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.     

Self-humidification of a PEM fuel cell using a novel Pt/SiO2/C anode catalyst

In this work, a membrane electrode assembly (MEA) for proton exchange membrane fuel cell (PEMFC) operating under no external humidification has been successfully fabricated by using a composite Pt/SiO₂/C catalyst at the anode. In the composite catalyst, amorphous silica, which originated from the hydrolysis of tetraethyl orthosilicate (TEOS), was immobilized on the surface of carbon powder to enhance the stability of silica and provide a well-humidified surrounding for proton transport in the catalyst layer. The characteristics of silica in the composite catalyst were investigated by XRD, SEM and XPS analysis. The single cell tests showed that the performance of the novel MEA was comparable to MEAs prepared using a standard commercial Pt/C catalyst with 100% external humidification, when both were operated on hydrogen and air. However, in the absence of humidification, the MEA using Pt/SiO₂/C catalyst at the anode continued to show excellent performance, while the performance of the MEA containing only the Pt/C catalyst rapidly decayed. Long-term testing for 80 h further confirmed the high performance of the non-humidified MEA prepared with the composite catalyst. Based on the experimental data, a possible self-humidifying mechanism was proposed.     

Non-platinum cathode catalyst layer composition for single Membrane Electrode Assembly Proton Exchange Membrane Fuel Cell

The performance of nano-structured templated non-platinum-based cathode electrocatalysts for proton exchange membrane fuel cells (PEMFC) was evaluated for different catalyst layer compositions. The effect of non-platinum catalyst, Nafion, and 35 wt% Teflon modified Vulcan XC-72 Carbon Blacks (XC-35) loadings were measured under H₂/air and H₂/O₂ conditions. Transport hindrances that occur in the catalyst layers are evaluated with ΔE vs. i analysis. It is shown that transport limitations in the cathode catalyst layer can limit the performance of the cell at relatively low current densities if the catalyst layer composition is not optimized. Further, a procedure is outlined here to aid in the implementation of non-traditional catalyst materials into fuel cell systems (i.e. templated electrocatalyst as compared to the standard supported material).     

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.     

Performance of a PEM electrolyzer using RuIrCoOx electrocatalysts for the oxygen evolution electrode

The Proton Exchange Membrane Water Electrolyzer (PEMWE) can be coupled to renewable energy sources (solar radiation and wave energy), which produce the necessary electricity for splitting the water. In this work the performance of a PEMWE using RuIrCoO_x as anodic electrocatalyst had been examined. The oxide powder was synthesized using a chemical reduction method, followed by thermal oxidation. The electrochemical properties of the electrocatalysts were examined by cyclical and lineal voltammetry in 0.5 M H₂SO₄. It was found that RuIrCoO_x oxide electrodes present a stable performance for OER. The PEMWE was designed and in-home built. Chrono-potentiometric experiments were recorded in the current range of 0.25 mA cm⁻² to 75 mA cm⁻² at 300 s. The current pulses length is chosen to be sufficiently long so that the voltage remains constant. Their intrinsic electrocatalytic activity in combination with their large surface area and stability are quite promising for the development of economically feasible electrocatalysts for (PEMWE).     

One-pot synthesis of Pt/CeO2/C catalyst for improving the ORR activity and durability of PEMFC

Oxygen reduction reaction (ORR) activity and durability of Pt catalysts should be both valued for successful commercialization of proton exchange membrane fuel cells (PEMFCs). We offer a facile one-pot synthesis method to prepare Pt/CeO₂/C composite catalysts. CeO₂ nanoparticles, with high Ce³⁺ concentration ranging from 30.9% to 50.6%, offers the very defective surface where Pt nanoparticles preferentially nuclear and growth. The Pt nanoparticles are observed sitting on the CeO₂ surface, increasing the PtCeO₂ interface. The high concentration of oxygen vacancies on CeO₂ surface and large PtCeO₂ interface lead to the strong PtCeO₂ interaction, effectively improving the ORR activity and durability. The mass activity is increased by up to 50%, from 36.44 mA mg^?1 of Pt/C to 52.09 mA mg^?1 of Pt/CeO₂/C containing 20 wt.% CeO₂. Pt/CeO₂/C composite catalysts containing 10–30 wt.% CeO₂ loss about 80% electrochemical surface area after 10,000 cycles, which is a fivefold enhancement in durability, compared to Pt/C losing 79% electrochemical surface area after 2000 cycles.     

Development of efficient membrane electrode assembly for low cost hydrogen production by anion exchange membrane electrolysis

Electrochemical production of hydrogen from water using anion exchange membranes (AEMs) can be achieved with non-noble catalysts, other than traditional proton exchange membranes that use platinum group metals. Using non-noble metals in the catalyst layer will reduce the capital costs associated with water electrolysis systems. The objectives of this study were to develop an effective membrane electrode assembly (MEA) for AEM electrolysis and to determine the effects of various operating parameters on AEM electrolysis. Here, the MEA consisted of the commercially available A-201 AEM and non-noble transition metal oxides as catalysts. The best electrolysis performance recorded was 500 mA cm^?2 for 1.95 V at 60 °C with 1% K₂CO₃ electrolyte. For the purpose of comparison, we also considered commercially available AEMs for AEM electrolysis: Fumapem^® FAA-3 and Fumapem^® FAA-3-PP-75. The performances achieved with these AEMs were comparable with the performance recorded for the conventional AEM A-201. Overall, our results indicated that AEM electrolysis clearly manifests the feasibility of commercial viability.     

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.     

Polyol synthesis of reduced graphene oxide supported platinum electrocatalysts for fuel cells: Effect of Pt precursor,support oxidation level and pH

In this work, a comprehensive study on the polyol synthesis of platinum supported on reduced graphene oxide (Pt/rGO) catalysts, including both ex-situ and in-situ characterizations of the prepared Pt/rGO catalysts, was performed. The polyol synthesis was studied considering the influence of the platinum precursor, oxidation level of graphite oxide and pH of reaction medium. The as-prepared catalysts were analyzed using thermo-gravimetric (TG) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and cyclic voltammetry (CV). The best results in terms of platinum particle size and distribution were obtained when the synthesis was performed in acidic medium, using chloroplatinic acid as precursor and using graphene oxide with high oxidation level. The most promising graphene-supported catalyst was used to prepare a polymer electrolyte membrane fuel cell electrode. The membrane electrode assembly (MEA) prepared with graphene-based electrode was compared with a MEA prepared with catalyst based on commercial platinum supported in carbon black (Pt/C). Single cell characterization included polarization curves and in-situ electrochemical impedance spectroscopy (EIS). The graphene-based electrode presented promising albeit unstable electrochemical performance due to water management issues. Additionally, EIS measurements revealed that the MEA made with Pt/rGO catalyst presented a lower mass transport resistance than the commercial Pt/C.     

RRDE study on Co@Pt/C core–shell nanocatalysts for the oxygen reduction reaction

Kinetics study of the oxygen reduction reaction (ORR) taking place on carbon supported Co@Pt/C core–shell nanocatalysts, were characterized by using the rotating ring-disc electrode (RRDE) technique and results compared to that of Pt/C (Etek). The supported catalyst was successfully synthesized through a simple procedure through sequential colloidal chemical reduction of Co and a galvanic replacement by Pt. X-ray diffraction results of the Co@Pt/C nanoparticles showed important structural changes which can be responsible for the observed enhanced catalytic activity. XRD Rietveld refinement confirmed the presence of metallic Pt and Co in the relative weight fraction of 12 wt% and 88 wt% respectively, as well as a Pt lattice contraction (i.e. 3.8741 Å) and Co lattice expansion (i.e. 3.6170 Å). Electrochemical results support the formation of a core–shell structure with double enhanced ORR activity and similar peroxide generation of the Co@Pt/C catalyst with respect to Pt/C (Etek).     

Effect of catalyst layer with zeolite on the performance of a proton exchange membrane fuel cell operated under low-humidity conditions

Proton exchange membrane fuel cells (PEMFCs) employ a proton conductive membrane as the separator to transport a hydrogen proton from the anode to the cathode. The membrane's proton conductivity depends on the water content in the membrane, which is affected by the operating conditions. A membrane electrode assembly (MEA) that can self-sustain water is the key component for developing a light-weight and compact PEMFC system without humidifiers. Hence, zeolite is employed to the anode catalyst layer in this study. The effect of the gas diffusion layer (GDL) materials, catalyst loading, binder loading, and zeolite loading on the MEA performance is investigated. The MEA durability is also investigated through the electrochemical impedance spectroscopy (EIS) method. The results suggest that the MEA with the SGL28BCE carbon paper, Pt loadings of 0.1 and 0.7 mg cm^?2 in the anode and cathode, respectively, Nafion-to-carbon weight ratio of 0.5, and zeolite-to-carbon weight ratio of 0.3 showed the best performance when the cell temperature is 60 °C and supplies with dry hydrogen and air from the environment. According to the impedance variation measured by EIS, the MEA with zeolite in the anode catalyst layer shows higher and more stable performance than those without zeolite.     

Investigation of membrane electrode assembly (MEA) hot-pressing parameters for proton exchange membrane fuel cell

The hot-pressing conditions for fabricating the membrane electrode assembly (MEA) of a proton exchange membrane fuel cell (PEMFC) was investigated by using a 2ⁿ full factorial design. Time, temperature and pressure were key parameters that were varied from 500 to 1500 psi, 1 to 5 min and 100 to 160 °C, respectively. The results from the full factorial analysis indicated that the order of significance of the main MEA fabricating effects was temperature, pressure, time–temperature interaction and pressure–time–temperature interaction. By examining the cell performance curves, the lower fabrication conditions of temperature and pressure were suitable for MEA preparation. The conductive layer between the membrane and the catalyst layer became thin at high pressure and high temperature, as seen from scanning electron microscopy (SEM) images. In the ranges of condition studied, the most suitable hot-pressing condition for MEA fabrication was at 100 °C, 1000 psi and 2 min. This condition provided the highest maximum power density from the MEA and the best contact at the interfaces between the gas diffusion layer, the active layer and the electrolyte membrane. The experimental results were verified by testing with a commercial MEA in the same operating condition and with the same equipment. The performance of the fabricated MEA was better than that of the commercial one.     

Performance of carbon-supported PtPd as catalyst for hydrogen oxidation in the anodes of proton exchange membrane fuel cells

In this work, the replacement of platinum by palladium in carbon-supported catalysts as anodes for hydrogen oxidation reaction (HOR), in proton exchange membrane fuel cells (PEMFCs), has been studied. Anodes with carbon-supported Pt, Pd, and equiatomic Pt:Pd, with various Nafion^® contents, were prepared and tested in H₂|O₂ (air) PEMFCs fed with pure or CO-contaminated hydrogen. An electrochemical study of the prepared anodes has been carried out in situ, in membrane electrode assemblies, by cyclic voltammetry and CO electrooxidation voltammetry. The analyses of the corresponding voltammograms indicate that the anode composition influences the cell performance. Single cell experiments have shown that platinum could be replaced, at least partially, saving cost with still good performance, by palladium in the hydrogen diffusion anodes of PEMFCs. The performance of the PtPd catalyst fed with CO-contaminated H₂ used in this work is comparable to Pt, thus justifying further work varying the CO concentration in the H₂ fuel to assert its CO tolerance and to study the effect of the Pt:Pd atomic ratio.     

Influence of ink preparation with the untreated and the burned Pt/C catalysts for proton exchange membrane fuel cells

This research discovers the burning reaction of the Pt/C catalyst on ink preparation and the effect of the untreated and burned Pt/C catalysts for the proton exchange membrane fuel cells (PEMFCs). The platinum nanoparticles on the carbon support aggregate to form bigger cluster sizes due to the burning reaction of the untreated Pt/C catalyst reacting with the Nafion solution or isopropyl alcohol. After several times of “purposely” burning reaction, the specific surface area of the fully burned Pt/C reduces from 150.9 to 46.6 m² g⁻¹ which is 3 times smaller than the untreated Pt/C catalyst. The crystallite size of platinum catalyst changes from 8.4 to 46.2 nm via the calculation of Debye–Scherrer equation from X-ray diffraction (XRD) and the electrochemical surface area (ECSA) obviously decreases from 85.6 to 14.8 m² g⁻¹. The variation of the ratio of Pt/C to Nafion influences the consequent electrochemical performances. Three catalyst coated membranes (CCMs) coated with untreated, fully burned, and partial burned Pt/C catalysts are analyzed and compared in this study. The CCM coated with the untreated Pt/C catalyst shows the best polarization curve which presents the peak power density, 897 mW cm⁻². Moreover, it presents the slowest degradation rate (0.1 mA min⁻¹) at a constant voltage of 0.4 V for 4000 min, even though the result of Nyquist plots is slightly worse than others The work confirms that the burning reaction of Pt/C catalyst influences the electrochemical performance and structural balance of the catalyst layer.     

Maximization of high-temperature proton exchange membrane fuel cell performance with the optimum distribution of phosphoric acid

A proton exchange membrane fuel cell (PEMFC) using a controlled amount of phosphoric acid (PA) in a membrane-electrode assembly (MEA) is operated at 150 °C without humidification of the cells. The effects on MEA performance of Pt loading and the amount of PA in the cathode are investigated. The catalyst utilization is maximized by optimizing the PA content in the cathodes and results in lowering of the Pt loading in the MEA. In-situ cyclic voltammetry is used to confirm that the highest value of the active electrochemical area is achieved with the optimum amount of PA in the cathode. The transient response of cell voltage during current density–voltage experiments (I–V curve) is also found to be affected by the amount of PA in the electrodes.     

The effect of materials on proton exchange membrane fuel cell electrode performance

This paper describes the optimisation in the fabrication materials and techniques used in proton exchange membrane fuel cell (PEMFC) electrodes. The effect on the performance of membrane electrode assemblies (MEAs) from the solvents used in producing catalyst inks is reported. Comparison in MEA performances between various gas diffusion layers (GDLs) and the importance of microporous layers (MPLs) in gas diffusion electrodes (GDEs) are also shown. It was found that the best performances were achieved for GDEs using tetrahydrofuran (THF) as the solvent in the catalyst ink formulation and Sigracet 10BC as the GDL. The results also showed that our in-house painted GDEs were comparable to commercial ones (using Johnson Matthey HiSpec™ and E-TEK catalysts).     

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%.