was focused on the fabrication of electrodes for hydrogen evolution reaction (HER). In particular, through metal displacement deposition, we have deposited nanoparticles of Pd on Ni nanowires electrodes with the aim to enhance the electrocatalytic performance of Ni nanowires shown in Figure 1. The results on the growth and characterization of nanostructured composite electrodes will be presented and discussed. Preliminary test on the electrolyzer performances, carried out at constant current in 30% w/w aqueous solution of potassium hydroxide, will be also reported

Fabrication and characterization of nanostructured Ni and Pd electrodes for hydrogen evolution reaction (HER) in water-alkaline electrolyzer

In the field of water-alkaline electrolyzer, the development of nanoporous low cost nickel electrodes is one of the potential approaches to increase electrocatalytic activity. Template electrodeposition is a facile and cheap technique for obtaining Ni nanowires (NWs) with high surface area. These nanostructures were fabricated by a two-step procedure. In the first step, a Ni compact layer was deposited on one side of the template where a gold film was previously sputtered, while, in the second-step, an ordered array of Ni-NWs was obtained by electrodeposition inside the template channels. The NWs were firmly connected to the underlying Ni layer, acting as a current collector. In order to enhance the catalytic activity, Pd nanoparticles were deposited onto the NW surface by metal displacement. All electrodes were characterized by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The comparison between the two types of electrodes revealed that the composite electrode (Ni+Pd) shows better electro-catalytic features, which quickly decay under operation, so that after 5 min. of polarization at a constant current in 30% w/w aqueous solution of potassium hydroxide, the other electrode performs better