Microfabricated polymer electrolyte membrane fuel cells with low catalyst loadings

Miniaturized fuel cells as compact power sources fabricated in Pyrex glass using standard polymer electrolyte membrane (PEM) and electrode materials are presented. Photolithographic patterned and wet chemically etched serpentine flow channels of 1 mm in width and 250  m in depth transport the fuels to the cell of 1.44 cm² active electrode area. Feeding H₂/O₂ a maximum power density of 149 mW cm⁻² is attained at a very low Pt loading of 0.054 mg cm⁻², ambient pressure, and room temperature. Operated with methanol and oxygen about 9 mW cm⁻² are achieved at ambient pressure, 60 °C, and 1 mg cm⁻² PtRu/Pt (anode/cathode) loading. A planar two-cell stack to demonstrate and investigate the assembly of a fuel cell system on Pyrex wafers has successfully been fabricated.     

Facile synthesis of bimodal porous silica and multimodal porous carbon as an anode catalyst support in proton exchange membrane fuel cell

A simple and easy sol-gel approach has been developed to directly synthesize in situ three-dimensionally interconnected uniform ordered bimodal porous silica (BPS) incorporating both the macroporosity and mesoporosity in the lattice without extra synthesis process performed in previous work. Multimodal porous carbon (MPC) was fabricated through the inverse replication of the BPS. The unique structural characteristics such as well-developed 3-D interconnected ordered macropore framework with open mesopores embedded in the macropore walls, large surface area (1120 m² g⁻¹) and mesopore volume (1.95 cm³ g⁻¹) make MPC very attractive as an anode catalyst support in polymer exchange membrane fuel cell. The MPC-supported Pt-Ru alloy catalyst has demonstrated much higher power density toward hydrogen oxidation than the commercial carbon black Vulcan XC-72-supported ones.     

Preparation of mesoporous carbon templated by silica particles for use as a catalyst support in polymer electrolyte membrane fuel cells

Mesoporous carbons were prepared using commercial silica particles and a formaldehyde–resorcinol resin as a template and carbon precursor, respectively. By changing the molar ratio of template to carbon precursor, mesoporous carbons with different mesoporosities (MC-X, X represents the molar ratio of template to carbon precursor) were produced. The resulting MCs had a high-surface area and large pore volume. In particular, the highest mesoporosity was observed for MC-3. Pt catalysts-supported on MC-X were prepared using formaldehyde as a reducing agent for use as a cathode catalyst in a polymer electrolyte fuel cell (PEMFC). The size of Pt crystallite was dependent on the properties of corresponding carbon support. As a whole, a carbon support with a high-surface area and high-mesoporosity served the best in terms of a high-dispersion of Pt nanoparticles. In a unit cell test of the PEMFC, a Pt catalyst with a high-mesoporosity and fine dispersion of metal showed an enhanced performance. The findings indicate that the surface area combined with the mesoporosity had a positive influence on the metal dispersion and the distribution of ionomer, leading to the enhanced cell performance.     

Hollow core/mesoporous shell carbon capsule as an unique cathode catalyst support in direct methanol fuel cell

Hollow core mesoporous shell (HCMS) carbon has been explored for the first time as a cathode catalyst support in direct methanol fuel cells (DMFCs). The HCMS carbon consisting of discrete spherical particles possesses unique structural characteristics including large specific surface area and mesoporous volume and well-developed interconnected void structure, which are highly desired for a cathode catalyst support in low temperature fuel cells. Significant enhancement in the electrocatalytic activity toward oxygen reduction reaction has been achieved by the HCMS carbon-supported Pt nanoparticles compared with carbon black Vulcan XC-72-supported ones in the DMFC. In addition, much higher power was delivered by the Pt/HCMS catalysts (i.e., corresponding to an enhancement of ca. 91–128% in power density compared with that of Pt/Vulcan), suggesting that HCMS carbon is a unique cathode catalyst support in direct methanol fuel cell.     

Methanol-tolerant electrocatalysts for oxygen reduction in a polymer electrolyte membrane fuel cell

Heat-treated -oxo-iron(iii) tetramethoxy phenyl porphyrin (Fe-TMPP)2O and iron(iii) tetramethoxy phenyl porphyrin (FeTMPP-Cl) as well as iron(iii) octaethyl porphyrin (FeOEP-Cl) adsorbed on high-area carbons such as deashed and un-deashed RB carbon (Calgon) and Black Pearls-2000 (Cabot) have been found to exhibit stable and very high oxygen reduction rates. Experiments done over a period of 24h showed no performance degradation. Measured performances were very similar to supported platinum (E-Tek), when tested in 85% H3PO4-equilibrated Nafion 117 membrane at 125°C and hydrated-Nafion membrane at 60°C in a minifuel cell. The macrocycle cathodes are insensitive to the presence of methanol whereas the platinum cathodes are very sensitive and show degradation in the oxygen reduction performance.     

The effect of platinum on carbon corrosion behavior in polymer electrolyte fuel cells

To assess the catalytic effect of platinum on the corrosion of the high surface area carbon support, single triangular potential sweeps with various upper and lower limits were applied to fuel cells comprising electrodes having different Pt/C compositions. Carbon loss rates in H₂/N₂ and air/air mode were determined by integration of the resulting CO₂ concentration peaks in the exhaust gas of the positive electrode. Generally, the contribution of platinum catalyzed carbon corrosion to total CO₂ evolution was found to decrease with increasing upper potential limit. Similar carbon loss rates obtained for Pt/C and pure carbon electrodes in case of lower potential limits of 1.0 V indicate that the catalytic activity of platinum is substantially lowered by the formation of a passivating oxide layer on the platinum particles. Changes in corrosion behavior in the potential range below 0.6 V, which cannot be attributed to platinum effects, are suggested to originate from modifications in carbon surface oxide composition. Due to the high oxygen equilibrium potential of approximately 1 V, carbon corrosion in air/air mode is significantly influenced by platinum oxide formation. However, the polarization of the negative electrode and the influence of platinum oxidation on the equilibrium potential results in a passivating effect that is less pronounced than expected from measurements in H₂/N₂ mode.     

Enhanced performance and improved interfacial properties of polymer electrolyte membrane fuel cells fabricated using sputter-deposited Pt thin layers

For this study, catalyst layers for polymer electrolyte membrane fuel cells (PEMFC) were prepared by spraying and sputtering to deposit Pt amount of 0.1 and 0.01 mg cm⁻², respectively. These Pt layers were then assembled to fabricate membrane electrode assemblies (MEA) having either single- or double-layered catalysts. The PEM fuel cell with double layers showed a current density of 777 mA cm⁻² at a cell voltage of 0.6 V, which is a higher current density than state-of-the-art fuel cells at 643 mA cm⁻². These results indicate that Pt loading in state-of-the-art PEMFCs could be reduced by approximately 50% with no performance loss by using both spraying and sputtering method in the MEA fabrication process.     

Characteristics of subzero startup and water/ice formation on the catalyst layer in a polymer electrolyte fuel cell

This work experimentally explores the fundamental characteristics of a polymer electrolyte fuel cell (PEFC) during subzero startup, which encompasses gas purge, cool down, startup from a subfreezing temperature, and finally warm up. In addition to the temperature, high-frequency resistance (HFR) and voltage measurements, direct observations of water or ice formation on the catalyst layer (CL) surface have been carried out for the key steps of cold start using carbon paper punched with microholes and a transparent cell fixture. It is found that purge time significantly influences water content of the membrane after purge and subsequently cold-start performance. Gas purge for less than 30 s appears to be insufficient, and that between 90 and 120 s is most useful. After gas purge, however, the cell HFR relaxation occurs for longer than 30 min due to water redistribution in the membrane-electrode assembly (MEA). Cold-start performance following gas purge and cool down strongly depends on the purge time and startup temperature. The cumulative product water measuring the isothermal cold-start performance increases dramatically with the startup temperature. The state of water on the CL surface has been studied during startup from ambient temperatures ranging from −20 to −1 °C. It is found that the freezing-point depression of water in the cathode CL is 1.0 ± 0.5 °C and its effect on PEFC cold start under automotive conditions is negligible.     

Sulfonated multiblock copolynaphthalimides for polymer electrolyte fuel cell application

Sulfonated multiblock copolynaphthalimides (multiblock co-SPIs) were prepared by two-pot polymerization method from 1,4,5,8-naphthalenetetracarboxylic dianhydride, sulfonated diamine of 4,4′-bis(4-aminophenoxy)-3,3′-bis(4-sulfophenyl)biphenyl (BAPSPB) and nonsulfonated diamine of 4,4′-diaminophenyl hexafluoropropane. The multiblock co-SPI (BA1) with hydrophilic/hydrophobic block length of 20/10 and ion exchange capacity (IEC) of 1.67 meq g⁻¹ exhibited larger water uptake, larger in-plane and through-plane proton conductivity (σ∥ and σ⊥, respectively) than the random co-SPI with the similar IEC. The multiblock co-SPI (BA2) with the longer block length of 20/20 exhibited the large σ∥ and σ⊥ comparable to those of BA1, in spite of the smaller IEC of 1.35 meq g⁻¹. Both the multiblock and random co-SPIs showed the moderate anisotropic proton conductivity (σ_⊥/σ_//≒ 0.70) as well as anisotropic membrane swelling with about three times larger through-plane swelling than in-plane swelling. The TEM observation revealed that BA2 had an isotropic and inhomogeneous morphology with indistinct microphase-separated structure, whereas the random co-SPIs had a homogeneous morphology. The behavior of BAPSPB-based multiblock co-SPI membranes were quite different from that of the multiblock co-SPIs based on 2,2′-bis(4-sulfophenoxy)benzidine, which was due to the presence of two flexible ether bonds in BAPSPB moiety of the main chain. Even under the low humidification of 27/27% RH at 90 °C and 0.2 MPa, BA2 exhibited the fairly high PEFC performance; namely, cell voltage of 0.67 V at load current density of 0.5 A cm⁻² and maximum output of 0.51 W cm⁻², which were much larger than those of BA1 and the random co-SPI (RA1) with IEC of 1.84 meq g⁻¹, and have the high potential as PEM for PEFC applications.     

Homogenization of the current density in polymer electrolyte fuel cells by in-plane cathode catalyst gradients

Polymer electrolyte fuel cells (PE fuel cells) working with air at low stoichiometries (<2.0) and standard electrochemical components show a high degree of inhomogeneity in the current density distribution over the active area. An inhomogeneous current density distribution leads to a non-uniform utilization of the active area, which could negatively affect the time of life of the cells. Furthermore, it is also believed to lower cell performance. In this work, the homogenization of the current density, realized by means of tailored cathodes with along-the-air-channel redistributed catalyst loadings, is investigated. The air stoichiometry range for which a homogenization of the current density is achieved depends upon the gradient with which the catalyst is redistributed along the air channel. A gentle increasing catalyst loading profile homogenizes the current density at relatively higher air stoichiometries, while a steeper profile is suited better for lower air stoichiometries. The results show that a homogenization of the current density by means of redistributed catalyst loading has negative effects on cell performance. Model calculations corroborate the experimental findings on homogenization of the current density and deliver an explanation for the decrease in cell performance.     

Computational fluid dynamics simulation of polymer electrolyte membrane fuel cells operating on reformate

Carbon monoxide (CO) can extremely diminish the polymer electrolyte membrane fuel cell (PEMFC) performance since it is preferentially absorbed on the platinum catalyst layer blocking and reducing the number of catalyst sites available for the hydrogen oxidation reaction. To gain a good insight of CO poisoning characteristics so as to provide a remedial solution for CO-poisoned PEMFCs, a two-dimensional, isothermal, and single phase CO poisoning numerical model taking into account the transport phenomena, electrochemical reactions and multi-component gas mixture transport is developed for such purpose. Linear and bridged-bonded adsorbed CO modes were considered to occur in parallel on the highly dispersed nano-crystalline Pt/C and PtRu/C catalysts. By performing computational fluid dynamics numerical simulations, this study clearly demonstrates the CO poisoning mechanisms and characteristics of PEMFCs. The numerical results obtained are in reasonably good agreement with the experimental data showing the predictive capability of the model.     

Characteristics and performance of membrane electrode assemblies with operating conditions in polymer electrolyte membrane fuel cell

The degradation behavior of a membrane-electrode assembly (MEA) was investigated in accelerated degradation tests under constant voltage (0.8 V and 0.7 V) and load cycling (from open circuit voltage to 0.35 V) conditions. Changes in the structural and electrochemical characteristics of MEA after the durability tests give information as to the degradation mechanism of MEAs. The results of cyclic voltammogram and postmortem analysis by X-ray diffraction and high resolution-transmission electron microscopy indicate that the cathode catalyst layers of the MEAs showed no extreme degradation under constant voltage mode, whereas MEAs under repetition of load cycling mode showed very severe degradation after 280 h. However, the single cell performance of the MEA under repetition of load cycling mode was higher than under constant voltage mode. In addition, although the Pt band in the membrane of the MEA under repetition of load cycling mode was observed by field emission scanning electron microscopy, it did not affect the ohmic resistance.     

A phenyl-sulfonic acid anchored carbon-supported platinum catalyst for polymer electrolyte fuel cell electrodes

A method, to anchor phenyl-sulfonic acid functional groups with the platinum catalyst supported onto a high surface-area carbon substrate, is reported. The use of the catalyst in the electrodes of a polymer electrolyte fuel cell (PEFC) helps enhancing its performance. Characterization of the catalyst by Fourier transform infra red (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and point-of-zero-charge (PZC) studies suggests that the improvement in performance of the PEFC is facilitated not only by enlarging the three-phase boundary in the catalyst layer but also by providing ionic-conduction paths as well as by imparting negative charge to platinum sites with concomitant oxidation of sulfur present in the carbon support. It is argued that the negatively charged platinum sites help repel water facilitating oxygen to access the catalyst sites. The PEFC with modified carbon-supported platinum catalyst electrodes exhibits 40% enhancement in its power density as compared to the one with unmodified carbon-supported platinum catalyst electrodes.     

Effects of MEA fabrication method on durability of polymer electrolyte membrane fuel cells

To study the effects of fabrication methods on the durability of polymer electrolyte membrane fuel cells (PEMFCs), membrane-electrode assemblies (MEAs) were fabricated using a conventional method, a catalyst-coated membrane (CCM) method, and a CCM-hot pressed method. Single cells assembled with the prepared MEAs were operated galvanostatically at 600 mA cm⁻² for 1000 h for the conventional MEA and the CCM MEA and for 500 h for the CCM-hot pressed MEA. During operation, i-V curves, impedance spectra, and cyclic voltammograms were measured roughly every 100 h. Before and after long-term operation, the physical and chemical characteristics of the MEAs were analyzed using mercury porosimetry, X-ray diffraction (XRD), scanning electron microscopy (SEM), electron probe microanalysis (EPMA), and Fourier transformation infrared spectroscopy (FTIR). Under the operating conditions, the CCM MEA exhibited the lowest degradation rate as well as the highest initial performance.     

Influence of hydrophilicity in micro-porous layer for polymer electrolyte membrane fuel cells

Water management is one of the most important factors for improving the performance in polymer electrolyte membrane fuel cells (PEMFCs). The micro-porous layers (MPLs) in the membrane-electrode assembly provide proper pores and paths for mass transport, thereby allowing for the control of the water balance. In this study, a copolymer containing hydrophilic functional groups is introduced into the binder materials of the MPL instead of a highly hydrophobic binder. When 10 wt.% of the binder is incorporated in the MPL on the cathode side, the best performance is exhibited and the ohmic resistance is decreased. Although the charge transfer resistance at low potential is higher than that of the hydrophobic treated MPL, due to the flooding effects, the charge transfer resistance at high potential becomes smaller. This indicates that excess liquid absorption from the catalyst layer to the hydrophilic MPL occurs more strongly than in the case of the hydrophobic MPL. This may bring about an increase in the accessibility of oxygen to the active sites, because the excess liquid near the catalyst agglomerates is expelled as fast as possible. Consequently, the hydrophilicity control in the MPL has a positive effect on the water management in PEMFCs.     

Fuel cell performance of polymer electrolyte membrane based on hexafluorinated sulfonated poly(ether sulfone)

The potential-current fuel cell characteristics of membrane electrode assemblies (MEAs) using hexafluorinated sulfonated poly(ether sulfone) copolymer are compared to those of Nafion^® based MEAs in the case of proton exchange membrane fuel cell (PEMFC) and direct methanol fuel cell (DMFC). The hexafluorinated copolymer with 60 mol% of monosulfonated comonomer based acid form membrane is chosen for this study due to its high proton conductivity, high thermal stability, low methanol permeability, and its insolubility in boiling water. The catalyst powder is directly coated on the membrane and the catalyst coated membrane is used to fabricate MEAs for both fuel cells. A current density of 530 mA cm^?2 at 0.6 V is obtained at 70 °C with H₂/air as the fuel and oxidant. The peak power density of 110 mW cm^?2 is obtained at 80 °C under specific DMFC operating conditions. Other electrochemical characteristics such as electrochemical impedance spectroscopy, cyclic voltammetry, and linear sweep voltammetry are also studied.     

Tantalum oxide-based compounds as new non-noble cathodes for polymer electrolyte fuel cell

Tantalum oxide-based compounds were examined as new non-noble cathodes for polymer electrolyte fuel cell. Tantalum carbonitride powder was partially oxidized under a trace amount of oxygen gas at 900 °C for 4 or 8 h. Onset potential for oxygen reduction reaction (ORR) of the specimen heat-treated for 8 h was 0.94 V vs. reversible hydrogen electrode in 0.1 mol dm⁻³ sulfuric acid at 30 °C. The partial oxidation of tantalum carboniride was effective to enhance the catalytic activity for the ORR. The partially oxidized specimen with highest catalytic activity had ca. 5.25 eV of ionization potential, indicating that there was most suitable strength of the interaction of oxygen and tantalum on the catalyst surface.     

Performance and durability of sulfonated poly(arylene ether sulfone) membrane-based membrane electrode assemblies fabricated by decal method for polymer electrolyte fuel cells

The combination of Nafion-based electrode and hydrocarbon-based membrane is an ideal choice for researcher in making membrane electrode assemblies (MEAs) containing alternative membranes replacing Nafion for polymer electrolyte fuel cells (PEFCs) due to their intrinsic properties. This advantage, however, is limited by the incompatibility between the membrane and the electrode, which results in MEA performance decay and low durability. In this study, we propose fabrication of MEA made of sulfonated poly(aryl ether sulfone) (SPES) membrane and Nafion-based electrode using the decal process. The decal process was found to be very effective in forming good interface between SPES and the electrode, although hot pressing temperature was relatively low (140 °C). The SPES-MEA revealed comparable performance to conventional Nafion-MEA at high humidity, indicating negligible contact resistance in the SPES–electrode interface. Open circuit voltage (OCV) drop of SPES-MEA during OCV holding at 40% RH for 200 h was from 0.975 V to 0.8 V, implying slight chemical degradation of SPES leading to increased hydrogen crossover in the membrane. However, it seems that the interfacial damage between the SPES and Nafion electrode in the SPES-MEA is negligible during the OCV test. Nonetheless, further investigation is necessary to confirm the long-term stability of the SPES-MEA fabricated by the decal process under harsher conditions such as dry/wet and freeze/thaw cycling.     

Multi-layer configuration for the cathode electrode of polymer electrolyte fuel cell

This paper conducts a one-dimensional theoretical study on the electrochemical phenomenon in the dual-layer cathode electrode of polymer electrolyte fuel cells (PEFCs) with varying sub-layer thicknesses, and further extends the analysis to a triple-layer configuration. We obtain the explicit solution for a general dual-layer configuration with different layer thicknesses. Distributions of the key quantities such as the local reaction current and electrolyte overpotential are exhibited at different ratios of the ionic conductivities, electrochemical kinetics, and layer thicknesses. Based on the dual-layer approach, we further derive the explicit solutions for a triple-layer electrode. Sub-layer performances are plotted and compared. The results indicate that the layer adjacent to the electrolyte membrane may contribute a major part of the electrode faradic current production. The theoretical analysis presented in this paper can be applied to assist electrode development through complicated multi-layer configuration for cost-effective high performance electrodes.