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.     

A Pt content and pore structure gradient distributed catalyst layer to improve the PEMFC performance

The catalyst layer is a key component in the proton exchange membrane fuel cell (PEMFC) for it is where the conversion of fuel into electricity takes place. Traditionally, electrocatalyst is uniformly distributed in the catalyst layers of the membrane electrode assembly (MEA) and the high Pt consumption in catalyst layers blocks the widely use of PEMFC. Here we proposed a Pt content and pore structure gradient distributed, two-layer catalyst layer for PEMFC to improve the MEA performance. Energy-dispersive X-ray (EDX) spectroscopy results show Pt nanoparticles gradient distributed on the vertical direction of catalyst layer. The pore size in the Pt poor layer is larger than that in the Pt rich layer, and this structure can improve the Pt utilization and enhance the mass transfer in the catalyst layer. The single cell test result shows this new MEA has a better performance (11%) than the traditional MEA.     

Investigation of the temperature‐related performance of proton exchange membrane fuel cell stacks in the presence of CO

H₂ is generally used as the fuel in proton exchange membrane fuel cells (PEMFCs). However, H₂ produced from reformate gas usually contains a trace of CO, which may severely affect the fuel cell performance. With the adoption of domestic short side chain, low equivalent weight perfluorosulphonic acid (PFSA) membrane, a 100 W stack is built and evaluated at elevated temperature of 95 °C for the purpose of improving its CO tolerance. The stack is operated with 5 ppm, 10 ppm and 20 ppm CO/H₂, respectively; better performance is obtained as expected. Furthermore, a 5 kW PEMFC stack is prepared with home‐made Ir–V/C and Pt/C as anode catalysts for the membrane electrode assemblies to compare their CO tolerance. Physical and electrochemical characterizations, such as transmission electron microscope and linear scan voltammogram are employed for catalyst investigation. The results demonstrate that the employment of domestic PFSA membrane enables the stack to be operated at 95 °C, which can improve the CO tolerance of all the anode catalysts. In addition, the effect of CO on cell polarization is insignificant at lower current densities. Under the same operating conditions, cells with Ir–V/C catalyst show better CO tolerance. Copyright © 2013 John Wiley & Sons, Ltd.     

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.     

Optimization of RuxSey electrocatalyst loading for oxygen reduction in a PEMFC

The synthesis, characterization and optimization of Ru_xSe_y catalyst loading as a cathode electrode for a single polymer electrolyte membrane fuel cell, PEMFC were investigated. Ru_xSe_y catalyst was synthesized via a decarbonylation of Ru₃(CO)₁₂ and elemental selenium in 1,6-hexanediol under refluxing conditions for 2 h. The powder electrocatalyst was characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and examined for the oxygen reduction reaction (ORR) in 0.5M H₂SO₄ by rotating disk electrode (RDE) and in membrane-electrode assemblies, MEAs for a single PEMFC. Results indicate the formation of agglomerates of crystalline particles with nanometric size embedded in an amorphous phase. The catalyst exhibited high current density and lower overpotential for the ORR compared to that of Ru_x cluster catalyst. Dispersed Ru_xSe_y catalyst loading on Vulcan carbon was optimized as a cathode electrode by performance testing in a single H₂–O₂ fuel cell.     

A novel Rh–Ir electrocatalyst for the oxygen reduction reaction and the hydrogen and methanol oxidation reactions

A novel Rh–Ir based material was synthesized by pyrolysis of an Ir₄(CO)₁₂/Rh₆(CO)₁₆ mixture in a reductive (H₂) atmosphere. The material was characterized by FTIR spectroscopy, X-ray diffraction, energy dispersive spectroscopy and scanning electron microscopy, and was evaluated as electrocatalyst for oxygen reduction and hydrogen and methanol oxidation by rotating disk electrode measurements. The bimetallic material shows a high catalytic activity for the oxygen reduction reaction and is also capable to carry out the hydrogen oxidation reaction even in the presence of carbon monoxide in different concentrations (100 ppm and 0.5%), in contrast with commercial platinum catalysts, which become easily deactivated by CO. The activity of the catalyst for methanol oxidation is acceptable but still low in comparison with Pt–Ru. The results show that the new bimetallic catalyst is a potential candidate to be evaluated as both cathode and anode in a reforming hydrogen PEMFC, and as an anode in a direct methanol fuel cell.     

The effect of internal air bleed on CO poisoning in a proton exchange membrane fuel cell

It is found that carbon monoxide (CO) poisoning could be mitigated by increasing only cathode backpressure for a proton exchange membrane fuel cell (PEMFC) with ultra-thin membranes (≤25 μm). This mitigation can be explained by a heterogeneous oxidation of CO on a Pt-Ru/C anode by the permeated O₂ which is known as “internal air bleed” in his paper. A steady-state model which accounts for this internal air bleed has been developed to model the Pt-Ru/C anode polarization data when 50 ppm CO in H₂ is used as anode feed gas. The modeling results show that the mitigation of CO poisoning by the internal air bleed even exists at ambient conditions for a PEMFC with an ultra-thin membrane. Therefore, the effect of internal air bleed must be considered for modeling fuel cell performance or anode polarization data if an ultra-thin membrane and a low level of CO concentration are used for a Pt-Ru/C anode. An empirical relationship between the amount of internal air bleed used for the mitigation of CO poisoning and the fraction of free Pt sites is provided to facilitate the inclusion of an internal air bleed term in the modeling of anode polarization and the fuel cell performance.     

Analysis of electrocatalyst degradation in PEMFC caused by cell reversal during fuel starvation

The damage caused by cell reversal during proton exchange membrane fuel cell (PEMFC) operation with fuel starvation was investigated by a single cell experiment. The samples from degraded membrane–electrode assemblies (MEAs) were characterized. Chemical analysis of the anode catalyst layer of MEA samples by energy dispersive X-ray analysis (EDX) clearly showed ruthenium dissolution from the anode catalyst particles. Severe ruthenium loss was observed especially in the fuel outlet region. A reduced carbon monoxide (CO) tolerance was found by CO stripping voltammetry and measurement of deteriorated the fuel cell performance. Surface area loss of the cathode platinum by sintering was also detected by transmission electron microscopy (TEM) analysis and cyclic voltammetry.     

Reformate gas composition and pressure effect on CO tolerant Pt/Ti0.8Mo0.2O2–C electrocatalyst for PEM fuel cells

Mixed-oxide coated Ti_0.8Mo_0.2O₂–C composite supported 20 wt% Pt electrocatalysts with Ti_0.8Mo_0.2O₂/C=75/25 mass ratio were developed for CO tolerance of polymer electrolyte membrane fuel cell (PEMFC) anode. Studies of the structure, composition and stability, as well as the results of CO_ads stripping confirmed that the mixed oxide composite support and the electrocatalyst prepared for this study show the well-documented characteristics of the Pt/Ti_1-xMo_xO₂-C systems with enhanced CO tolerance compared to the Pt/C catalyst.Dilution of hydrogen with CO₂ and CH₄ had negligible negative impact on the fuel cell performance. Switching gas composition between hydrogen and reformate shows recovery of potential after CO poisoning. Nevertheless, anode catalyst loading of 0.25 and 0.5 mgPt/cm² was not enough to give reasonable performance when CO impurity was present. Loading of 0.85 mgPt/cm² Ti_0.8Mo_0.2O₂–C supported catalyst was effective to give 1000 mA/cm² current density at 0.6 V under 25 ppm CO and 30 psig. Higher loading was needed at mass transfer limited region to overcome poisoning. However, loadings higher than 0.85 mgPt/cm² caused mass transfer limitations. Hence higher loadings is proposed with 40 wt% Pt/Ti_0.8Mo_0.2O₂–C support catalyst.     

A novel proton exchange membrane fuel cell anode for enhancing CO tolerance

A novel proton exchange membrane fuel cell (PEMFC) anode which can facilitate the CO oxidation by air bleeding and reduce the direct combustion of hydrogen with oxygen within the electrode is described. This novel anode consists of placing Pt or Au particles in the diffusion layer which is called Pt- or Au-refined diffusion layer. Thus, the chemical oxidation of CO occurs at Pt or Au particles before it reaches the electrochemical catalyst layer when trace amount of oxygen is injected into the anode. All membrane electrode assemblies (MEAs) composed of Pt- or Au-refined diffusion layer do perform better than the traditionary MEA when 100 ppm CO/H₂ and 2% air are fed and have the performance as excellent as the traditionary MEA with neat hydrogen. Furthermore, CO tolerance of the MEAs composed of Au-refined diffusion layer was also assessed without oxygen injection. When 100 ppm CO/H₂ is fed, MEAs composed of Au-refined diffusion layer have the slightly better performance than traditionary MEA do because Au particles in the diffusion layer have activity in the water gas shift (WGS) reaction at low temperature.     

A study on composite PtRu(1:1)-PtSn(3:1) anode catalyst for PEMFC

Composite PtRu(1:1)/C-PtSn(3:1)/C catalyst layers with various geometries and loadings were designed for a proton exchange membrane fuel cell (PEMFC) anode to improve carbon monoxide (CO) tolerance of the conventional PtRu(1:1)/C catalyst. The idea was based on an experimental finding that the onset potential of the PtSn for CO oxidation was lower than that of the PtRu and the resultant expectation that there seemed to be a possibility of using the PtSn as a CO filter. The CO tolerance of the composite catalyst of each design was judged by the cell performance obtained through a single cell test using H₂/CO gases of various CO concentrations and compared to that of the PtRu/C catalyst. The highest CO tolerance among the composite catalysts tested in this study was obtained for the one with geometry of double layers in the order of PtRu/C and PtSn/C from the electrolyte layer and with respective PtRu and PtSn loadings of 0.25 and 0.12 mg cm⁻². The cell with this composite catalyst showed better performance than the one with the PtRu/C catalyst. When a H₂/100 ppmCO gas was used as the fuel in the single cell test, the cell voltages were measured to be 0.49 and 0.44 V at a current density of 500 mA cm⁻², respectively for the cell with the composite and PtRu/C catalyst.     

Pt/C catalyst impregnated with tungsten-oxide – Hydrogen oxidation reaction vs. CO tolerance

Hydrogen Oxidation Reaction (HOR) is anode reaction in Proton exchange membrane fuel cells (PEMFCs) and it has very fast kinetics. However, the purity of fuel (H₂) is very important and can slow down HOR kinetics, affecting the overall PEMFC performance. The performance of commercial Pt/C catalyst impregnated with WO_x, as a catalyst for HOR, was investigated using a set of electrochemical methods (cyclic voltammetry, linear scan voltammetry and rotating disk electrode voltammetry). In order to deepen the understanding how WO_x species can contribute CO tolerance of Pt/C, a particular attention was paid to CO poisoning. In the absence of CO, HOR is under diffusion limitations and HOR kinetics is not affected by WO_x species. Appreciable HOR current on the electrodes pre-saturated with CO_ads at potentials above 0.3 V vs. RHE, which is not observed for pure Pt/C, was discussed in details. HOR liming diffusion currents for higher concentrations of W are reached at high anodic potentials. The obtained results were explained by donation of OH_ads by WO_x phase for CO_ads removal in the mid potential region and reduced reactivity of Pt surface sites in the vicinity of the Pt|WO_x interface. The obtained results can provide guidelines for development of novel CO tolerant PEMFC anode catalysts.     

Effect of CO in the anode fuel on the performance of PEM fuel cell cathode

Even trace amounts of CO in the fuel for a proton-exchange membrane fuel cell (PEMFC) could poison not only the anode, which is directly exposed to the fuel, but also the cathode, which is separated from the fuel by a proton-exchange membrane; and the performance decline of the cathode is sometimes more than that of the anode. Adsorption of CO on the cathode catalyst has been detected electrochemically, and this indicates that CO can pass through the membrane to reach the cathode. To reduce such a poisoning effect, fuel cell operation conditions (e.g. level of membrane humidification, gas pressure difference between cathode and anode), membrane and catalyst layer structures, and CO-tolerant cathode catalysts should be further explored.     

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.     

Non-stoichiometric tungsten-carbide-oxide-supported Pt–Ru anode catalysts for PEM fuel cells – From basic electrochemistry to fuel cell performance

Durability and cost of Proton Exchange Membrane fuel cells (PEMFCs) are two major factors delaying their commercialization. Cost is associated with the price of the catalysts, while durability is associated with degradation and poisoning of the catalysts, primarily by CO. This motivated us to develop tungsten-carbide-oxide (W_xC_yO_z) as a new non-carbon based catalyst support for Pt–Ru–based anode PEMFC catalyst. The aim was to improve performance and obtain higher CO tolerance compared to commercial catalysts. The performance of obtained PtRu/W_xC_yO_z catalysts was investigated using cyclic voltammetry, linear scan voltammetry and rotating disk electrode voltammetry. Particular attention was given to the analysis of CO poisoning, to better understand how W_xC_yO_z species can contribute to the CO tolerance of PtRu/W_xC_yO_z. Improved oxidation of CO_ads at low potentials (E < 0.5 V vs. RHE) was ascribed to OH provided by the oxide phase at the interfacial region between the support and the PtRu particles. On the other hand, at high potentials (E > 0.5 V vs. RHE) CO removal proceeds dominantly via OH provided from the oxidized metal sites. The obtained catalyst with the best performance (30% PtRu/W_xC_yO_z) was tested as an anode catalyst in PEM fuel cell. When using synthetic reformate as a fuel in PEMFC, there is a significant power drop of 35.3 % for the commercial 30% PtRu/C catalyst, while for the PtRu/W_xC_yO_z anode catalyst this drop is around 16 %.     

Enhancing the CO tolerance of PEMFC MEAs by combining sputter-deposited and direct-printed composite anode catalyst layers

Two composite electrode structures for proton exchange membrane fuel cells, comprising an outer and an inner catalyst layer, are proposed to improve the CO tolerance and utilization efficiency of the catalyst. These two composite anodes have structures I and II, and are prepared by a combination of direct printing and magnetron sputtering deposition. The only difference between them is the third layer of the outer catalyst layer, which is a layer of deposited _Pt29${\mathrm{Pt}}_{29}$–_Ru71${\mathrm{Ru}}_{71}$ alloy nanoparticles in structure II and a screen-printed _Pt50–_Ru50${\mathrm{Pt}}_{50}–{\mathrm{Ru}}_{50}$ layer in structure I. The loadings of each layer at the anode for these two membrane electrode assemblies (MEAs) are identical. The electrode performance and CO tolerance of the proposed catalyst layer structure are compared to those of the conventional structure. The roles of the outer and inner catalyst layers in improving the CO tolerance and utilization efficiency of the catalyst are studied. The results indicate that the structure II anode catalyst layer outperforms the conventional structure, with a higher utilization efficiency of the catalyst and a similar CO tolerance. The structure I anode catalyst layer has a greater CO tolerance and outperforms the conventional and Huag's structures in 50 ppm CO-containing hydrogen fuels and pure hydrogen fuel. The filtering effect of the outer catalyst layer improves the CO tolerance. The electron probe micro-analysis result reveals that the composite anode has an effective catalyst distribution. This proposed composite MEA is expected to have the advantage of ease of process and is suited for mass production.     

Investigations of a platinum-ruthenium/carbon nanotube catalyst formed by a two-step spontaneous deposition method

Platinum (Pt) is a popular catalyst for hydrogen oxidation on the anode side of solid polymer fuel cells (SPFC). It increases the electrode activity, which catalyzes the reaction of the fuel cell. There are two methods commonly used to produce hydrogen for SPFC: fuel reforming and methanol decomposition. Both of these methods produce carbon monoxide, which is considered to be a poison for SPFC because it deactivates Pt easily. Adding ruthenium (Ru) to a Pt catalyst is an efficient way to improve the inhibition of carbon monoxide (CO) formation and reduce the Pt loading requirement.This study introduces a method to synthesize a bimetal catalyst that is suitable for SPFC. To improve the electrocatalyst activity, a new process with two spontaneous deposition steps is adopted. In the first step, Ru is deposited on the wall of carbon nanotubes (CNTs) to obtain Ru/CNTs. Pt is then added in the second deposition step to form Pt-Ru/CNTs. The morphology and microstructure of catalysts are characterized with microscopes, and the performance of membrane electrode assembly is evaluated by cyclic voltammetry method. Experimental results have proved that even with a lower Pt loading, this home-brewed bimetal catalyst performs a compatible electrocatalytic activity, and is capable of resisting attack from CO when a syngas (H₂ + 20 ppm CO) is provided.     

Overview of the development of CO-tolerant anode electrocatalysts for proton-exchange membrane fuel cells

Poisoning of Pt anode electrocatalysts by carbon monoxide (CO) is deemed to be one of the most significant barriers to be overcome in the development of proton-exchange membrane fuel cell systems (PEMFCs). The use of CO-tolerant electrocatalysts serves as the most hopeful way to solve this problem. It is well established that Pt-based alloy systems of CO-tolerant electrocatalysts can substantially withstand the presence of CO in the fuel stream. Based on literature starting in 2000, a few efforts have still been conducted at developing a more CO-tolerant anode electrocatalyst than the traditional Pt/C or PtRu/C systems. This review introduces and discusses these efforts.Pt-based electrocatalysts, including PtSn/C, PtMo/C (atomic ratio = 5:1), PtRuMo/C (Mo = 10 wt.%), PtRu–H_xMoO₃/C and PtRu/(C nanotubes), appear to be poisoned by CO at the same, or a lower, level than traditional Pt/C or PtRu/C electrocatalysts. Platinum-free electrocatalysts, such as PdAu/C, have proven to be less strongly poisoned by CO than PtRu/C counterparts at temperatures of 60 °C.A greater tolerance to CO can be achieved by modifying the structure of the electrocatalyst. This involves the use of a composite or double-layer that is designed to make the CO react with one of the electrocatalyst in advance while the main hydrogen reacts at another layer with a traditional Pt/C electrocatalyst.     

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.