High performance membrane electrode assembly with ultra-low platinum loading prepared by a novel multi catalyst layer technique

An ultra-low platinum loading membrane electrode assembly (MEA) with a novel double catalyst layer (DCL) structure was prepared by using two layers of platinum catalysts with different loadings. The inner layer consisted of a high loading platinum catalyst and high Nafion content for keeping good platinum utilization efficiency and the outer layer contained a low loading platinum catalyst with low Nafion content for obtaining a proper thickness thereby enhancing mass transfer in the catalyst layers. Polarization characteristics of MEAs with novel DCL, conventional DCL and single catalyst layer (SCL) were evaluated in a H₂–air single cell system. The results show that the performance of the novel DCL MEA is improved substantially, particularly at high current densities. Although the platinum loadings of the anode and cathode are as low as 0.04 and 0.12 mg cm⁻² respectively, the current density of the novel DCL MEA still reached 0.73 A cm⁻² at a working voltage of 0.65 V, comparable to that of the SCL MEA. In addition, the maximum power density of the novel DCL MEA reached 0.66 W cm⁻² at 1.3 A cm⁻² and 0.51 V, 11.9% higher than that of the SCL MEA, indicative of improved mass transfer for the novel MEA. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) tests revealed that the novel DCL MEA possesses an efficient electrochemical active layer and good platinum utilization efficiency.     

The dependence of performance degradation of membrane electrode assembly on platinum loading in polymer electrolyte membrane fuel cell

The durability of membrane electrode assemblies (MEAs) with varying amounts of Pt loading on the cathode of polymer electrolyte membrane fuel cells was investigated using load cycling as an accelerated degradation test (ADT). The single-cell performance of the MEA as determined by the ADT declined by approximately 34, 48, and 78%, when cathode Pt loading in the MEA was reduced to 0.3, 0.2, and 0.1 mg cm⁻², respectively. The increase in MEA performance declined at higher cathode Pt loading conditions, and the degradation rate of MEA performance was also diminished. To characterize the electrochemical and structural properties of the MEAs, cyclic voltammograms, electrochemical impedance spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy were utilized before and after ADT.     

Performance optimization of ultra-low platinum loading membrane electrode assembly prepared by electrostatic spraying

To improve the utilization of platinum and reduce the manufacturing cost of proton exchange membrane fuel cell (PEMFC), the electrostatic spraying was used to prepare the cathode catalyst layer of membrane electrode assembly (MEA) with platinum loading varying from 0.1 to 0.01 mg cm^?2. The performance of fuel cell was tested and analyzed by electrochemical impedance and polarization curve. Our results show that the platinum carbon (Pt/C) particles deposited by electrostatic spraying were well dispersed and the microporous structure of catalyst layer (CL) were relatively uniform. Replacing the CCS type MEA (catalyst coated on gas diffusion layer substrate) with the CCM type MEA (catalyst coated on proton exchange membrane) can reduce its electrochemical impedance and improve the power density of fuel cell. Compared to the Pt/C catalyst with a platinum mass fraction of 60%, a lower platinum-carbon ratio catalyst is more conducive to the uniform dispersion of catalyst particles and efficient utilization of platinum in the preparation of MEA with ultra-low platinum loading. However, their difference in peak power density decreases with the increase of platinum loading. Besides, increasing the back pressure can improve the performance of fuel cell, when the back pressure increased to 0.15 Mpa and the feeding gases were set as H₂/O₂, the peak power density of 0.56 W cm^?2 was obtained by the MEA with cathode platinum loading of 0.01 mg cm^?2, which is corresponding to the cathode platinum utilization of 56 kW·g_Pt^?1_cathode.     

Performance of membrane electrode assemblies using PdPt alloy as anode catalysts in polymer electrolyte membrane fuel cell

Pd-based nanoparticles, such as 40 wt.% carbon-supported Pd₅₀Pt₅₀, Pd₇₅Pt₂₅, Pd₉₀Pt₁₀ and Pd₉₅Pt₅, for anode electrocatalyst on polymer electrolyte membrane fuel cells (PEMFCs) were synthesized by the borohydride reduction method. PdPt metal particles with a narrow size distribution were dispersed uniformly on a carbon support. The membrane electrode assembly (MEA) with Pd₉₅Pt₅/C as the anode catalyst exhibited comparable single-cell performance to that of commercial Pt/C at 0.7 V. Although the Pt loading of the anode with Pd₉₅Pt₅/C was as low as 0.02 mg cm⁻², the specific power (power to mass of Pt in the MEA) of Pd₉₅Pt₅/C was higher than that of Pt/C at 0.7 V. Furthermore, the single-cell performance with Pd₅₀Pt₅₀/C and Pd₇₅Pt₂₅/C as the anode catalyst at 0.4 V was approximately 95% that of the MEA with the Pt/C catalyst. This indicated that a Pd-based catalyst that has an extremely small amount of Pt (only 5 or 50 at.%) can be replaced as an anode electrocatalyst in PEMFC.     

Performance enhancement of membrane electrode assemblies with plasma etched polymer electrolyte membrane in PEM fuel cell

In this work, a surface modified Nafion 212 membrane was fabricated by plasma etching in order to enhance the performance of a membrane electrode assembly (MEA) in a polymer electrolyte membrane fuel cell. Single-cell performance of MEA at 0.7 V was increased by about 19% with membrane that was etched for 10 min compared to that with untreated Nafion 212 membrane. The MEA with membrane etched for 20 min exhibited a current density of 1700 mA cm⁻² at 0.35 V, which was 8% higher than that of MEA with untreated membrane (1580 mA cm⁻²). The performances of MEAs containing etched membranes were affected by complex factors such as the thickness and surface morphology of the membrane related to etching time. The structural changes and electrochemical properties of the MEAs with etched membranes were characterized by field emission scanning electron microscopy, Fourier transform-infrared spectrometry, electrochemical impedance spectroscopy, and cyclic voltammetry.     

Effect of platinum amount in carbon supported platinum catalyst on performance of polymer electrolyte membrane fuel cell

The performance of polymer electrolyte membrane fuel cells fabricated with different catalyst loadings (20, 40 and 60 wt.% on a carbon support) was examined. The membrane electrode assembly (MEA) of the catalyst coated membrane (CCM) type was fabricated without a hot-pressing process using a spray coating method with a Pt loading of 0.2 mg cm⁻². The surface was examined using scanning electron microscopy. The catalysts with different loadings were characterized by X-ray diffraction and cyclic voltammetry. The single cell performance with the fabricated MEAs was evaluated and electrochemical impedance spectroscopy was used to characterize the fuel cell. The best performance of 742 mA cm⁻² at a cell voltage of 0.6 V was obtained using 40 wt.% Pt/C in both the anode and cathode.     

Self-humidifying membrane electrode assembly prepared by adding PVA as hygroscopic agent in anode catalyst layer

In this work, a novel self-humidifying membrane electrode assembly (MEA) with addition of polyvinyl alcohol (PVA) as the hygroscopic agent into anode catalyst layer was developed for proton exchange membrane fuel cell (PEMFC). The MEA shows good self humidification performance, for the sample with PVA addition of 5 wt.% (MEA PVA5), the maximum power density can reach up to 623.3 mW·cm⁻², with current densities of 1000 mA·cm⁻² at 0.6 V and 600 mA·cm⁻² at 0.7 V respectively, at 50 °C and 34% of relative humidity (RH). It is interesting that the performance of MEA PVA5 hardly changes even if the relative humidity of both the anode and cathode decreased from 100% to 34%. The MEA PVA5 also shows good stability at low humidity operating conditions: keeping the MEA discharged at constant voltage of 0.6 V for 60 h at 34% of RH, the attenuation of the current density is less than 10%, whilst for the MEA without addition of PVA, the attenuation is high up to 80% within 5 h.     

Low temperature decal transfer method for hydrocarbon membrane based membrane electrode assemblies in polymer electrolyte membrane fuel cells

Decal transfer is an effective membrane electrode assembly (MEA) fabrication method known for its low interfacial resistance and suitability for mass processing. Previously decal transfer for hydrocarbon membranes was performed at temperatures above 200 °C. Here a novel low temperature decal transfer (LTD) method for hydrocarbon membranes is introduced. The new method applies a small amount (2.2 mg cm⁻²) of liquid (1-pentanol) onto the membrane separator before decal transfer to lower the T_g of the membrane and achieves complete decal transfer at 110 °C and 6 MPa. Nafion binder amount in the catalyst layer and catalyst layer annealing temperature is controlled to optimize the fuel cell performance. Compared to conventional decal transfer (CDT), the novel LTD method shows enhancement in energy efficiency, simplicity in the process scheme, and improvement in fuel cell performance.     

Correlation between performance of polymer electrolyte membrane fuel cell and degradation of the carbon support in the membrane electrode assembly using image processing method

Long-time operation and various conditions cause the membrane electrode assembly (MEA) of polymer electrolyte membrane fuel cells (PEMFCs) to degrade, which results in decreased performance. The degradation of the MEA appears as various symptoms, such as the loss of carbon support and agglomeration of the Pt catalyst. In this paper, damage on the surface of the MEA by long-time operation and various conditions is induced intentionally by high-temperature conditions in a thermostat chamber. The MEA surface damage is photographed by scanning electron microscopy (SEM), and the loss of the carbon support that fixes the platinum catalyst is judged. Image processing is used to analyze damage on the MEA surface, and binarization processing is applied to the image processing method. SEM imagery is taken at magnifications of 100 × and the trends in quantified surface damage on the MEA according to the degradation temperature are analyzed. The correlation between the quantitative damage on the MEA surface and the performance of the PEMFC is checked. As a result, the tendency of decreasing PEMFC performance is derived from increasing quantified damage on the MEA surface.     

Study of the influence of Nafion/C composition on electrochemical performance of PEM single cells with ultra-low platinum load

The electrochemical performance of membrane electrode assemblies (MEAs) with ultra-low platinum load (0.02 mg_Pt cm^?2) and different compositions of Nafion/C in the catalytic layer have been investigated. The electrodes were fabricated depositing the catalytic ink, prepared with commercial catalyst (HiSPEC 2000), onto the gas diffusion layers by wet powder spraying. The MEAs were electrochemically tested using current-voltage curves and electrochemical impedance spectroscopy measurements. The experiments were carried out at 70 °C in H₂/O₂ and H₂/air as reactant gases at 1 and 2 bar pressure and 100% of relative humidity. For all MEAs tested, power density increases when the gasses pressure is increased from 1 to 2 bar. On the other hand, power density also increased when oxygen is used instead of air as oxidant gas in cathode. The lower power density (34 mW cm^?2) and power per Pt loading (0.86 kW g_Pt^?1) corresponds to the MEA prepared without Nafion in anode and cathode catalytic layers working with hydrogen and air at 1 bar pressure as reactants gas. The MEA with 30% wt Nafion/C reached the highest power density (422 mW cm^?2) and power per Pt loading (10.60 kW g_Pt^?1) using hydrogen and oxygen at 2 bar pressure. Finally, electrode surface microstructure and cross sections of MEAs were analyzed by Scanning Electron Microscopy (SEM). Examination of the electrodes, revealed that the most uniform ionomer network surface corresponds to the electrode with 40 wt% Nafion/C, and MEA ionomer-free catalytic layer shows delamination, it leads to low electrochemical performance.     

Ultra-low catalyst loading cathode electrode for anion-exchange membrane fuel cells

A new cathode architecture for anion-exchange membrane fuel cells (AEMFCs) is proposed and fabricated by direct deposition of palladium (Pd) particles onto the surface of the micro-porous layer (MPL) that is interfaced with a backing layer. The MPL is composed of carbon nanotubes while the backing layer is made of a carbon paper. The sputter-deposited electrode with a worm-like shape not only extends the electrochemical active surface area, but also facilitates the oxygen transport. This new cathode, albeit with a Pd loading as low as 0.035 mg cm⁻², enables the peak power density of an AEM direct ethanol fuel cell to be as high as 88 mW cm⁻² (at 60 °C), which is even higher than that using a conventional cathode with a 15-times higher Pd loading. The significance of the present work lies in the fact that the new sputter-deposited electrode is more suitable for fuel-electrolyte-fed fuel cells than the conventional electrode designed for proton-exchange membrane fuel cells (PEMFCs).     

Improvement of PEMFC performance with Nafion/inorganic nanocomposite membrane electrode assembly prepared by ultrasonic coating technique

Membrane electrode assemblies with Nafion/nanosize titanium silicon dioxide (TiSiO₄) composite membranes were manufactured with a novel ultrasonic-spray technique and tested in proton exchange membrane fuel cell (PEMFC). Nafion/TiO₂ and Nafion/SiO₂ nanocomposite membranes were also fabricated by the same technique and their characteristics and performances in PEMFC were compared with Nafion/TiSiO₄ mixed oxide membrane. The composite membranes have been characterized by thermogravimetric analysis, scanning electron microscopy, X-ray diffraction, water uptake, and proton conductivity. The composite membranes gained good thermal resistance with insertion of inorganic oxides. Uniform and homogeneous distribution of inorganic oxides enhanced crystalline character of these membranes. Gas diffusion electrodes (GDE) were fabricated by Ultrasonic Coating Technique. Catalyst loading was 0.4 mg Pt/cm² for both anode and cathode sides. Fuel cell performances of Nafion/TiSiO₄ composite membrane were better than that of other membranes. The power density obtained at 0.5 V at 75 °C was 0.456 W cm⁻², 0.547 W cm⁻², 0.477 W cm⁻² and 0.803 W cm⁻² for Nafion, Nafion/TiO₂, Nafion/SiO₂, and Nafion/TiSiO₄ composite membranes, respectively.     

High temperature operation of PEMFC: A novel approach using MEA with silica in catalyst layer

Composite membranes with inorganic substances can retain water and allow the operation of polymer electrolyte membrane fuel cells (PEMFCs) at high temperature under low humidity. In this work, the single cell was operated at high temperature using silica–Nafion composite membrane in addition with silica in catalyst layer. The cell was operated at various temperatures under different relative humidity conditions. We observed that the single cell performance decreased steeply as the cell temperature increased. The role of silica in the catalyst layer at high temperature operation was studied by varying the silica content in the catalyst layers. There was a gradual decrease in cell performance when the silica content increased in catalyst layer. The single cell performance of membrane electrode assemblies (MEAs) with composite membrane and electrode was higher than that of MEA with commercial Nafion 112 membrane for high temperature operation.     

A novel self-humidifying membrane electrode assembly with water transfer region for proton exchange membrane fuel cells

A novel self-humidifying membrane electrode assembly (MEA) with the active electrode region surrounded by a unactive “water transfer region (WTR)” was proposed to achieve effective water management and high performance for proton exchange membrane fuel cells (PEMFCs). By this configuration, excess water in the cathode was transferred to anode through Nafion membrane to humidify hydrogen. Polarization curves and power curves of conventional and the self-humidifying MEAs were compared. The self-humidifying MEA showed power density of 85 mW cm⁻² at 0.5 V, which is two times higher than that of a conventional MEA with cathode open. The effects of anode hydrogen flow rates on the performance of the self-humidifying MEA were investigated and its best performance was obtained at a flow rate of 40 ml min⁻¹. Its performance was the best when the environmental temperature was 40 °C. The performance of the self-humidifying MEA was slightly affected by environmental humidity. The area of WTR was optimized, and feasible area ratio of the self-humidifying MEA was 28%.     

Impact of the patterned membrane morphology on PEMFC performances of ultra-low platinum loaded MEAs

Two types of patterns were achieved on the surface of NR211 membranes: holes and knolls. These patterns were produced on only one side of the membrane at the cathode. For equivalent specific surfaces, these two membrane patterning morphologies were tested in fuel cell conditions with very low platinum loading (30 μg/cm²). Catalyst loading was achieved by magnetron plasma deposition either on the microporous carbon electrode or directly on the patterned membrane. The fuel cell performances in dry conditions were found to be highly dependent on the morphology of the membrane surface. Results showed that the knoll morphology gave better fuel cell performances than the hole morphology. For the knoll morphology the current density increased by a factor of 1.78 at 0.7 V versus a pristine membrane, whereas the hole morphology appeared in some cases to deteriorate the fuel cell performances, despite an increase in the specific surface by a factor of 1.87 versus a pristine membrane. The concepts of top level (extreme surface of the patterned membranes) and bottom level (the pattern base) were introduced to highlight the phenomena of micro water management on the areas of the micro-patterns which act on the local conductivity of the protonic membranes. These results suggest that it is necessary to choose the morphology of the patterns very carefully before simply increasing the specific surface of protonic membranes.     

Enhancement of polymer electrolyte membrane fuel cell performance by boiling a membrane electrode assembly in sulfuric acid solution

A catalyst-coated membrane (CCM) as used in the membrane electrode assembly (MEA) of a polymer electrolyte membrane fuel cell is treated by dilute sulfuric acid solution (0.5 M) at boiling temperature for 1 h. This treatment improves the single-cell performance of the CCM without further addition of Pt catalyst. The changed microstructure and electrochemical properties of the catalyst layer are investigated by field emission scanning electron microscopy with energy dispersive X-ray, mercury intrusion porosimetry, waterdrop contact angle measurement, Fourier transform-infrared spectrometry in attenuated total reflection mode, electrochemical impedance spectroscopy, and cyclic voltammetry. The results indicate that this pretreatment enhances MEA performance by changing the microstructure of the catalyst layer and thus changing the degree of hydration, and by modifying the Pt surface, thus enhancing the oxygen reduction reaction.     

Operation of a proton exchange membrane fuel cell under non-humidified conditions using a membrane–electrode assemblies with composite membrane and electrode

Composite membranes with hydrophilic substances can retain water and allow the operation of proton exchange membrane fuel cells (PEMFCs) under non-humidified conditions. In this work, thin Nafion composite membranes with silica are prepared to operate a PEMFC with dry fuel and oxidant. In addition, the role of silica in the catalyst layer as a water retainer is studied. In particular, the anode and the cathode are modified separately to elucidate the effect of silica. The incorporation of silica in the membrane and the catalyst layer enhances single-cell performance under non-humidified operation. The cell performance of membrane–electrode assemblies using the composite membrane and electrode is higher than that of a MEA using commercial Nafion 111 membrane under non-humidified conditions.     

Demonstration of a 20 W class high-temperature polymer electrolyte fuel cell stack with novel fabrication of a membrane electrode assembly

Acid-doped polybenzimidazole (PBI) membrane and polytetrafluoroethylene (PTFE)-based electrodes are used for the membrane electrode assembly (MEA) in high-temperature polymer electrolyte fuel cells (HTPEFCs). To find the optimum PTFE content for the catalyst layer, the PTFE ratio in the electrodes is varied from 25 to 50 wt%. To improve the performance of the electrodes, PBI is added to the catalyst layer. With a weight ratio of PTFE to Pt/C of 45:55 (45 wt% PTFE in the catalyst layer), the fuel cell shows good performance at 150 °C under non-humidified conditions. When 5 wt% PBI is added to the electrodes, performance is further improved (250 mA cm⁻² at 0.6 V). Our 20 W class HTPEFC stack is fabricated with a novel MEA. This MEA consists of 8 layers (1 phosphoric acid-doped PBI membrane, 2 electrodes, 1 sub-gasket, 2 gas-diffusion media, 2 gas-sealing gaskets). The sub-gasket mitigates the destruction of a highly acid-doped PBI membrane and provides long-term durability to the fuel cell stack. The stack operates for 1200 h without noticeable cell degradation.     

Dissolution and migration of platinum after long-term operation of a polymer electrolyte fuel cell under various conditions

The distribution patterns of Pt crystals that have moved from electrodes to the membrane phase of membrane electrode assembly (MEA) are monitored using transmission electron microscopy (TEM) after long-term operation (>1000 h) of a polymer electrolyte membrane fuel cell (PEMFC) at various operating and feed conditions. The dissolution of cathode Pt and subsequent migration to the membrane is readily observed when residual oxygen concentrations inside the cathode are kept high under low current density conditions. Dissolution of anodic Pt can also be observed under constant-current operation when hydrogen feed is kept low to induce a hydrogen shortage on the Pt surface. It is postulated that the Pt at the both electrodes is dissolved by chemical oxidation to PtO in the presence of residual oxygen. The Pt ions that are dissolved in water migrate to the membrane phase and undergo repeated oxidation/dissolution and reduction/deposition by crossover of oxygen and hydrogen, respectively. As a result, the distribution patterns and crystal sizes of the migrated Pt are strongly dependent on the relative concentrations of the crossover oxygen and hydrogen. The final position of the deposited Pt band is located at the point where crossover oxygen becomes depleted, typically between 1 and 10 μm from the cathode–membrane interface. Higher concentrations of oxygen and hydrogen in the membrane yield sharper and narrower Pt bands with large Pt aggregates, whereas lower concentrations yield wider distribution bands with smaller Pt crystals.