F. Zaza

Molten carbonate fuel cells fed with biogas: Combating H2S

The use of biomass and waste to produce alternative fuels, due to environmental and energy security reasons, is a high-quality solution especially when integrated with high efficiency fuel cell applications. In this article we look into the coupling of an anaerobic digestion process of organic residues to electrochemical conversion to electricity and heat through a molten carbonate fuel cell (MCFC). In particular the pathway of the exceedingly harmful compound hydrogen sulphide (H(2)S) in these phases is analysed. Hydrogen sulphide production in the biogas is strongly interrelated with methane and/or hydrogen yield, as well as with operating conditions like temperature and pH. When present in the produced biogas, this compound has multiple negative effects on the performance and durability of an MCFC. Therefore, there are important issues of integration to be solved. Three general approaches to solve the sulphur problem in the MCFC are possible. The first is to prevent the formation of hydrogen sulphide at the source: favouring conditions that inhibit its production during fermentation. Secondly, to identify the sulphur tolerance levels of the fuel cell components currently in use and develop sulphur-tolerant components that show long-term electrochemical performance and corrosion stability. The third approach is to remove the generated sulphur species to very low levels before the gas enters the fuel cell.

Characterization of Gas Diffusion Electrodes for Polymer Electrolyte Fuel Cells

Gas diffusion electrodes (GDEs), applied in polymer electrolyte fuel cells, are composed of a multilayer structure containing porous carbon materials and noble metal catalyst. Gas diffusion layer (GDL), a GDE component, consists of a thin layer of carbon black mixed with an organic binder, frequently polytetrafluoroethylene, which is coated onto a sheet of macroporous carbon backing cloth or paper. GDL serves as a current collector that allows ready access of fuel and oxidant to the anode and the cathode catalyst surfaces, respectively. In this work, a complete GDL state-of-the-art is first presented. Then, the effects of different fabrication methods and composition of gas diffusion layer are investigated and discussed in the light of gas permeability, thermal analysis, morphology, and electrical resistance. Besides, performances in H2/air fed cell at 50°C in different humidity conditions were discussed, and a comparison with own products and commercial GDLs was carried out. It was found that the different preparation methods influence the GDL properties, allowing the most suitable choice depending on the cell humidity conditions.

Novel Sol-Gel Synthesis of LiMn2O4 and LiNixCo1-xO2 Powders

A modified complex sol-gel process was developed to synthesize LiMn2O4 and LiNixCo1-xO2 powders. Sols were prepared from 1.5 M of Mn2+ or 1 M of xNi2+ and (1-x)Co2+ acetates plus ascorbic acid aqueous solutions by alkalizing them with LiOH and NH4OH. Ascorbic acid was added to prevent precipitation in the precursor solutions. When the sols were concentrated to one-third of their initial volume under reduced pressure and then gelled by drying for 10 days, heat treatment to ≥700 °C was accompanied by foaming, violent self-ignition, and formation of carbonates in the Ni-containing species. Significant improvements to the process and resulting powders were gained by modifying the gelation step. When gelation and drying were carried out under reduced total pressure, subsequent heating produced self-ignition, but no foaming, for all heating rates. The resulting products were determined to be nearly phase pure and carbonate free by thermogravimetric, differential thermal, X-ray, and infrared spectroscopy methods.

Vitrification of Nuclear Wastes by Complex Sol-Gel Process

For synthesis of silica glasses designed to contain high-level nuclear wastes，a patented complex sol-gel process has been used. Surrogates of the nuclear waste elements Cs, Sr, Co, and Nd (generically denoted Me) were used. Gels in the forms of powders and sintered compacts were prepared by hydrolysis and polycondensation of tetraethoxide/Me nitrate solutions, which contained ascorbic acid as a catalyst. Transformation to final products was studied by thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction. Preliminary testing of Me leaching was also completed in water. Most of the final products were porous; only a single dense form was resistant to leaching.

Performance Study of Nickel Covered by Lithium Cobaltite Cathode for Molten Carbonate Fuel Cells: A Comparison in Li/K and Li/Na Carbonate Melts

The slow dissolution of the lithiated NiO cathode represents one of the main causes of performance degradation in molten carbonate fuel cells. Two main approaches are usually investigated to overcome this problem: modifying the electrolyte composition and studying innovative cathode. In this work, the production of an alternative material as well as a study in different carbonate melt mixtures (62/38 mol % Li/K and 52/48 mol % Li/Na) of this innovative cathode have been taken into account. The issue of cathode surface protection was attained covering a nickel substrate with a thin layer of lithium cobaltite doped with magnesium (LiMg 0.05 Co 0 . 95 O 2 ); a sol impregnation technique was used to deposit gel precursors on the porous surface of the substrate. Chemical analysis, electrical conductivity measurements and scanning electron microscopy were used to characterize the cathodes before and after in-cell tests. The cathodic performance was tested in two 3 cm 2 area cells assembled with the following electrolyte compositions: Li/K=62/38 mol % and Li/Na =52/48 mol % in order to investigate the cathode behavior in different carbonate melt environments. Polarization curves and electrochemical impedance spectroscopy measurements were carried out during cell lifetime (about 850 h). Finally, different compositions of the cathodic gas were used to study the influence of oxygen and carbon dioxide on the electrode kinetics.

Solutions for Material Corrosion Problems in MCFC

It is widely recognized that metallic corrosion of the cathode current collector is a key technological problem that must be fully resolved before Molten Carbonate Fuel Cells can be commercialized on a more competitive basis. This paper presents a short overview on the corrosion mitigation strategies that appear more appropriate for MCFC current collectors. As alternative to the current use of the 300-series austenitic stainless steels, specialty high-Mn stainless steels, corrosion-resistant Ni-based alloys and sol-gel coatings of thin conductive spinel or perovskite ceramic layers are seen as the most promising corrosion solutions for the cathode-side environment. The use of basic additives into electrolyte for inhibiting molten carbonate corrosion is a further mitigation option yet with less practical perspectives due to the high constraints on the electrolyte properties. Recent and current studies conducted at ENEA on MCFC corrosion solutions are also mentioned.

Perovskite sensing materials for syngas composition monitoring and biomass gasifier numerical model validation: A preliminary approach

Biomass gasification represents a suitable choice for global environmental impact reduction, but more efforts on the process efficiency need to be conducted in order to enhance the use of this technology. Studies on inputs and outputs of the process, as well as measurements and controls of syngas composition and correlated organic and inorganic impurities, are crucial points for the optimization of the entire process: models of the system and sensing devices are, thus, very attractive for this purpose. In particular, perovskite based chemoresistive sensors could represent a promising technology, since their simplicity in function, relatively low cost and direct high temperature operation. The aim of this work is to develop a steam fluidized bed biomass gasifier model, for the prediction of the process gas composition, and new perovskite compounds, LaFeO3 based, as sensing material of chemoresistive sensors for syngas composition and impurities measurements. Chemometric analysis on the combustion synthesis...