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.     

A novel bifunctional electrocatalyst for unitized regenerative fuel cell

5 wt.% of platinum (Pt) nanoparticles are highly dispersed on the surface of IrO₂ by chemical reduction, and the catalyst is mixed with Pt black to be used as a novel bifunctional oxygen electrocatalyst for the unitized regenerative fuel cell (URFC). The novel cell has been evaluated in the hydrogen and oxygen fuel cell and water electrolysis modes, and compared to a similar cell with an oxygen electrode using conventional mixed Pt black and IrO₂ catalyst. With the novel oxygen electrode catalyst, the highest fuel cell power density is 1160 mW cm⁻² at 2600 mA cm⁻²; the overall performance is close to that with the commercial Pt supported on carbon catalyst and about 1.8 times higher than that with the conventional mixed Pt black and IrO₂ catalyst. Additionally, the cell performance for water electrolysis is also slightly improved, which is probably the result of lower interparticle catalyst resistance with 5 wt.% Pt on IrO₂ compared to no Pt on IrO₂.     

Thickness effects of anode catalyst layer on reversal tolerant performance in proton exchange membrane fuel cell

Real-world driving conditions will likely cause hydrogen starvation at the anode chambers of stacks to trigger voltage reversal events, posing a tremendous challenge to the durability of proton exchange membrane fuel cells (PEMFCs). The reversal-tolerant anode (RTA), a material-based solution, that inclusion of oxygen evolution reaction (OER) catalyst into the anode is usually employed to cope with the voltage reversal issue. In this work, we investigate the impact of anode catalyst layer thickness on the voltage reversal performance of the membrane-electrode assemblies (MEAs) with conventional anodes (Pt/C catalyst) and RTAs doped with IrO₂ catalyst, a representative OER catalyst. We find that regardless of how thick the anode catalyst layer is, the conventional MEAs exhibit almost similar voltage reversal behaviors and times, only about 1 min to reach the shutdown voltage (?2.5 V). As for the RTA MEAs, a surprising thickness effect that the thinner RTA with the same IrO₂ loading shows superior voltage reversal tolerance. Notably, an ultra-thin RTA (~2 μm) exhibits the reversal tolerance time of 310 min, which is five times higher reversal tolerance time than most of the reported RTAs. We conclude that this thickness effect mainly results from the ionomer distribution on the OER catalyst. Besides, we observe that the RTA with a higher ionomer content shows the better reversal tolerance performance. Our work highlights the importance of the OER Triple-Phase-Boundary (TPB) and the need for improved electrode designs for robust RTAs.     

Effect of anode iridium oxide content on the electrochemical performance and resistance to cell reversal potential of polymer electrolyte membrane fuel cells

An ideal polymer electrolyte membrane fuel cell (PEMFC) is one that continuously generates electricity as long as hydrogen and oxygen (or air) are supplied to its anode and cathode, respectively. However, internal and/or external conditions could bring about the degradation of its electrodes, which are composed of nanoparticle catalysts. Particularly, when the hydrogen supply to the anode is disrupted, a reverse voltage is generated. This phenomenon, which seriously degrades the anode catalyst, is referred to as cell reversal. To prevent its occurrence, iridium oxide (IrO₂) particles were added to the anode in the membrane-electrode assembly of the PEMFC single-cells. After 100 cell reversal cycles, the single-cell voltage profiles of the anode with Pt/C only and the anodes with Pt/C and various IrO₂ contents were obtained. Additionally, the cell reversal-induced degradation phenomenon was also confirmed electrochemically and physically, and the use of anodes with various IrO₂ contents was also discussed.     

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.     

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.     

The inhibition of electrochemical carbon corrosion in polymer electrolyte membrane fuel cells using iridium nanodendrites

The addition of Ir-based water electrolysis catalysts to the catalyst layer in polymer electrolyte membrane fuel cells was examined as a promising approach for preventing electrochemical carbon corrosion under severely corrosive conditions. Electrochemical carbon corrosion of membrane electrode assemblies containing different amounts of IrO₂ or shape-controlled Ir dendrite catalysts were characterized using on-line mass spectrometry. In particular, Ir dendrite catalysts possess high activity toward oxygen evolution reactions when compared to IrO₂. As a result, Ir dendrites provided a very effective method of removing water from the catalyst layer. Therefore, the addition of 1 wt% Ir dendrite (0.008 mg cm⁻²) to the catalyst layer of the cathode decreased electrochemical carbon corrosion by 84% at 1.6 V_NHE compared with a conventional membrane electrode assembly in the absence of water electrolysis catalysts.     

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.     

Effects of Pt loading in the anode on the durability of a membrane–electrode assembly for polymer electrolyte membrane fuel cells during startup/shutdown cycling

A polymer electrolyte membrane fuel cell (PEMFC) stack of a fuel cell vehicle (FCV) is inevitably exposed to reverse current conditions, which are formed by the oxygen reduction reaction (ORR) induced at the anode with a hydrogen/air boundary during startup/shutdown processes. With an increase in the reverse current, the degradation rate of the cathode that experiences a highly corrosive condition (locally high potential) increases. In this work, the anode Pt loading is decreased from 0.4 to 0.1 mg cm⁻² to decrease the reverse current. The decrease in the anode Pt loading is found to decrease the hydrogen oxidation rates (HOR) during normal operation, but this loading decrease barely affected the cell performance. However, a decrease in the anode Pt loading can significantly decrease the reverse current, leading to a diminished cathode degradation rate during startup/shutdown cycling. It is revealed by slow decreases in the cell performance (i–V curves) and electrochemical active surface area (EAS), and a slow increase in the charge-transfer resistance (R_ct), which can be attributed to corrosion of the carbon support and dissolution/migration/agglomeration of the platinum catalyst.     

Study of the cell reversal process of large area proton exchange membrane fuel cells under fuel starvation

In this research, the fuel starvation phenomena in a single proton exchange membrane fuel cell (PEMFC) are investigated experimentally. The response characteristics of a single cell under the different degrees of fuel starvation are explored. The key parameters (cell voltage, current distribution, cathode and anode potentials, and local interfacial potentials between anode and membrane, etc.) are measured in situ with a specially constructed segmented fuel cell. Experimental results show that during the cell reversal process due to the fuel starvation, the current distribution is extremely uneven, the local high interfacial potential is suffered near the anode outlet, hydrogen and water are oxidized simultaneously in the different regions at the anode, and the carbon corrosion is proved to occur at the anode by analyzing the anode exhaust gas. When the fuel starvation becomes severer, the water electrolysis current gets larger, the local interfacial potential turns higher, and the carbon corrosion near the anode outlet gets more significant. The local interfacial potential near the anode outlet increases from ca. 1.8 to 2.6 V when the hydrogen stoichiometry decreases from 0.91 to 0.55. The producing rate of the carbon dioxide also increases from 18 to 20 ml min⁻¹.     

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 direct methanol fuel cell using carbon nanotube-supported Pt–Ru anode catalyst with controlled composition

The performance of a single-cell direct methanol fuel cell (DMFC) using carbon nanotube-supported Pt–Ru (Pt–Ru/CNT) as an anode catalyst has been investigated. In this study, the Pt–Ru/CNT electrocatalyst was successfully synthesized using a modified polyol approach with a controlled composition very close to 20 wt.%Pt–10 wt.%Ru, and the anode was prepared by coating Pt–Ru/CNT electrocatalyst on a wet-proof carbon cloth substrate with a metal loading of about 4 mg cm⁻². A commercial gas diffusion electrode (GDE) with a platinum black loading of 4 mg cm⁻² obtained from E-TEK was employed as the cathode. The membrane electrode assembly (MEA) was fabricated using Nafion^® 117 membrane and the single-cell DMFC was assembled with graphite endplates as current collectors. Experiments were carried out at moderate low temperatures using 1 M CH₃OH aqueous solution and pure oxygen as reactants. Excellent cell performance was observed. The tested cell significantly outperformed a comparison cell using a commercial anode coated with carbon-supported Pt–Ru (Pt–Ru/C) electrocatalyst of similar composition and loading. High conductivity of carbon nanotube, good catalyst morphology and suitable catalyst composition of the prepared Pt–Ru/CNT electrocatalyst are considered to be some of the key factors leading to enhanced cell performance.     

Anode bleeding experiments to improve the performance and durability of proton exchange membrane fuel cells

Cost, durability, efficiency and fuel utilization are important issues that remain to be resolved for commercialization of proton exchange membrane fuel cells (PEMFC). Anode flow mode, which includes recirculation, dead-ended and exit bleeding operation, plays an important role in fuel utilization, durability, performance and the overall cost of the fuel cell system. Depending on the flow mode, water and nitrogen accumulation in the anode leads to voltage transients and local fuel starvation, which causes cell potential reversal and carbon corrosion in the cathode catalyst layers. Controlled anode exit bleeding can avoid the accumulation of nitrogen and water and improve fuel utilization. In this study, we present a method to control the bleed rate with high precision in experiments and demonstrate that hydrogen utilization as high as 0.9988 for a 25 cm² single cell and 0.9974 for an 8.17 cm² single cell can be achieved without significant performance loss. In the experiments, anode pressure is kept at 1 bar higher than the cathode pressure to decrease nitrogen crossover from the cathode, decreasing the crossover from the cathode. Moreover, four load cycle profiles are applied to observe the cumulative loss in the electrochemical surface area (ECSA), which are acquired from cyclic voltammetry (CV) analysis. Experiments confirm that the ECSA loss and severe voltage transients are indicative of fuel starvation induced by prolonged dead-ended or low exit-bleed operation modes whereas bleed rates that are larger than the predicted crossover rate are sufficient to operate the fuel cell without voltage transients and detrimental ECSA loss.     

Synthesis and electrochemical properties of nano-composite IrO2/TiO2 anode catalyst for SPE electrolysis cell

A composite catalyst of nano-grade IrO₂/TiO₂ powder is synthesized by Adams’ fusion method for reducing overvoltage of solid polymer electrolyte (SPE) cell and cost-down of noble metal catalyst, simultaneously. The IrO₂/TiO₂ catalysts, which has a porous composite nanostructure, are prepared according to molar ratio of Ir and Ti element with a specific surface area of 34.1–55.3 m² g^?1. It is found that crystal structure of TiO₂ is more dominated by the rutile phase than by Anatase. For a SPE system, total catalyst loading of anode which made of TiO₂ and IrO₂ is prepared as low as 0.77 mg cm^?2 or less, in which the loading amount of the IrO₂ only is set to 0.6 mg cm^?2 or less. The anode catalyst layer of about 10 ? thickness is coated on the membrane (Nafion 212) for the membrane electrode assembly (MEA) by the decal method. The strong adhesion between the catalyst electrode the membrane is observed by Scanning electron microscopy (SEM). Linear sweep voltammetry (LSV) results shows that the nano-composite IrO₂/TiO₂ catalysts has better oxygen evolution reaction (OER) than that of the synthesis IrO₂ only. Finally, the IrO₂/TiO₂ catalysts is applied as anode electrode for SPE cells and it is observed that in spite of the lower loading amount of the IrO₂ less than 0.5 mg cm^?2, working voltage of 1.68 V is observed at a current density of 1 A cm^?2 and operating temperature of 80 °C.     

Fine interface contact and high activity of nickel-based anode modified by gadolinium for hydrogen and methane fuel

In this work, gadolinium is used to modify nickel catalyst, which can improve the properties of nickel oxide particle and inhibit its sintering and grain growth. Interface contact between nickel catalyst and YSZ is significantly improved and fine anode microstructure can be obtained when gadolinium is used to modify Ni-YSZ anode. Fine interface contact of GdNi-YSZ anode can accelerate charge transfer process and steam formation process, which leads to high activity for electrochemical oxidation of hydrogen and low impedance resistance. The remarkable characteristic of GdNi-YSZ anode cell is that the cell performance for humidified methane fuel is greatly improved due to the high anode activity for methane reforming and electrochemical oxidation of hydrogen. The maximum power density of GdNi-YSZ anode cell with humidified methane as fuel can reach 1.59 W/cm² at 800 °C and 0.46 W/cm² at 650 °C. High performance of GdNi-YSZ anode cell with humidified methane as fuel leads to much H₂O produced during the electrochemical oxidation process, which can depress carbon deposition and improve the cell stability for humidified methane fuel.     

An investigation into factors affecting the stability of carbons and carbon supported platinum and platinum/cobalt alloy catalysts during 1.2 V potentiostatic hold regimes at a range of temperatures

To meet automotive targets for fuel cell operation and allow higher temperature operation an understanding of the factors affecting carbon and platinum stability is critical. The stability of both carbons and carbon supported platinum and platinum/cobalt alloy catalysts was studied during 1.2 V versus RHE potentiostatic hold tests using carbon and catalyst coated electrodes in a three-chamber wet electrolyte cell at a range of temperatures. At 80 °C the wt% of carbon corroded increases with increasing BET area. Surface oxidation was followed electrochemically using the quinone/hydroquinone redox couple. Increasing temperature, time at 1.2 V and wt% platinum on the carbon increases surface oxidation. Although increasing temperature was shown to increase the extent of carbon corrosion, catalysing the carbon did not significantly change how much carbon was corroded. Platinum stability was investigated by electrochemical metal area loss (ECA). Platinum catalysts on commercial carbons lost more ECA with increasing temperature. A platinum/cobalt alloy on a low surface area carbon was demonstrated to be more stable to both carbon corrosion and metal area loss at temperatures up to 80 °C than platinum catalysts on commercial carbons, making this material an excellent candidate for higher temperature automotive operation.     

Characterization of the Ni-ScSZ anode with a LSCM-CeO2 catalyst layer in thin film solid oxide fuel cell running on ethanol fuel

Solid oxide fuel cell (SOFC) running directly on hydrocarbon fuels has attracted much attention in recent years. In this paper, a dual-layer structure anode running on ethanol is fabricated by tape casting and screen-printing method, the addition of a LSCM-CeO₂ catalyst layer to the supported anode surface yields better performance in ethanol fuel. The effect that the synthesis conditions of the catalyst layer have on the performances of the composite anodes is investigated. Single cells with this anode are also fabricated, of which the maximum power density reaches 669 mW cm⁻² at 850 °C running on ethanol steam. No significant degradation in performance has been observed after 216 h of cell testing when the Ni-ScSZ13 anode is exposed to ethanol steam at 700 °C. Very little carbon is detected on the anode, suggesting that carbon deposition is limited during cell operation. Consequently, the LSCM-CeO₂ catalyst layer on the surface of the supported anode makes it possible to have good stability for long-term operation in ethanol fuel due to low carbon deposition.     

Performance studies of Pd–Pt and Pt–Pd–Au catalyst for electro-oxidation of glucose in direct glucose fuel cell

Platinum is employed as anode catalyst for low temperature electro-oxidation of glucose in direct glucose fuel cell (DGFC), but it suffers from poisoning by intermediate oxidation products. In the present investigation, palladium and gold precursors are added with platinum precursor to form low metal loading (∼15–20% by wt.) carbon supported catalyst by NaBH₄ reduction technique. The prepared PtPdAu/C (metal ratio 1:1:1) and PdPt/C (metal ratio 4:1) catalysts are tested in DGFC. The Physical characterization of electro-catalysts by scanning electron microscope, transmission electron microscope, energy dispersive X-ray, X-ray diffraction and thermo-gravimetric analysis confirms the formation of nano-sized metal particles on carbon substrate with two prominent homogeneous bi- or tri-metallic crystal phases for PtPdAu/C. The cyclic voltammetry studies carried out for glucose (0.05 M) oxidation in (0.5 M KOH) alkaline medium shows the metal catalysts can efficiently electro-oxidize glucose. The catalysts tested as anode in a batch type DGFC using commercial activated charcoal as cathode produced peak power density of 0.52 mW cm⁻² for both PdPt/C and PtPdAu/C in 0.3 M glucose in 1 M KOH solution.     

Analysis of degradation in PEMFC caused by cell reversal during air starvation

The damage caused by cell reversal during proton exchange membrane fuel cells (PEMFCs) operation with air starvation was investigated by a single-cell experiment. Samples from degraded membrane–electrode assemblies (MEAs) were characterized. The loss of electrochemical surface area of the cathode platinum was detected by in situ cyclic voltammetry, and platinum sintering was detected by transmission electron microscopy (TEM) analysis. Degradation at the anode was not detected in the chemical analysis of the anode catalyst layer of MEA samples by energy dispersive X-ray analysis (EDX) and TEM. An obvious decrease in the performance of PEMFC was observed in a sample degraded by cell reversal for 120 min.     

Methoxy methane (dimethyl ether) as an alternative fuel for direct fuel cells

The electrooxidation of methoxy methane (dimethyl ether) was studied at different Pt-based electrocatalysts in a standard three-electrode electrochemical cell. It was shown that alloying platinum with ruthenium or tin leads to shift the onset of the oxidation wave towards lower potentials. On the other hand, the maximum current density achieved was lower with a bimetallic catalyst compared to that obtained with a Pt catalyst. The direct oxidation of dimethoxy methane in a fuel cell was carried out with Pt/C, PtRu/C and PtSn/C catalysts. When Pt/C catalyst is used in the anode, it was shown that the pressure of the fuel and the temperature of the cell played important roles to enhance the fuel cell electrical performance. An increase of the pressure from 1 to 3 bar leads to multiply by two times the maximum achieved power density. An increase of the temperature from 90 to 110 °C has the same effect. When PtRu/C catalyst is used in the anode, it was shown that the electrical performance of the cell was only a little bit enhanced. The maximum power density only increased from 50 to 60 mW cm⁻² at 110 °C using a Pt/C anode and a Pt_0.8Ru_0.2/C anode, respectively. But, the maximum power density is achieved at lower current densities, i.e. higher cell voltages. The addition of ruthenium to platinum has other effect: it introduces a large potential drop at relatively low current densities. With the Pt_0.5Ru_0.5/C anode, it has not been possible to applied current densities higher than 20 mA cm⁻² under fuel cell operating conditions, whereas 250 and almost 400 mA cm⁻² were achieved with Pt_0.8Ru_0.2/C and Pt/C anodes. The Pt_0.9Sn_0.1/C anode leads to higher power densities at low current densities and to the same maximum power density as the Pt/C anode.