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.     

Enhanced low-humidity performance of proton exchange membrane fuel cell by incorporating phosphoric acid-loaded covalent organic framework in anode catalyst layer

Developing self-humidifying membrane electrode assembly (MEA) is of great significance for the practical use of proton exchange membrane fuel cell (PEMFC). In this work, a phosphoric acid (PA)-loaded Schiff base networks (SNW)-type covalent organic framework (COF) is proposed as the anode catalyst layer (CL) additive to enhance the PEMFC performance under low humidity conditions. The unique polymer structure and immobilized PA endow the proposed COF network with not only excellent water retention capacity but also proton transfer ability, thus leading to the superior low humidity performance of the PEMFC. The optimization of the additive content, the effect of relative humidity (RH) and PEMFC operating temperature are investigated by means of electrochemical characterization and single cell test. At a normal operation temperature of 60 °C and 38% RH, the MEA with optimized COF content (10 wt%) showes the maximum power density of 582 mW cm^?2, which is almost 7 times higher than that of the routine MEA (85 mW cm^?2). Furthermore, a preliminary durability test demonstrates the potential of the proposed PEMFC for practice operation under low humidity environment.     

Self-humidified operation of a PEM fuel cell using a novel silica composite coating method

A proton exchange membrane fuel cell operating with no external humidification support was successfully reported using a novel silica composite layer on the anode side (Pt/C/SiO₂/Nafion). The nanosilica derived from tetramethoxy silane (TMOS) provided excellent porous morphology to retain water and hydrate protons. This layer provides a well-humidified environment for protons and easy proton transfer from the catalyst surface to the membrane electrolyte. The characteristics of the silica composite layer were investigated by various characterization methods: SEM, XRD, TEM, XPS, EIS, and TGA. A single cell fabricated with the anode containing this new silica composite layer showed a performance of 0.9 W/cm² which is two folds greater when tested with the commercial catalyst MEA (0.45 W/cm²). MEA delivered a constant output power (at 0.6 V) under dry and humidified gas conditions which shows excellent electrochemical stability and durability.     

High Performance plasma sputtered PdPt fuel cell electrodes with ultra low loading

A PdPt (10 wt% Pt) catalyst is used to replace platinum at the cathode of a proton exchange membrane fuel cell membrane electrode assembly (PEMFC MEA) whereas pure palladium is used as the anode catalyst. The catalysts are deposited on commercial carbon woven web and carbon paper GDLs by plasma sputtering. The relations between the depth density profiles, the electrode support and the fuel cell performances are discussed. It is shown that the catalyst gradient is an important parameter which can be controlled by the catalyst depth density profile and/or the choice of electrode support. An optimised electrode structure has been obtained, which allows limiting the platinum requirement. Under suitable conditions of a working PEMFC (80 °C and 3 bar absolute pressure), very high catalysts utilization is obtained at both electrodes, leading to 250 kW g_Pt⁻¹ and 12.5 kW g_Pd⁻¹ with a monocell fitted with a PdPt (10:1 weight ratio) cathode and a pure Pd anode.     

Ir-Pt/C composite with high metal loading as a high-performance anti-reversal anode catalyst for proton exchange membrane fuel cells

Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO₂) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm² when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm². Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.     

Experimental investigation on dynamic characteristics of proton exchange membrane fuel cells at subzero temperatures

Cold start and operation of a proton exchange membrane fuel cell (PEMFC) at the cold temperatures are crucial to the commercialization of it in the field of transportation. A 32 cm² two cell stack is prepared to conduct the experiments at subzero temperatures, including cold start processes and cell performance testing, aiming of the characteristics of the cell. The startup study under subfreezing temperatures is conducted by galvanostatic method at various operation conditions, i.e. ambient temperature (−3 and −5 °C), current density and anode stoichiometry. The results show that the voltage evolutions are proportional to the operating current densities under the former two conditions, but the relationship becomes the opposite at the last condition. It is also found that the time constant for the cell to reach steady status is no more than 100 s and highly depends on the startup mode. In addition, the performance of the cell is tested at the temperature of 0 °C and −3 °C. The comparison of pre-humidification and normal operations indicate that the initial water content of membrane affects the cell performance.     

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.     

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.     

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.     

Effects of reverse voltage and subzero startup on the membrane electrode assembly of a PEMFC

Effects of reverse voltage and frozen fuel cell startup on the membrane electrode assembly (MEA) were investigated for a proton exchange membrane fuel cell (PEMFC). A single cell was started from a subzero temperature by applying reverse voltage. The voltages applied to the cell were 0.8 and 1.2 V. The fuel cell performance was measured with a polarization curve and by cyclic voltammetry (CV), electrochemical impedance spectra (EIS), linear scan voltammetry (LSV) after each experiment. From the results, it was concluded that the catalyst activity, electrochemical active surface area (ECA) and the membrane were not damaged by the reverse voltage if the voltage was below 0.85 V. In contrast, a reverse voltage improved cell performance slightly. If the reverse voltage was larger than 0.85 V, the cell performance degraded. Another single cell with an active area of 128 cm² was started up at −15 °C by applying reverse voltage. The cell performance and MEA physical characteristic were tested before and after the freeze startup. From the results, the cell performance decayed MEA delamination was observed and the pore size distribution of the MEA changed.     

Sulfonated poly(ether sulfone) for universal polymer electrolyte fuel cell operations

The performances of the proton exchange membrane fuel cell (PEMFC), direct formic acid fuel cell (DFAFC) and direct methanol fuel cell (DMFC) with sulfonated poly(ether sulfone) membrane are reported. Pt/C was coated on the membrane directly to fabricate a MEA for PEMFC operation. A single cell test was carried out using H₂/air as the fuel and oxidant. A current density of 730 mA cm⁻² at 0.60 V was obtained at 70 °C. Pt–Ru (anode) and Pt (cathode) were coated on the membrane for DMFC operations. It produced 83 mW cm⁻² maximum power density. The sulfonated poly(ether sulfone) membrane was also used for DFAFC operation under several different conditions. It showed good cell performances for several different kinds of polymer electrolyte fuel cell applications.     

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.     

Improving cell performance and alleviating performance degradation by constructing a novel structure of membrane electrode assembly (MEA) of DMFCs

The conventional electrodes of direct methanol fuel cells (DMFCs) usually encounter a problem that the catalysts sink into the diffusion layer after a period of operation, causing a lowered catalyst utilization and degraded cell performance. Aiming to alleviate this problem, in this work a novel anode electrode structure is proposed, in which a microporous layer containing Nafion polymer is added between the catalyst layer and the microporous layer with PTFE. The presence of the Nafion-contained layer can expand the three-phase interface region of the electrochemical reactions and improve the utilization of the catalyst. The single cell test showed that the peak power densities of the novel membrane electrode assembly (MEA) fed with 0.5 M and 2 M methanol solutions reached 38.35 mW cm⁻² and 101.82 mW cm⁻², which increased by 100.42% and 15.27% compared with those of conventional single microporous layer. Electrochemical impedance spectroscopy (EIS) measurements indicated the charge transfer resistance of the conventional MEA structure was increased by 303.78%, while the new one was decreased by 47.91% after continuously operating for 48 h. The anode electrochemical active surface area (ECSA) values of the novel MEA and the conventional MEA were 52.6 m² g^-1 and 44.3 m² g^-1. These experimental results showed that the performance of the double microporous layer MEA was higher than that of the conventional MEA. This new microporous layer structure is promising to be used in fuel cells to improve cell performance and alleviate performance degradation after long-term operating.     

CO tolerance of nano-architectured Pt–Mo anode electrocatalysts for PEM fuel cells

PEM fuel cell membrane electrode assemblies with Nafion electrolytes and commercial Pt-based cathodes were tested with Pt_0.8Mo_0.2 alloy and MoO_x@Pt core–shell anode electrocatalysts for CO tolerance and short-term stability to corroborate earlier thin-film RDE results. Polarization curves at 70 °C for the Pt_0.8Mo_0.2 alloy in H₂ with 25–1000 ppm CO showed a significant increase in CO tolerance based on peak power densities in comparison to PtRu electrocatalysts. MoO_x@Pt core–shell electrocatalysts, which showed extremely high activity for H₂ in 1000 ppm CO during RDE studies, performed relatively poorly in comparison to the Pt_0.8Mo_0.2 and PtRu alloys for the same total catalyst loading on a per area basis in MEA testing. The discrepancy is attributed to residual stabilizer from the core–shell synthesis impacting catalyst-ionomer interfaces. Nonetheless, the MoO_x@Pt electrochemical performance is superior on a per-gram-of-precious-metal basis to the Pt_0.8Mo_0.2 electrocatalyst for CO concentrations below 100 ppm. Due to cross-membrane Mo migration, the stability of the Mo-containing anode electrocatalysts remains a challenge for developing stable enhanced CO tolerance for low-temperature PEM fuel cells.     

Membrane electrode assemblies with low noble metal loadings for hydrogen production from solid polymer electrolyte water electrolysis

High performance membrane electrode assemblies (MEAs) with low noble metal loadings (NMLs) were developed for solid polymer electrolyte (SPE) water electrolysis. The electrochemical and physical characterization of the MEAs was performed by I–V curves, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). Even though the total NML was lowered to 0.38 mg cm⁻², it still reached a high performance of 1.633 V at 2 A cm⁻² and 80 °C, with IrO₂ as anode catalyst. The influences of the ionomer content in the anode catalyst layer (CL) and the cell temperature were investigated with the purpose of optimizing the performance. SEM and EIS measurements revealed that the MEA with low NML has very thin porous cathode and anode CLs that get intimate contact with the electrolyte membrane, which makes a reduced mass transport limitation and lower ohmic resistance of the MEA. A short-term water electrolysis operation at 1 A cm⁻² showed that the MEA has good stability: the cell voltage maintained at ∼1.60 V without distinct degradation after 122 h operation at 80 °C and atmospheric pressure.     

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.     

Electrochemical oxidation of catalytic grown carbon fiber in a direct carbon fuel cell using Ce0.8Sm0.2O1.9-carbonate electrolyte

The electrochemical oxidation of catalytic grown carbon fiber has been examined in a direct carbon fuel cell (DCFC). The single cell contains a composite electrolyte layer made of a samarium doped ceria (SDC) and a eutectic carbonate phase. The cathode is a mixture of lithiated NiO and the composite electrolyte, while the anode is composed of NiO and SDC powder. Catalytic carbon fiber and the eutectic carbonate is premixed and used as the feed of the anode fuel. The effects of the cell pellet configuration, cathode gas composition and the operation temperature on the DCFC performance have been examined in this work. At 700 °C, the maximum power output achieves 112 mW cm⁻² with a current density of 249 mA cm⁻². The anode off-gas is analyzed with a gas chromatograph, and the Boudouard reaction is found suppressed by the electrical field in the fuel cell operation.     

Enhancement of proton exchange membrane fuel cell performance by titanium-coated anode gas diffusion layer

Titanium was coated onto an anode gas diffusion layer (GDL) by direct current sputtering to improve the performance and durability of a proton exchange membrane fuel cell (PEMFC). Scanning electron microscopy (SEM) images showed that the GDLs were thoroughly coated with titanium, which showed angular protrusion. Single-cell performance of the PEMFCs with titanium-coated GDLs as anodes was investigated at operating temperatures of 25 °C, 45 °C, and 65 °C. Cell performances of all membrane electrode assemblies (MEAs) with titanium-coated GDLs were superior to that of the MEA without titanium coating. The MEA with titanium-coated GDL, with 10 min sputtering time, demonstrated the best performance at 25 °C, 45 °C, and 65 °C with corresponding power densities 58.26%, 32.10%, and 37.45% higher than that of MEA without titanium coating.     

Highly efficient,cell reversal resistant PEMFC based on PtNi/C octahedral and OER composite catalyst

In order to obtain a fuel cell with both enhanced power generation performance and cell reversal resistance, the composite catalyst consisting of the self-made PtNi/C octahedral and the oxygen evolution reaction (OER) catalyst IrO₂ and RuO₂ is mixed and applied in the anode, and the only octahedral catalyst is employed as the cathode to prepare the membrane electrode assembly (MEA). The electrochemical activity of the composite catalyst decreases slightly, but its performance retention after the accelerated durability test (ADT) is higher. In the single cell test, the MEA fabricated using the composite catalyst maintains good single cell power generation performance. Compared with the control fabricated with Pt/C (JM), the cell voltage at 1 A cm⁻² and the maximum power density are increased by 23 mV and 119 mW cm⁻², respectively. Especially, its durability under continuous cell reversal condition is also improved significantly, and the holding time is prolonged by 1 h. This work realizes the transformation of the octahedral catalyst from the laboratory research to the actual application, and solves the difficulties in fuel cell application, and promotes its commercialization.     

Impact of anode catalyst loadings and carbon supports to CO contamination in PEM fuel cells

Hydrogen fuel quality is important for the successful commercialization of PEM (proton exchange membrane) fuel cell vehicles (FCVs) because impurities can adversely affect the normal operation of FCVs both immediately and during their lifetime operation. Among the impurities specified in H₂ quality standards, CO (carbon monoxide) is known to have one of the greatest impacts on fuel cells because of the immediate decrease in performance at low concentrations. CO impurity levels of only 0.2 ppm, as specified in the H₂ quality standards, were found in H₂ refueling stations with adverse impacts to PEM fuel cell operation. In this study CO impurity testing was conducted on single cells based on an extensive design of experiments (DOE) that was performed using several MEAs with two levels of anode platinum loading (0.05 mg_Pt/cm² and 0.1 mg_Pt/cm²) and two different materials for platinum carbon support (Highly Graphitized Carbon and High Surface Area Carbon). Contamination testing for each MEA design configuration was performed at four different CO impurity levels (0.1 ppm, 0.2 ppm, 0.3 ppm, and 0.4 ppm) and three current densities (0.1 A/cm², 1.0 A/cm², and 1.7 A/cm²) at each impurity level. The results indicate that the most significant factor to improve MEA tolerance to CO contamination was the choice of carbon support. The use of high surface area carbon had an even greater impact than the use of higher Pt loading, which suggests paths toward addressing CO contamination that avoid higher catalyst cost.