Improvement in high temperature proton exchange membrane fuel cells cathode performance with ammonium carbonate

Proton exchange membrane (PEM) fuel cells with optimized cathode structures can provide high performance at higher temperature (120 °C). A “pore-forming” material, ammonium carbonate, applied in the unsupported Pt cathode catalyst layer of a high temperature membrane electrode assembly enhanced the catalyst activity and minimized the mass-transport limitations. The ammonium carbonate amount and Nafion^® loading in the cathode were optimized for performance at two conditions: 80 °C cell temperature with 100% anode/75% cathode R.H. and 120 °C cell temperature with 35% anode/35% cathode R.H., both under ambient pressure. A cell with 20 wt.% ammonium carbonate and 20 wt.% Nafion^® operating at 80 °C and 120 °C presented the maximum cell performance. Hydrogen/air cell voltages at a current density of 400 mA cm⁻² using the Ionomem/UConn membrane as the electrolyte with a cathode platinum loading of 0.5 mg cm⁻² were 0.70 V and 0.57 V at the two conditions, respectively. This was a 19% cell voltage increase over a cathode without the “pore-forming” ammonium carbonate at the 120 °C operating condition.     

Optimal composition of polymer electrolyte fuel cell electrodes determined by the AC impedance method

A proton exchange membrane fuel cell (PEMFC) electrode having a modified morphology of conventional Teflon (PTFE) bonded electrodes was studied using the AC impedance method. The electrode differs from other types of electrodes in the presence of a thin catalyst-supporting layer between the gas diffusion backing and the catalyst layer. The thickness and composition of the supporting layer were optimized on the basis of the information from AC impedance measurements. The optimal thickness of the supporting layer and its PTFE content turned out to be approximately 3.5 mg cm⁻² and 30 wt.%, respectively. The catalyst layer was cast on top of the supporting layer, from solution that has the proper ratio of ionomer Nafion and Pt/C catalyst. The optimal amount of the ionomer in the catalyst layer was approximately 0.8 mg cm⁻² when Pt loading was kept at 0.4 mg cm⁻². These values are rationalized in terms of the catalyst active area and the transport of the involved species for the electrode reaction.     

Improved photographic production of Pt nano-particles for fuel cell electrodes

An improved photographic Pt printing process has been developed, which is called the print-out process (POP). No developer is required in this process and the deposition efficiency was significantly improved by more than 6 times on carbon paper (CP) and 22 times on carbon-black-coated carbon paper (CB/CP) over the previously reported develop-out process (DOP) [1]. The Pt particle size can be easily controlled by varying the moisture content in the substrate and was reduced to 5 nm on blank CP by adding a stabilizing agent, ethylene glycol (EG), to the photo-emulsion. Due to the hydrophobic nature of CB/CP, both Nafion ionomer solution and ethylene glycol (EG) were mixed with the emulsion during the printing. SEM revealed that on this substrate Pt was distributed as ∼25 nm clusters consisting of 5 nm particles on the carbon-black. The mass specific catalytic activity for methanol oxidation of Pt printed on CB/CP by POP was increased five times compared to that of Pt printed by the previous DOP. The performance of the POP Pt in a H₂ PEM single fuel cell (5 cm²) was also evaluated. A peak power density of 288 mW cm⁻² was achieved with an anode POP Pt catalyst loading of 0.16 mg cm⁻² at 70 °C and 0.9 mg cm⁻² JM Pt at the cathode. Compared to the DOP Pt catalyst at about the same loading, peak power density was improved more than four times by using the POP Pt.     

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.     

Characterisation of zirconium and titanium phosphates and direct methanol fuel cell (DMFC) performance of functionally graded Nafion(R) composite membranes prepared out of them

Pure layered phosphates of varying crystalline phases and crystallinity and composites of gradient layers of zirconium phosphate in Nafion 117-membranes have been prepared. The proton conductivity and, in case of the composites, also the dynamic mechanical properties of these materials were measured under different conditions of temperature and humidity. Membrane-electrode assemblies with low platinum catalyst loading of 0.4 mg cm⁻² Pt at the cathode and 1.9 mg cm⁻² Pt–Ru at the anode were examined in a direct methanol fuel cell (DMFC) at medium temperatures (130 °C). The conductivity of the layered zirconium phosphates is superior to the titanium phosphates and increases with decreasing crystallite size. The electrical performance of the composites in a DMFC-environment is slightly decreased as compared to the unmodified membrane but taking the reduced methanol crossover into account, higher efficiencies can be reached with the zirconium phosphate modified membrane. Furthermore, the mechanical properties are significantly improved by the presence of the inorganic compound.     

Identification of the key variables in membrane electrode preparation for PEM fuel cells by a factorial design

This work aimed to characterize and optimize the variables that influence membrane electrode preparation using a design of experiment (DOE) approach in two steps. First, in the process of electrode preparation, the quantity of PTFE and drying time were found to have no significant influence whereas the drying temperature and atmosphere, and their interactions, were the significant variables on the Membrane Electrode Assembly (MEA) performance; a low drying temperature under the air atmosphere being the proper condition. In the second step, investigating the effect of Nafion content and drying temperature, it was found that the level of Nafion is critical to the cell performance. There was an optimal Nafion content. In the study, a 15% (w/w) level of Nafion and 80 °C drying temperature for 0.5 h under the air atmosphere were the optimal condition for prepartion of a MEA with 1 mg cm^?2 of Pt loading.     

Direct formic acid fuel cells

The performance of formic acid fuel oxidation on a solid PEM fuel cell at 60 °C is reported. We find that formic acid is an excellent fuel for a fuel cell. A model cell, using a proprietary anode catalyst produced currents up to 134 mA/cm² and power outputs up to 48.8 mW/cm². Open circuit potentials (OCPs) are about 0.72 V. The fuel cell runs successfully over formic acid concentrations between 5 and 20 M with little crossover or degradation in performance. The anodic polarization potential of formic acid is approximately 0.1 V lower than that for methanol on a standard Pt/Ru catalyst. These results show that formic acid fuel cells are attractive alternatives for small portable fuel cell applications.     

Advanced air-breathing direct methanol fuel cells for portable applications

A novel MEA is fabricated to improve the performance of air-breathing direct methanol fuel cells. A diffusion barrier on the anode side is designed to control methanol transport to the anode catalyst layer and thus suppressing the methanol crossover. A catalyst coated membrane with a hydrophobic gas diffusion layer on the cathode side is employed to improve the oxygen mass transport. It is observed that the maximum power density of the advanced DMFC with 2 M methanol solution achieves 65 mW cm⁻² at 60 °C. The value is nearly two times more than that of a commercial MEA. At 40 °C, the power densities operating with 1 and 2 M methanol solutions are over 20 mW cm⁻² with a cell potential at 0.3 V.     

Development and demonstration of a higher temperature PEM fuel cell stack

Research and development was conducted on a proton exchange membrane (PEM) fuel cell stack to demonstrate the capabilities of Ionomem Corporation's composite membrane to operate at 120 °C and ambient pressure for on-site electrical power generation with useful waste heat. The membrane was a composite of polytetrafluoroethylene (PTFE), Nafion^®, and phosphotungstic acid. Studies were first performed on the membrane, cathode catalyst layer, and gas diffusion layer to improve performance in 25 cm², subscale cells. This technology was then scaled-up to a commercial 300 cm² size and evaluated in multi-cell stacks. The resulting stack obtained a performance near that of the subscale cells, 0.60 V at 400 mA cm⁻² at near 120 °C and ambient pressure with hydrogen and air reactants containing water at 35% relative humidity. The water used for cooling the stack resulted in available waste heat at 116 °C. The performance of the stack was verified. This was the first successful test of a higher-temperature, PEM, fuel-cell stack that did not use phosphoric acid electrolyte.     

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.     

Organic–inorganic composites based on room temperature ionic liquid and 12-phosphotungstic acid salt with high assistant catalysis and proton conductivity

Proton-conducting composite material was synthesized from 1-butyl-3-methyl-imidazolium chloride (BMImCl) and 12-phosphotungstic acid (PWA). The structure, assistant catalytic effect and ionic conductivity of the composites for the as-synthesized, 200 and 400 °C annealed samples were studied, respectively. The as-synthesized salt was crystal and kept Keggin structure even being annealed at 400 °C, but the organic part was partly decomposed with increasing of the annealing temperature. The partly decomposed BMIm/PWA salt formed by annealing at 400 °C associated with Pt catalyst had excellent assistant catalytic effect on methanol electro-oxidation and displayed a high proton conductivity of 2 mS cm⁻¹ at 30 °C under 96% relative humidity condition.     

Preparation and characterization of sulfonated PEEK-WC membranes for fuel cell applications: A comparison between polymeric and composite membranes

Sulfonated poly(etheretherketone) with a cardo group (SPEEK-WC) exhibiting a wide range of degree of sulfonation (DS) was used to prepare polymeric membranes and composite membranes obtained by incorporation of an amorphous zirconium phosphate sulfophenylenphosphonate (Zr(HPO₄)(O₃PC₆H₄SO₃H), hereafter Zr(SPP)) in a SPEEK-WC matrix. The nominal composition of the composite membranes was fixed at 20 wt% of Zr(SPP). Both types of membrane were characterized for their proton conductivity, methanol permeability, water and/or methanol uptake, morphology by SEM and mechanical properties. For comparison, a commercial Nafion 117 membrane was characterized under the same operative conditions. The composite membranes exhibited a reduced water uptake in comparison with the polymeric membranes especially at high DS values and temperature higher than 50 °C. As a result, the water uptake into composite membranes remained about constant in the range 20–70 °C. The methanol permeability (P) of both polymeric and composite membranes was always lower than that of a commercial Nafion 117 membrane. At 22 °C and 100% relative humidity (RH), the proton conductivities (σ) of the polymeric membranes increased from 6 × 10⁻⁴ to 1 × 10⁻² S cm⁻¹ with the increase of DS from 0.1 to 1.04. The higher conductivity value was comparable with that of Nafion 117 membrane (3 × 10⁻² S cm⁻¹) measured under the same operative conditions. The conductivities of the composite membranes are close to that of the corresponding polymeric membranes, but they are affected to a lesser extent by the polymer DS. The maximum value of the σ/P ratio (about 7 × 10⁴ at 25 °C) was found for the composite membrane with DS = 0.2 and was 2.5 times higher than the corresponding value of the Nafion membrane.     

Dependence of high-temperature PEM fuel cell performance on Nafion® content

Operating a proton exchange membrane (PEM) fuel cell at elevated temperatures (above 100 °C) has significant advantages, such as reduced CO poisoning, increased reaction rates, faster heat rejection, easier and more efficient water management and more useful waste heat. Catalyst materials and membrane electrode assembly (MEA) structure must be considered to improve PEM fuel cell performance. As one of the most important electrode design parameters, Nafion^® content was optimized in the high-temperature electrodes in order to achieve high performance. The effect of Nafion^® content on the electrode performance in H₂/air or H₂/O₂ operation was studied under three different operation conditions (cell temperature (°C)/anode (%RH)/cathode (%RH)): 80/100/75, 100/70/70 and 120/35/35, all at atmospheric pressure. Different Nafion^® contents in the cathode catalyst layers, 15–40 wt%, were evaluated. For electrodes with 0.5 mg cm⁻² Pt loading, cell voltages of 0.70, 0.68 and 0.60 V at a current density of 400 mA cm⁻² were obtained at 35 wt% Nafion^® ionomer loading, when the cells were operated at the three test conditions, respectively. Cyclic voltammetry was conducted to evaluate the electrochemical surface area. The experimental polarization curves were analyzed by Tafel slope, catalyst activity and diffusion capability to determine the influence of the Nafion^® loading, mainly associated with the cathode.     

Thin yttria-stabilized zirconia electrolyte and transition layers fabricated by particle suspension spray

In order to develop high performance intermediate temperature (<800 °C) solid oxide fuel cells (SOFCs) with a lower fabrication cost, a pressurized spray process of ceramic suspensions has been established to prepare both dense yttria-stabilized zirconia (YSZ) electrolyte membranes and transition anode layers on NiO + YSZ anode supports. A single cell with 10 μm thick YSZ electrolyte on a porous anode support and ∼20 μm thick cathode layer showed peak power densities of only 212 mW cm⁻² at 700 °C and 407 mW cm⁻² for 800 °C. While a cell with 10 μm thick YSZ electrolyte and a transition layer on the porous anode support using a ultra-fine NiO + YSZ powder showed peak power densities of 346 and 837 mW cm⁻² at 700 and 800 °C, respectively. The dramatic improvement of cell performance was attributed to the much improved anode microstructure that was confirmed by both scanning electron microscopes (SEM) observation and impedance spectroscopy. The results have demonstrated that a pressurized spray coating is a suitable technique to fabricate high performance SOFCs and at lower cost.     

Methanol conditioning for improved performance of formic acid fuel cells

This paper considers the effect of methanol pretreatment on the performance of a direct formic acid fuel cell (DFAFC). We find that conditioning of the cell in methanol results in a substantial increase in current. The current at 60 °C increases from 95 to 320 mA/cm² at 0.3 V. The maximum power density increases from 33 to 119 mW/cm². The cell resistance decreases from 0.37 to 0.32 Ω cm². CO stripping experiments show that the catalyst is not being greatly affected by these changes. Our interpretation of the data is that the anode layer of membrane electrolyte assembly (MEA) undergoes some change during the methanol conditioning. The change improves the performance.     

Fabrication and characterization of a YSZ/YDC composite electrolyte by a sol–gel coating method

The compatibility of a composite electrolyte composed of a yttria stabilized zirconia (YSZ) film and a yttria-doped ceria (YDC) substrate in a solid oxide fuel cell (SOFC) that can be operated under 800 °C was evaluated. The YSZ film coated on a YDC substrate was derived from a polymeric YSZ sol using a sol–gel spin coating method followed by heat-treatment at 1400 °C for 2 h. The SEM and XRD analysis indicated that there were no cracks, pinholes, or byproducts. The composite electrolyte comprising a YSZ film of 2 μm thickness and a YDC substrate of 1.6 mm thickness was used in a single cell performance test. A 0.5 V higher value of open circuit voltage (OCV) was found for the composite electrolyte single cell compared with an uncoated YDC single cell between 700 and 1050 °C and confirmed that the YSZ film was an electron blocking layer. The maximum power density of the composite electrolyte single cell at 800 °C, 122 mW/cm² at 285 mA/cm², is comparable with that of a YSZ single cell with the same thickness at 1000 °C, namely 144 mW/cm² at 330 mA/cm². The hypothetical oxygen partial pressure at the interface between the YSZ film and the YDC substrate for the composite electrolyte with the same thickness ratio at 800 °C is 5.58×10⁻¹⁸ atm which is two orders of magnitude higher than the equilibrium oxygen partial pressure of Ce₂O₃/CeO₂, 2.5×10⁻²⁰ atm, at the same temperature.     

Preparation and evaluation of electrodeposited platinum nanoparticles on in situ carbon nanotubes grown carbon paper for proton exchange membrane fuel cells

Multi-walled carbon nanotubes (MWCNTs) based microporous layer on the non-woven carbon paper substrates was prepared by in situ growth in a chemical vapor deposition method. Pt with a loading of ～0.13 mg cm^?2 was electrodeposited at ?0.3, ?0.6, ?1.2, ?2.4, and ?3.6 V vs SCE in a chloroplatinic acid (60 g/L) and hydrochloric acid (10 g/L) bath using a potentiostat. Scanning electron micrographs showed that the Pt nanoparticles decorated on the MWCNTs/carbon paper are highly uniform, especially at an electrodeposition voltage of ?0.6 V vs SCE. Pt particles' size at various deposition potentials, as estimated by X-ray diffraction analysis is in nanosize range with an average diameter of 6 nm. Fuel cell performance of the Pt deposited in situ grown MWCNTs carbon paper was evaluated using Nafion-212 membrane at various operating conditions. The cathode with Pt deposition at ?0.6 V showed a power density of ～640 mW cm^?2 at 80 °C using H₂ and O₂ at 90% RH and 101 kPa.     

Evaluation of nafion based double layer capacitors by electrochemical impedance spectroscopy

In this work some electrochemical characteristics of all solid double layer capacitors prepared by high surface carbon and Nafion polymer electrolyte are reported. Carbon composite electrodes with a Nafion loading of 30 wt.% were prepared and evaluated. Nafion 115 membrane, recast Nafion membrane and 1 M H₂SO₄ solution in a matrix of glass fiber have been used as electrolyte, in the double layer capacitors. The different double layer capacitors (DLCs) have been evaluated by electrochemical impedance spectroscopy. The capacitor with a recast Nafion electrolyte exhibits a proton conductivity of about 3×10⁻² S cm⁻¹ at ambient temperature, that is higher of that reported for solid electrolytes (10⁻³ to 10⁻⁴ S cm⁻¹) in the current literature on capacitors. A maximum of specific capacitance of 13 F/g of active materials (carbon+Nafion) corresponding to 52 F/g for a single electrode measured in a three-electrode arrangement has been achieved with the capacitor with recast Nafion. The capacitance of the capacitor with recast Nafion electrolyte, evaluated in low-frequency region below 10 mHz, was practically equivalent at that with sulphuric acid electrolyte. The interpretation of the characteristics of the microporous structure of carbon material of the electrodes by impedance analysis is also discussed.     

Effects of platinum loading on performance of proton-exchange membrane fuel cells using surface-modified Nafion® membranes

The interface between the electrolyte and electrode catalyst plays an important role in determining the performance of proton-exchange membrane fuel cells (PEMFCs) since the electrochemical reactions take place at the interface in contact with the reactant gases. To enhance catalyst activity by enlarging the interfacial area, the surface of a Nafion^® membrane is roughened by Ar⁺ ion beam bombardment that does not change the chemical structure of the membrane, as confirmed by FT-IR spectra. Among the membranes treated with ion dose densities of 0, 10¹⁵, 10¹⁶, 5 × 10¹⁶ and 10¹⁷ ions cm⁻² at ion energy of 1 keV, the membrane treated at ion dose density of 5 × 10¹⁶ ions cm⁻² exhibits the highest performance. Using the untreated and the treated membrane with 5 × 10¹⁶ ions cm⁻², the effects of platinum loading on cell performance are examined with Pt loadings of 01, 0.2, 0.3, 0.4 and 0.55 mg cm⁻². Except for a Pt loading of 0.55 mg cm⁻² where mass transport limits the cell performance, the single cell using a treated membrane gives a higher performance than that using an untreated membrane. This implies that the cell performance can be improved and the Pt loading can be reduced by ion beam bombardment.     

Solid oxide fuel cells operated by internal partial oxidation reforming of iso-octane

Two types of solid oxide fuel cells (SOFCs), with thin Ce_0.85Sm_0.15O_1.925 (SDC) or 8 mol% Y₂O₃-stabilized ZrO₂ (YSZ) electrolytes, were fabricated and tested with iso-octane/air fuel mixtures. An additional Ru–CeO₂ catalyst layer, placed between the fuel stream and the anode, was needed to obtain a stable output power density without anode coking. Thermodynamic analysis and catalysis experiments showed that H₂ and CO were primary reaction products at ≈750 °C, but that these decreased and H₂O and CO₂ increased as the operating temperature dropped below ≈600 °C. Power densities for YSZ cells were 0.7 W cm⁻² at 0.7 V and 790 °C, and for SDC cells were 0.6 W cm⁻² at 0.6 V and 590 °C. Limiting current behavior was observed due to the relatively low (≈20%) H₂ content in the reformed fuel.