V. Baglio

Hybrid Nafion–silica membranes doped with heteropolyacids for application in direct methanol fuel cells

Nafion–silica composite membranes doped with phosphotungstic and silicotungstic acids have been investigated for application in direct methanol fuel cells at high temperature (145°C). The phosphotungstic acid-based membrane showed better electrochemical characteristics at high current densities with respect to both silicotungstic acid-modified membrane and silica–Nafion membrane. A maximum power density of 400 mW cm−2 was obtained at 145°C in the presence of oxygen feed, whereas the maximum power density in the presence of air feed was approaching 250 mW cm−2. The results indicate that the addition of inorganic hygroscopic materials to recast Nafion extends the operating range of a direct methanol fuel cell. Operation at high temperatures significantly enhances the kinetics of methanol oxidation.

Influence of the acid-base characteristics of inorganic fillers on the high temperature performance of composite membranes in direct methanol fuel cells

Various recast Nafion® composite membranes containing ceramic oxide fillers with different surface characteristics (SiO2, SiO2–PWA, Al2O3, ZrO2) have been investigated for application in high temperature direct methanol fuel cells (DMFCs). Cell resistance at 145 °C increases as a function of the pH of slurry of the inorganic filler indicating a strong influence of the acid–base characteristics on the electrolyte conductivity. This effect has been attributed to the different water retention capabilities of the various membranes. Fuel cell performance at 145 °C, expressed as both maximum power density and current density at 0.5 V cell potential, increases almost linearly as the pH of slurry of the oxide materials decreases. Appropriate selection of the surface properties for the inorganic fillers allows to enhance the proton conductivity and extends the operating temperature range of composite membranes. The influence of fuel cell operating pressure on the humidification properties of these electrolytes at high temperature has been also investigated.

Influence of flow field design on the performance of a direct methanol fuel cell

Serpentine (SFF) and interdigitated (IFF) flow fields were investigated with regard to their use in a direct methanol fuel cell (DMFC). The DMFC equipped with SFFs showed lower methanol cross-over, higher fuel utilisation and slightly larger voltage efficiency at low current densities. IFFs enhanced mass transport and membrane humidification allowing to achieve high power densities of 450 and 290 mW cm−2 in the presence of oxygen and air feed, respectively, at 130°C. A fuel efficiency of 90% was obtained with the IFFs in the presence of 1 M methanol feed at 130°C and a current load of 500 mA cm−2.

Investigation of direct methanol fuel cells based on unsupported Pt-Ru anode catalysts with different chemical properties

The structure, chemistry and morphology of commercial unsupported Pt–RuOx and in-house prepared Pt–Ru catalysts were analysed. The catalytic activity of these materials towards electro-oxidation of methanol in solid-polymer-electrolyte direct methanol fuel cells have been investigated at 130°C. The in-house prepared unsupported Pt–Ru catalyst showed higher performance with lower activation control and mass polarisation losses in relation to the Pt–RuOx catalyst. An enhancement of mass-transport properties was obtained in the presence of interdigitated flow-fields. Maximum power densities of about 0.45 and 0.29 W cm−2 in the presence of oxygen and air-feed, respectively, were obtained at 130°C. Methanol cross-over rates and fuel efficiency were determined under various conditions.

Polymer electrolyte membrane water electrolysis: status of technologies and potential applications in combination with renewable power sources

Technological improvements in polymer electrolyte membrane water electrolysers (PEMWEs) are promoted by their exciting possibilities to operate with renewable power sources. In this paper, a synopsis of the research efforts concerning with the development of electrocatalysts, polymer electrolytes and stack hardware components is presented. The most challenging problem for the development of PEMWEs is the enhancement of oxygen evolution reaction rate. At present, there are no practical alternatives to noble metal-based oxide catalysts such as IrO2 and RuO2. As well as carbon supported Pt nanoparticles are the benchmark cathode catalysts for hydrogen evolution. High noble metal loading on the electrodes and the use of perfluorosulfonic membranes significantly contribute to the cost of these devices. Critical areas include the design of appropriate mixed electrocatalysts and their dispersion on low cost Ti-oxide like supports to increase catalyst utilization. Moreover, the development of alternative membranes with enhanced mechanical properties for high pressure applications, proper conductivity and reduced gas cross-over is strongly required. This latter aspect is also addressed by the development of proper recombination catalysts. The development of anodic mixed non-noble transition metal oxides with spinel or perovskite structure and proper resistance to chemical degradation in the acidic environment and electrochemical corrosion is also an active area of research. Similarly, efforts are also being addressed to Pd and Ru based cathode formulations with cheaper characteristics than Pt. Whereas, concerning with stack hardware, cost reduction may be addressed by replacing Ti-based diffusion media and bipolar plates with appropriate and cost-effective stainless steel materials with enhanced resilience to chemical and electrochemical corrosion. Regarding the combination with renewable power sources, PEM electrolysers can find suitable applications for peak shaving in integrated systems grid connected or in grid independent operating conditions where hydrogen generated through electrolysis is stored and then via fuel cell converted back to electricity when needed or used to refill fuel cell-based cars. Hydrogen is the most promising clean energy carrier to accomplish the sustainable production of energy and a synergy among hydrogen, electricity and renewable energy sources is highly desired.

Composite Mesoporous Titania Nafion-Based Membranes for Direct Methanol Fuel Cell Operation at High Temperature

Composite Nafion-based membranes, containing 5 wt % of high-purity mesoporous titania with an average pore size of about 3.5 nm heated to 350, 450, and 600 degrees C as a filler were successfully recasted. Field emission scanning electron microscopy observations showed a high degree of dispersion of mesoporous titania particles in Nafion. Direct methanol fuel cell investigation of such membranes at temperatures higher than 100 degrees C revealed a considerable influence of the presence of the ceramic oxide and of its specific surface area on the electrochemical behavior. The composite membranes allowed operation up to 145 degrees C, showing a significant performance improvement with respect to pure Nafion. At 145 degrees C with oxygen feed, a power density of about 335 mW/cm(2) was recorded for the composite Nafion-based membranes, containing 5 wt % of mesoporous titania calcined at 450 degrees C. (c) 2005 The Electrochemical Society. All rights reserved.

High Performance and Cost-Effective Direct Methanol Fuel Cells: Fe-N-C Methanol-Tolerant Oxygen Reduction Reaction Catalysts

Direct methanol fuel cells (DMFCs) offer great advantages for the supply of power with high efficiency and large energy density. The search for a cost-effective, active, stable and methanol-tolerant catalyst for the oxygen reduction reaction (ORR) is still a great challenge. In this work, platinum group metal-free (PGM-free) catalysts based on Fe-N-C are investigated in acidic medium. Post-treatment of the catalyst improves the ORR activity compared with previously published PGM-free formulations and shows an excellent tolerance to the presence of methanol. The feasibility for application in DMFC under a wide range of operating conditions is demonstrated, with a maximum power density of approximately 50 mW cm(-2) and a negligible methanol crossover effect on the performance. A review of the most recent PGM-free cathode formulations for DMFC indicates that this formulation leads to the highest performance at a low membrane-electrode assembly (MEA) cost. Moreover, a 100 h durability test in DMFC shows suitable applicability, with a similar performance-time behavior compared to common MEAs based on Pt cathodes.

Development of Pt and Pt – Fe Catalysts Supported on Multiwalled Carbon Nanotubes for Oxygen Reduction in Direct Methanol Fuel Cells

Pt and Pt-Fe catalysts supported on multiwalled carbon nanotubes (MWCNTs) were prepared by impregnation and reduction at intermediate temperature (400°C). The MWCNTs with diameters ranging from 20 to 100 nm were synthesized by a spray pyrolysis technique. Pt/MWCNTs and Pt-Fe/MWCNT catalysts were characterized by X-ray diffraction, X-ray fluorescence, scanning electron microscope-energy dispersive X-ray analysis, and transmission electron microscopy techniques. The electrocatalytic behavior for the oxygen reduction reaction was investigated in rotating disk electrode configuration in an acidic medium, also in the presence of various methanol concentrations (0.01, 0.1, and 1 M). An anodic shift of the peak potential for methanol oxidation of ∼150 mV was observed in the presence of 1 M methanol concentration for the Pt-Fe catalyst compared to the Pt catalyst. Both materials were used as cathodes in a direct methanol fuel cell at 30 and 60°C. A better performance was obtained for the cell based on Pt-Fe/MCWNTs as cathode catalyst. Although slight iron dissolution was observed after two weeks of discontinuous operation, the performance of the Pt-Fe catalyst was larger than the Pt catalyst.

Synthesis of Pd3Co1@Pt/C Core‐Shell Catalysts for Methanol‐Tolerant Cathodes of Direct Methanol Fuel Cells

A composite Pd-based electrocatalyst consisting of a surface layer of Pt (5 wt.%) supported on a core Pd3Co1 alloy (95 wt.%) and dispersed as nanoparticles on a carbon black support (50 wt.% metal content) was prepared by using a sulphite-complex route. The structure, composition, morphology, and surface properties of the catalyst were investigated by XRD, XRF, TEM, XPS and low-energy ion scattering spectroscopy (LE-ISS). The catalyst showed an enrichment of Pt on the surface and a smaller content of Co in the outermost layers. These characteristics allow a decrease the Pt content in direct methanol fuel cell cathode electrodes (from 1 to 0.06 mg cm(-2)) without significant decay in performance, due also to a better tolerance to methanol permeated through the polymer electrolyte membrane.

Towards new generation fuel cell electrocatalysts based on xerogel–nanofiber carbon composites

Xerogel–nanofiber carbon composites (XNCCs) have been easily synthesized by using a Ni catalyst supported on carbon xerogel (CXG), growing randomly oriented carbon nanofibers (CNFs) within the coralline-like structure of the xerogel (CXG). This novel composite combines the advantages of xerogel and fiber nanostructures. The interactions between these phases as well as their effect as a support on Pt electrocatalysts for the oxygen reduction reaction (ORR) have been investigated. Platinum catalysts supported on different XNCCs (varying in terms of CXG and CNF contents) as well as on bare CXG and CNFs have been synthesized using a microemulsion route. They have been characterized in terms of structure, morphology and porosity and investigated for the ORR in a half-cell configuration. The catalyst supported on the XNCC with a 44% CNF content shows the best electrochemical behavior. This catalyst formulation leads to a catalytic activity 5 times higher than that obtained on a Vulcan-based catalyst at low overpotential and 2.5 times higher at large overpotential. Accelerated degradation tests also show better stability for the composite support-based catalyst. Compared to bare CNF and CXG supports, a stabilization effect is envisaged by the presence of highly graphitic CNFs within the composite structure.