Ultra-low Pt loading for proton exchange membrane fuel cells by catalyst coating technique with ultrasonic spray coating machine

This paper reports use of an ultrasonic spray for producing ultra-low Pt load membrane electrode assemblies (MEAs) with the catalyst coated membrane (CCM) fabrication technique. Anode Pt loading optimization and rough cathode Pt loading were investigated in the first stage of this research. Accurate cathode Pt coating with catalyst ink using the ultrasonic spray method was investigated in the second stage. It was found that 0.272 mg_Pt/cm² showed the best observed performance for a 33 wt% Nafion CCM when it was ultrasonically spray coated with SGL 24BC, a Sigracet manufactured gas diffusion layer (GDL). Two different loadings (0.232 and 0.155 mg_Pt/cm²) exposed to 600 mA/cm² showed cathode power mass densities of 1.69 and 2.36 W/mg_Pt, respectively. This paper presents impressive cathode mass power density and high fuel cell performance using air as the oxidant and operated at ambient pressure.     

The effects of Nafion ionomer content in PEMFC MEAs prepared by a catalyst-coated membrane (CCM) spraying method

We analyzed the effects of ionomer content on the proton exchange membrane fuel cell (PEMFC) performance of membrane electrode assemblies (MEAs) fabricated by a catalyst-coated membrane (CCM) spraying method in partially humidified atmospheric air and hydrogen. When high loading Pt/C catalysts (45.5 wt.%) were used, we observed that catalytic activity was not directly proportional to electrochemical active surface area (EAS). This suggests that ionic conductivity through ionomers in catalyst layers is also an important factor affecting MEA performance. In addition, the effects of mass transport were experimentally evaluated by manipulating the air stoichiometry ratio at the cathodes. MEA performance was more sensitive to flow rates under conditions of higher ionomer content. Due to the combined effect of EAS, ionic conductivity, and mass transfer characteristics (all of which varied according to the ionomer content), an MEA with 30 wt.% ionomer content at the cathode (25 wt.% at the anode) was shown to yield the best performance.     

Effect of the Pt precursor on the morphology and catalytic performance of Pt-impregnated on Pd/C for the oxygen reduction reaction in polymer electrolyte fuel cells

We describe how the morphology and electrocatalytic activity of Pt-Pd with low levels of Pt are dependent on the type of Pt precursor that is used for the impregnation on to Pd/C. When a Pt precursor with a negative charge (H₂PtCl₆) is used in the preparation medium (Pt-Pd/C-H), its electrostatic interaction with the carbon surface results in some Pt nanoparticles being deposited on the carbon separately from the Pd surface. Due to the absence of such an electrostatic interaction with the Pt(NH₃)₄Cl₂ precursor, more selective deposition of Pt can be achieved on the Pd surface (Pt-Pd/C-N). Depending on the morphology, different electrocatalytic performance in oxygen reduction reaction would be observed. Compared to Pt-Pd/C-H, Pt-Pd/C-N shows 180% (half-cell at 0.9 V) and 160% (unit-cell at 0.8 V) enhanced performance, which is comparable to that on Pt/C. It is believed that the interaction between the Pt and the Pd substrate is more extensive in Pt-Pd/C-N than in Pt-Pd/C-H, and this is responsible for the large difference in the catalytic performances between these two catalysts.     

Pt/C catalyst degradation in proton exchange membrane fuel cells due to high-frequency potential cycling induced by switching power converters

Proton exchange membrane fuel cells are operated using switching power converters that produce high-frequency ripple currents. These ripples cause high-frequency potential cycling of cells, which is believed to lead premature deterioration in the electrochemical surface area (ECA) of Pt/C catalysts. The qualitative relationship between ECA losses and the frequency of potential cycling was investigated in the range of 1 Hz to 1 kHz. For frequencies higher than 100 Hz, ECA losses were comparable with those at the potential hold condition. However, for lower frequencies, ECA decreased significantly with decreasing frequency. TEM observations showed that there was marked Pt particle growth for the 1-Hz cycling condition, whereas particle size distributions at 100 Hz and potential hold conditions were comparable. The currents associated with Pt oxidation and reduction during potential cycling were also investigated at various potentials and frequencies, and the charges associated with Pt loss (ΔQ) were determined by integrating the measured current. A correlation between the ECA trend and ΔQ was observed. The results obtained in this study are considered informative for electrical engineering research, because it relates to the design of switching power converters that do not negatively influence the Pt/C catalyst durability.     

Effect of ionomer content and relative humidity on polymer electrolyte membrane fuel cell (PEMFC) performance of membrane-electrode assemblies (MEAs) prepared by decal transfer method

Membrane-electrode assemblies (MEAs) were fabricated by the decal transfer method with various Nafion ionomer contents (10–40 wt%) and their single cell performance and electrochemical characteristics were examined in atmospheric air at relative humidities of 25–95%. At high humidity (95%), the MEA performance was the highest with a cathode ionomer content of 30 and 20 wt% at 0.6 and 0.4 V, respectively. The optimum ionomer content of the decal MEAs increased with decreasing humidity, because of the change in the oxygen transport rate (water flooding) and number of active sites (ionic resistance). The concentration overpotential gradually increased with relative humidity up to about 0.4 V at 0.8 A/cm², which was not considered in previous studies using pressurized air and oxygen. The combined effect of the electrochemical active surface area and ionic resistance of the cathodes on the activation overpotential was also investigated, focusing on intermediate and low humidity levels, using a newly developed impedance analysis method.     

Novel silica/poly(2,6-dimethyl-1,4-phenylene oxide) hybrid anion-exchange membranes for alkaline fuel cells: Effect of silica content and the single cell performance

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO)-based organic-inorganic hybrid alkaline membranes with enhanced hydroxyl (OH⁻) conductivity are prepared in response to the relatively low conductivity of previously reported PPO-based systems. The membranes also exhibit higher swelling-resistant properties and the hydroxyl (OH⁻) conductivity values are comparable to previously reported fluoropolymer-containing membranes: 0.012-0.035 S cm⁻¹ in the temperature range 30-90 °C. Other favorable properties for fuel cell application include high tensile strengths up to 25 MPa and large ion-exchange capacities in the range 2.01-2.27 mmol g⁻¹. Beginning-of-life fuel cell testing of a membrane with a thickness of 140 μm yielded an acceptable H₂/O₂ peak power density of 32 mW cm⁻² when incorporated into an alkaline membrane electrode assembly. Therefore, this class of hybrid membrane is suitable for application in alkaline membrane fuel cells.     

Effects of sulfonated polyether-etherketone (SPEEK) and composite membranes on the proton exchange membrane fuel cell (PEMFC) performance

Sulfonated polyether-etherketone (SPEEK) has a potential for proton exchange fuel cell applications. However, its conductivity and thermohydrolytic stability should be improved. In this study the proton conductivity was improved by addition of an aluminosilicate, zeolite beta. Moreover, thermohydrolytic stability was improved by blending poly-ether-sulfone (PES). Sulfonated polymers were characterized by H-NMR. Composite membranes prepared were characterized by Electrochemical Impedance Spectroscopy (EIS) for their proton conductivity. Degree of sulfonation (DS) values calculated from H-NMR results, and both proton conductivity and thermohydrolytic stability was found to strongly depend on DS. Therefore, DS values were controlled time in the range of 55–75% by controlling the reaction time. Zeolite beta fillers at different SiO₂/Al₂O₃ ratios (20, 30, 40, 50) were synthesized and characterized by XRD, EDX, TGA, and SEM. The proton conductivity of plain SPEEK membrane (DS = 68%) was 0.06 S/cm at 60 °C and the conductivity of the composite membrane containing of zeolite beta filled SPEEK was found to increase to 0.13 S/cm. Among the zeolite Beta/SPEEK composite membranes the best conductivity results were achieved with zeolite beta having a SiO₂/Al₂O₃ ratio of 50 at 10 wt% loading.     

Study of morphological characteristics on hydrophilicity‐enhanced SiO2/Nafion composite membranes by using multimode atomic force microscopy

Air‐breathing proton exchange membrane fuel cells (AB‐PEMFCs) have a great potential for commercialization owing to their simple mechanical configuration and low cost compared with traditional proton exchange membrane fuel cells (PEMFCs). However, AB‐PEMFCs perform worse than traditional PEMFCs owing to the omission of the humidifier and a poor air supply system. In this study, hygroscopic metal oxide materials with good water absorption characteristics were employed in a Nafion membrane without humidification to compensate for the lack of performance owing to low proton conductivity. Among the various metal oxide materials, mesoporous structured silica has been synthesized with Nafion to increase the water content in nonhumidified conditions. The local morphological variation and surface charge distribution on the pristine Nafion and SiO₂/Nafion composite membranes were analyzed by using multimode atomic force microscopy and force distance analyses. Several remarkable results were revealed, including considerable morphological changes and a locally separated water cluster network structure.