X-ray absorption analysis of nitrogen contribution to oxygen reduction reaction in carbon alloy cathode catalysts for polymer electrolyte fuel cells

The electronic structure of nitrogen introduced into various carbon-based cathode catalysts for the polymer electrolyte fuel cell (PEFC) is investigated using X-ray absorption spectroscopy (XAS). The profile of π* peaks at the pre-edge of N 1s XAS spectra is used to determine the chemical state of nitrogen, which can be an indicator of oxygen reduction reaction (ORR) activity. It is found that catalysts with a relatively larger amount of graphite-like nitrogen exhibit a higher ORR activity than those with a relatively larger amount of pyridine-like nitrogen. We propose that effective doping with graphite-like nitrogen is a practical guideline for the synthesis of active carbon alloy catalysts.     

Role of residual transition-metal atoms in oxygen reduction reaction in cobalt phthalocyanine-based carbon cathode catalysts for polymer electrolyte fuel cell

The electronic structure of Co atoms in cobalt phthalocyanine (CoPc)-based carbon catalysts, which were prepared by pyrolyzing a mixture of CoPc and phenol resin polymer up to 1000 °C, has been investigated using X-ray absorption fine structure (XAFS) analysis and hard X-ray photoemission spectroscopy (HXPES). The CoK XAFS spectra show that most of the Co atoms are in the metallic state and small quantities of oxidized Co components are present in the samples even after acid washing to remove Co atoms. Based on the difference in probing depth between XAFS and HXPES, it was found that after acid washing, the surface region with the aggregated Co clusters observed by transmission electron microscopy is primarily composed of metallic Co. Since the electrochemical properties remain almost unchanged even after the acid washing process, the residual metallic and oxidized Co atoms themselves will hardly contribute to the oxygen reduction reaction activity of the CoPc-based carbon cathode catalysts, implying that the active sites of the CoPc-based catalysts primarily consist of light elements such as C and N.     

Preparation of carbon alloy catalysts for polymer electrolyte fuel cells from nitrogen-containing rigid-rod polymers

‘Carbon Alloy Catalysts’ (CAC), non-precious metal catalysts for the oxygen reduction reaction (ORR), were prepared from various kinds of nitrogen-containing rigid-rod aromatic polymers, polyimides, polyamides and azoles, by carbonization at 900 °C under nitrogen flow. The catalytic activity for ORR was evaluated by the onset potential, which was taken at a current density of −2 μA cm⁻². Carbonized polymers having high nitrogen content showed higher onset potential. In particular, CACs derived from azole (Az5) had an onset potential of 0.8 V, despite being was prepared without any metals.     

Nitrogen-modified carbon-based catalysts for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Nitrogen-modified carbon-based catalysts for oxygen reduction were synthesized by modifying carbon black with nitrogen-containing organic precursors. The electrocatalytic properties of catalysts were studied as a function of surface pre-treatments, nitrogen and oxygen concentrations, and heat-treatment temperatures. On the optimum catalyst, the onset potential for oxygen reduction is approximately 0.76 V (NHE) and the amount of hydrogen peroxide produced at 0.5 V (NHE) is approximately 3% under our experimental conditions. The characterization studies indicated that pyridinic and graphitic (quaternary) nitrogens may act as active sites of catalysts for oxygen reduction reaction. In particular, pyridinic nitrogen, which possesses one lone pair of electrons in addition to the one electron donated to the conjugated π bond, facilitates the reductive oxygen adsorption.     

Electrocatalytic activity of iridium oxide nanoparticles coated on carbon for oxygen reduction as cathode catalyst in polymer electrolyte fuel cell

The iridium oxide nanoparticles supported on Vulcan XC-72 porous carbon were prepared for cathode catalyst in polymer electrolyte fuel cell (PEFC). The catalyst has been characterized by transmission electron microscopy (TEM) and in PEFC tests. The iridium oxide nanoparticles, which were uniformly dispersed on carbon surface, were 2-3 nm in diameter. With respect to the oxygen reduction reaction (ORR) activity was also studied by cyclic voltammetry (CV), revealing an onset potential of about 0.6 V vs. an Ag/AgCl electrode. The ORR catalytic activity of this catalyst was also tested in a hydrogen-oxygen single PEFC and a power density of 20 mW cm⁻² has been achieved at the current density of 68.5 mA cm⁻². This study concludes that carbon-supported iridium oxide nanoparticles have potential to be used as cathode catalyst in PEFC.     

Development of tellurium-modified carbon catalysts for oxygen reduction reaction in PEM fuel cells

Tellurium (Te)-modified carbon catalyst for oxygen reduction reaction was prepared through chemical reduction of telluric acid followed by the pyrolysis process at elevated temperatures. The catalyst was found to be active for oxygen reduction reaction. High-temperature pyrolysis plays a crucial role in the formation of the active sites of the catalysts. When the pyrolysis was conducted at 1000 °C, the catalyst exhibited the onset potential for oxygen reduction as high as 0.78 V vs. NHE and generated less than 1% H₂O₂ during oxygen reduction. The performance of the membrane–electrode assembly prepared with the Te-modified carbon catalyst was also evaluated.     

Development of group 4 and 5 metal oxide-based cathodes for polymer electrolyte fuel cell

Partially oxidized zirconium, niobium, and tantalum carbonitrides were prepared to discuss a characteristic common to all. The onset potential for the ORR of partially oxidized carbonitrides reached above ca. 0.85 V. The XRD and XPS analyses suggested that both the crystalline structure and the chemical bonding state of the surface of the partially oxidized carbonitrides were very similar to those of the oxides. However, the partially oxidized carbonitrides had lower ionization potential than the oxides. The lower ionization potential indicated that the partially oxidized carbonitrides had some defects on the surface. From these results, the structure of oxides and the highest oxidation state of surface metal with some oxygen defects were essential to have high ORR activity for group 4 and 5 oxide-based compounds. Such oxygen defects might be responsible for the oxygen reduction capability by creating electronically favorable oxygen adsorption sites.     

Non precious metal catalysts for the PEM fuel cell cathode

Low temperature fuel cells, such as the proton exchange membrane (PEM) fuel cell, have required the use of highly active catalysts to promote both the fuel oxidation at the anode and oxygen reduction at the cathode. Attention has been particularly given to the oxygen reduction reaction (ORR) since this appears to be responsible for major voltage losses within the cell. To provide the requisite activity and minimse losses, precious metal catalysts (containing Pt) continue to be used for the cathode catalyst. At the same time, much research is in progress to reduce the costs associated with Pt cathode catalysts, by identifying and developing non-precious metal alternatives. This review outlines classes of non-precious metal systems that have been investigated over the past 10 years. Whilst none of these so far have provided the performance and durability of Pt systems some, such as transition metals supported on porous carbons, have demonstrated reasonable electrocatalytic activity. Of the newer catalysts, iron-based nanostructures on nitrogen-functionalised mesoporous carbons are beginning to emerge as possible contenders for future commercial PEMFC systems.     

Changes in electronic states of platinum-cobalt alloy catalyst for polymer electrolyte fuel cells by potential cycling

Changes in the electronic states of platinum-cobalt (Pt-Co) alloy catalysts through potential cycling between 0.6 and 1.0 V were investigated by X-ray photoemission spectroscopy (XPS) using synchrotron radiation. The electrochemical surface area loss and the particle size growth of the Pt catalyst were larger than those of the Pt-Co alloy catalyst. Pt 4f XPS spectra of the Pt-Co alloy catalyst do not show any change through the potential cycling, indicating that most part of Pt is stable during the potential cycling. Larger amount of Pt(OH)₂ existed in the initial MEA of the Pt catalyst than the Pt-Co alloy catalyst, indicating that the Pt catalyst has a tendency to be oxidized. The Pt(OH)₂ decreased and metallic platinum increased in the cycle-tested MEA, suggesting that the Pt(OH)₂ dissolved and re-deposited as metallic states. The oxidation tendency explains the less durability of the Pt catalyst than the Pt-Co alloy catalyst. Co 2p XPS spectra imply that cobalt is absent on the surface of the catalyst particles and the Pt skin layer is thicker than 1.4 nm (4 mono-layers). The absence of the cobalt oxide in the cycle-tested MEA demonstrates that the Pt-Co core under the Pt skin layer is stable during the potential cycling.     

Electrochemical impedance analysis with transmission line model for accelerated carbon corrosion in polymer electrolyte membrane fuel cells

The effects of varying the applied voltage and relative humidity of feed gases in degradation tests of polymer electrolyte membrane fuel cells (PEMFCs) were analyzed using electrochemical impedance spectroscopy (EIS). A transmission line model that considers the proton-transport resistance in the cathode catalyst layer was used to analyze impedance spectra obtained from degraded PEMFCs. As the applied cell voltage was increased from 1.3 to 1.5 V to induce accelerated degradation, the cell performance decayed significantly due to increased charge- and proton-transfer resistance. The PEMFC degradation was more pronounce at higher relative humidity (RH), i.e. 100% RH, as compared with that observed under 50% RH. Furthermore, changes in the charge transfer resistance of the electrode accompanied changes in the ionic conductivity in the PEMFC catalyst layer. Although the initial ionic and charge-transfer resistances in the catalyst layer were lower under higher RH conditions, the impedance results indicated that the performance degradation was more significant at higher water contents in the electrode due to the consequential carbon corrosion, especially when higher voltages, i.e. 1.5 V, were applied to the PEMFC single cell.     

An electro-kinetic study of oxygen reduction in polymer electrolyte fuel cells at intermediate temperatures

The oxygen reduction process in polymer electrolyte fuel cells (PEMFCs) was in-situ investigated at intermediate temperatures (80°–130 °C) by using a carbon supported PtCo catalyst and Nafion membrane as electrolyte. To overcome the Nafion dehydration above 100 °C, the experiments were carried out under pressurized conditions. Electro-kinetic parameters such as reaction order and activation energy were determined from the steady-state galvanostatic polarization curves obtained for the PEM single cell. Negative activation energies of 40 kJ mol⁻¹ and 18 kJ mol⁻¹ were observed at 0.9 V and 0.65 V, respectively, in the temperature range 100°–130 °C. This was a consequence of ionomer and membrane dry-out. The ionomer dry-out effect appears to depress reaction kinetics as the temperature increases above 100 °C since the availability of protons at the catalyst–electrolyte interface is linked to the presence of proper water contents. An oxygen reduction reaction of the first order with respect to the oxygen partial pressure was determined at low current densities. Maximum power densities of 990 mW cm⁻² and 780 mW cm⁻² at 100 °C and 110 °C (H₂–O₂) with 100% R.H., were achieved at 3 bars abs.     

X-ray imaging of water distribution in a polymer electrolyte fuel cell

At present, water management in a polymer electrolyte fuel cell (PEFC) is a major subject of research. In fact, proper water management is vital to achieve maximum performance and durability from a PEFC. Consequently, this study is conducted to visualize quantitatively the water distribution in a PEFC by means of an X-ray imaging technique. The X-ray images of the PEFC components with and without water are clearly distinguished. Reference to the visualized X-ray images, enables quantitative evaluation of the water distribution in the region between the separator and the gas-diffusion layer (GDL). Likewise, the meniscus of water in the channels of the PEFC is clearly observed.     

Direct growth of carbon nanofibers on carbon-based substrates as integrated gas diffusion and catalyst layer for polymer electrolyte fuel cells

One-dimensional carbon nanostructures are considered promising for application as catalyst support in polymer electrolyte fuel cells, replacing the most widely used carbon black, due to their physico-chemical properties and high surface area. Different morphologies of carbon nanofibers, by varying the graphene layers orientation with respect to the fibre axis, exhibit different amount of available open edges that can act as anchorage site for catalyst nanoparticles. CNF are grown on graphite paper by a controlled plasma enhanced chemical vapour deposition and then used as substrates for Pt electrodeposition. The CNF direct growth on carbon paper allows having single layer electrodes with both diffusive and catalytic layer function. Moreover, the replacement of conventional ink deposition methods with electrodeposition for platinum dispersion, allows greatly reducing the catalyst load, increasing at the same time its utilization and performance. The innovative electrodes are characterized by field emission gun scanning electron microscopy and X-ray photoelectron spectroscopy to assess the morphological properties, and by cyclic voltammetry in H₂SO₄ and H₂SO₄ + CH₃OH to determine the electrocatalytic activity and long term stability. The comparison with an electrode made of conventionally deposited Pt catalyst by ink method on commercial carbon black shows better performance for the developed Pt/CNF electrodes.     

Numerical study of a new cathode flow-field design with a sub-channel for a parallel flow-field polymer electrolyte membrane fuel cell

The cathode flow-field design of a polymer electrolyte membrane (PEM) fuel cell is crucial to its performance, because it determines the distribution of reactants and the removal of liquid water from the fuel cell. In this study, the cathode flow-field of a parallel flow-field PEM fuel cell was optimized using a sub-channel. The main-channel was fed with moist air, whereas the sub-channel was fed with dry air. The influences of the sub-channel flow rate (SFR, the amount of air from the sub-channel inlet as a percentage of the total cathode flow rate) and the inlet positions (SIP, where the sub-channel inlets were placed along the cathode channel) on fuel cell performance were numerically evaluated using a three-dimensional, two-phase fuel cell model. The results indicated that the SFR and SIP had significant impacts on the distribution of the feed air, removal of liquid water, and fuel cell performance. It was found that when the SIP was located at about 30% along the length of the channel from main-channel inlet and the SFR was about 70%, the PEM fuel cell exhibited much better performance than seen with a conventional design.     

Particle size dependence of CO tolerance of anode PtRu catalysts for polymer electrolyte fuel cells

An anode catalyst for a polymer electrolyte fuel cell must be CO-tolerant, that is, it must have the function of hydrogen oxidation in the presence of CO, because hydrogen fuel gas generated by the steam reforming process of natural gas contains a small amount of CO. In the present study, PtRu/C catalysts were prepared with control of the degree of Pt-Ru alloying and the size of PtRu particles. This control has become possible by a new method of heat treatment at the final step in the preparation of catalysts. The CO tolerances of PtRu/C catalysts with the same degree of Pt-Ru alloying and with different average sizes of PtRu particles were thus compared. Polarization curves were obtained with pure H₂ and CO/H₂ (CO concentrations of 500-2040 ppm). It was found that the CO tolerance of highly dispersed PtRu/C (high dispersion (HD)) with small PtRu particles was much higher than that of poorly dispersed PtRu/C (low dispersion (LD)) with large metal particles. The CO tolerance of PtRu/C (HD) was higher than that of any commercial PtRu/C. The high CO tolerance of PtRu/C (HD) is thought to be due to efficient concerted functions of Pt, Ru, and their alloy.     

Effects of cathode catalyst layer design parameters on cold start behavior of polymer electrolyte fuel cells (PEFCs)

We present a theoretical study on the effects of key catalyst layer (CL) design parameters on the cold start behavior of a polymer electrolyte fuel cell (PEFC) using a three-dimensional transient cold start model developed in a previous study 1 and 2. Among several CL design parameters, we adopt the ionomer fraction (?_I) and weight ratio of Pt to carbon support (wt%_Pt–C) in the cathode CL as CL design variables for this study. Therefore, other design parameters such as CL thickness and the oxygen reduction reaction (ORR) kinetic parameter are accordingly adjusted due to changes in ?_I and wt%_Pt–C for cold start simulations. The calculated results confirm that these two design parameters provide control of the ice storage capacity and water absorption potential of the cathode CL, and consequently have a substantial influence on the cold start behavior of a PEFC. We provide a guideline to design and optimize a cathode CL and membrane electrode assembly (MEA) for improved PEFC cold start capability.     

Sulfonation of carbon-nanotube supported platinum catalysts for polymer electrolyte fuel cells

Sulfonic acid groups were grafted onto the surface of carbon-nanotube supported platinum (Pt/CNT) catalysts to increase platinum utilization in polymer electrolyte fuel cells (PEFCs) by both thermal decomposition of ammonium sulfate and in situ radical polymerization of 4-styrenesulfonate. The resultant sulfonated Pt/CNT catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectrometry, thermal gravimetric analysis (TGA) and electrochemical methods. The electrodes with the Pt/CNT catalysts sulfonated by the in situ radical polymerization of 4-styrenesulfonate exhibited better performance than did those with the unsulfonated counterparts, mainly because of the easier access with protons and well dispersed distribution of the sulfonated Pt/CNT catalysts, indicating that sulfonation is an efficient approach to improve performance and reduce cost for the Pt/CNT-based PEFCs. The electrodes with the Pt/CNT catalysts sulfonated by the thermal decomposition of ammonium sulfate, however, did not yield the expected performance as in the case of carbon black supported platinum (Pt/C) catalysts, probably due to the significant agglomeration of platinum particles on the CNT surface at high temperatures, indicating that the Pt/CNT catalysts are more sensitive to temperature than the Pt/C catalysts.     

An innovative membrane-electrode assembly for efficient and durable polymer electrolyte membrane fuel cell operations

An innovative membrane-electrode assembly, based on a polyoxometalate (POM)-modified low-Pt loading cathode and a sulphated titania (S-TiO₂)-doped Nafion membrane, is evaluated in a polymer electrolyte membrane fuel cell. The modification of fuel cell cathode with Cs₃HPMo₁₁VO₄₀ polyoxometalate is performed to enhance particles dispersion and increase active area, allowing low Pt loading while maintaining performance. The POM's high surface acidity favors kinetics of oxygen reduction reaction. The mesoporous features of POM allow the embedding of Pt inside the micro-mesopores, avoiding the Pt aggregation during fuel cell operation and delaying the aging process, with consequent increase of lifetime. On the other hands, commercial Nafion is modified with superacidic sulphated titanium oxide nanoparticles, allowing operation at low relative humidity and controlled polarization of the MEA. Further MEAs, formed by unmodified Nafion membrane and the POM-based cathode, as well as sulphated titanium-added Nafion and commercial Pt-based electrodes, are used as terms of comparison. The cell performances are studied by polarization curves, electrochemical impedance spectroscopy, Tafel plot analysis and high frequency resistance measurements. The dependence of cell performances on relative humidity is also studied. The catalytic and transport properties are improved using the coupled system, despite the reduced Pt loading, thanks to rich proton environment provided by cathode and membrane.     

Macroscopic analysis of characteristic water transport phenomena in polymer electrolyte fuel cells

Comprehensive analytical and numerical analyses were performed, focusing on anode water loss, cathode flooding, and water equilibrium for polymer electrolyte fuel cells. General features of water transport as a function of membrane thickness and current density were presented to illustrate the net effect of back-diffusion of water from the cathode to anode over a polymer electrolyte fuel cell domain. First, two-dimensional numerical simulation were performed, showing that the difference in molar concentration of water at the channel outlet is widened as the operating current density increases with a thin membrane (Nafion^®${\mathrm{Nafion}}^{\circledR }$ 111), which was verified by Dong et al. [Distributed performance of polymer electrolyte fuel cells under low-humidity conditions. J Electrochem Soc 2005; 152: A2114–22]. Then, analytical solutions were compared with computational results in predicting those characteristics of water transport phenomena. It was theoretically estimated that the high pressure operation of fuel cells expedites water condensing and results in shorter anode water loss and cathode flooding locations. In this study, it was also found that a thin membrane (Nafion^®${\mathrm{Nafion}}^{\circledR }$ 111) facilitates water transport in the through-membrane direction and therefore water concentration at the anode and cathode channel outlets reaches an equilibrium state particularly at low operating current densities. Moreover, the difference in the anode water concentration between Nafion^®${\mathrm{Nafion}}^{\circledR }$ 111 and Nafion^®${\mathrm{Nafion}}^{\circledR }$ 115 membranes becomes intensified in the in-plane direction under the same water production condition, while the cathode water concentration profiles remains almost same.     

Non-platinum cathode catalysts for alkaline membrane fuel cells

Hydrogen–oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm⁻² using H₂ and O₂ gases.