Operating characteristics of direct methanol fuel cell using a platinum–ruthenium catalyst supported on porous carbon prepared from mesophase pitch

The characteristics of a platinum–ruthenium catalyst supported on porous carbon (PC) are analysed by X-ray diffraction, scanning electron microscopy, cyclic voltammetry and chemisorption techniques. Single-cell tests are carried out in order to compare the performance of these catalysts as an anode in a direct methanol fuel cell with respect to that of a commercial-grade catalyst. The methanol oxidation rate on a Pt–Ru catalyst supported on PC with a pore size of 20 nm is about 35% higher than that on a commercial E-TEK catalyst. The catalyst (Pt–Ru/K20) in the single-cell test gives a power density of 90 and 126 mW cm⁻² under air and oxygen at 60 °C, respectively. These values are 15–16% higher than those obtained with a commercial E-TEK catalyst.     

Effect of support materials on the performance of direct ethanol fuel cell anode catalyst

Pt–Ru catalysts supported on mesoporous carbon nitride (MCN), multiwall carbon nano tubes (MWCNTs), treated MWCNTs (t-MWCNTS) and Vulcan-XC were prepared using co-impregnation reduction method for the oxidation of ethanol in direct ethanol fuel cell (DEFC) to study the effect of support material. The MCN support was prepared using SBA-15 as template and t-MWCNTs were prepared by refluxing in HNO₃ and H₂SO₄ mixture (1:3) using MWCNTs. XRD shows the formation of Pt–Ru bi-metallic catalyst with size ranges from 7 to 17 nm using different supports. The catalyst and its supports were characterized by physically and electrochemically. Linear sweep voltammetry, cyclic voltammetry and chrono amperometry studies of the above systems reveal that MCN supported Pt–Ru catalyst shows higher electro-catalytic activity towards ethanol oxidation compared to Pt–Ru in treated t-MWCNTs, MWCNts and Vulcan-XC supports. The performance of DEFC based on maximum power density is found to be in the order Pt–Ru/MCN > Pt–Ru/t-MWCNTs > Pt–Ru/MWCNTs > Pt–Ru/Vulcan-XC. The Pt–Ru/MCN shows highest power density of 61.1 mW cm⁻² at 100 °C, 1 bar pressure with catalyst loading of 2 mg cm⁻² using 2 M ethanol feed.     

Direct alkaline fuel cell for multiple liquid fuels: Anode electrode studies

A direct alkaline fuel cell with a liquid potassium hydroxide solution as an electrolyte is developed for the direct use of methanol, ethanol or sodium borohydride as fuel. Three different catalysts, e.g., Pt-black or Pt/Ru (40 wt.%:20 wt.%)/C or Pt/C (40 wt.%), with varying loads at the anode against a MnO₂ cathode are studied. The electrodes are prepared by spreading the catalyst slurry on a carbon paper substrate. Nickel mesh is used as a current-collector. The Pt–Ru/C produces the best cell performance for methanol, ethanol and sodium borohydride fuels. The performance improves with increase in anode catalyst loading, but beyond 1 mg cm⁻² does not change appreciably except in case of ethanol for which there is a slight improvement when using Pt–Ru/C at 1.5 mA cm⁻². The power density achieved with the Pt–Ru catalyst at 1 mg cm⁻² is 15.8 mW cm⁻² at 26.5 mA cm⁻² for methanol and 16 mW cm⁻² at 26 mA cm⁻² for ethanol. The power density achieved for NaBH₄ is 20 mW cm⁻² at 30 mA cm⁻² using Pt-black.     

A comparative study of electrochemical methods on Pt–Ru DMFC anode catalysts: The effect of Ru addition

In the present study comparative electrochemical study of methanol electro-oxidation reaction, the effect of ruthenium addition and experimental parameters on methanol electro-oxidation reaction at high performance carbon supported Pt and Pt–Ru catalysts have been studied by cyclic voltammetry (CV), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) in H₂SO₄ (0.05–2.00 M) + CH₃OH (0.01–4.00 M) at 20–70 °C. Tafel plots for the methanol oxidation reaction on Pt and Pt–Ru catalysts show reasonably well-defined linear region with the slopes of 128–174 mV dec⁻¹(α = 0.34–0.46). The activation energies from Arrhenius plots have been found as 39.06–50.65 kJ mol⁻¹. As a result, methanol oxidation is enhanced by the addition of ruthenium. Furthermore, Pt–Ru (25:1) catalyst shows best electro–catalytic activity, higher resistance to CO, and better long term stability compared to Pt–Ru (3:1), Pt–Ru (1:1), and Pt. Finally, the EIS measurements on Pt–Ru (25:1) catalyst reveals that methanol electro-oxidation reaction consists of two process: methanol dehydrogenation step at low potentials (<700 mV) and the oxidation removal of CO_ads by OH_ads at higher potentials (>700 mV).     

Mesoporous carbon supported PtRu as anode catalyst for direct methanol fuel cell: Polarization measurements and electrochemical impedance analysis of mass transport

The performance of membrane electrode assembly (MEA) prepared with PtRu nanoparticles supported on a mesoporous carbon as anode catalyst are presented and compared against PtRu synthesized over Vulcan carbon. Polarization and power curves were obtained using 1 M methanol aqueous solution at the anode and O₂ at the cathode. The mesoporous carbon supported catalyst shows peak power of 40 mW cm⁻² and 67 mW cm⁻² at 30 °C and 60 °C respectively, that is, 15–30% higher than the Vulcan supported catalyst, and exhibits a wider range of operating current. Moreover, an improvement in the mass transport is observed for the catalyst supported on mesoporous carbon, yielding a lower voltage drop at high current density. This behavior was confirmed by electrochemical impedance spectroscopy (EIS), where an increases of the Warburg coefficient value by a factor 3–4 for the catalyst supported on mesoporous carbon as compared with that supported on Vulcan, would indicate a more facile diffusion of methanol through the mesoporous carbon.     

Electrochemical impedance studies on carbon supported PtRuNi and PtRu anode catalysts in acid medium for direct methanol fuel cell

The anodic Pt–Ru–Ni/C and the Pt–Ru/C catalysts for potential application in direct methanol fuel cell (DMFC) were prepared by chemical reduction method. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measurements were carried out by using a glassy carbon working electrode covered with the catalyst powder in a solution of 0.5 mol L⁻¹ CH₃OH and 0.5 mol L⁻¹ H₂SO₄ at 25 °C. EIS information discloses that the methanol electrooxidation on the Pt–Ru–Ni/C catalyst at various potentials shows different impedance behaviors. The mechanism and the rate-determining step of methanol electrooxidation are changed with increasing potential. Its rate-determining steps are the methanol dehydrogenation and the oxidation reaction of adsorbed intermediate CO_ads and OH_ads in low (400–500 mV) and high (600–800 mV) potentials, respectively. The catalytic activity of the Pt–Ru–Ni/C catalyst is higher for methanol electrooxidation than that of the Pt–Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol dehydrogenation is also better than that of the Pt–Ru/C catalyst.     

Stability and durability of PtRu catalysts supported on carbon nanofibers for direct methanol fuel cells

The chemical stability and durability of PtRu catalysts supported on carbon nanofibers (CNFs) for the anode electrode of a direct methanol fuel cell (DMFC) are investigated by Pt and Ru dissolution tests in sulfuric acid and long-term performance tests of a single cell discharging at a constant current density of 150 mA cm⁻² for approximately 2000 h. A CNF with a herringbone-type structure, which is characterized by the alignment of graphene symmetrically angled to the fiber axis, was selected as the catalyst support because it has an edge-rich surface and a high surface area. In the metal dissolution test, the PtRu/CNF catalysts showed 1.5–2 times lower Ru leaching than a tested commercial catalyst (supported on activated carbon). The results of long-term performance tests also prove the higher durability of the anode catalyst compared with the commercial catalyst, when the anode polarization is compared before and after operation for 2000 h. Some analytical measurements, including X-ray diffraction, energy dispersive spectroscopy, and transmission electron microscopy were conducted to study the degradation of the catalyst activity.     

Electrochemical synthesis and characterization of carbon-supported Pt and Pt–Ru nanoparticles with Cu cores for CO and methanol oxidation in polymer electrolyte fuel cells

Pt and Pt–Ru shells on Cu cores supported on Vulcan carbon XC72R have been synthesized and tested as possible anode electrocatalysts for polymer electrolyte fuel cells. Pt(Cu)/C was prepared by Cu electrodeposition on the black carbon support at constant potential followed by Pt deposition on Cu by galvanic exchange, whereas Pt–Ru(Cu)/C was prepared by spontaneous deposition of Ru species on Pt(Cu)/C. The corresponding cyclic voltammograms in 0.5 M H₂SO₄ solution showed the hydrogen adsorption/desorption peaks and no Cu oxidation. The respective CO stripping peak potentials of Pt(Cu)/C and Pt–Ru(Cu)/C were about 0.1 and 0.2 V more negative than those corresponding to Pt/C and Ru-decorated Pt/C. The best conditions for CO oxidation were found for Cu deposition potentials between −0.2 and −0.4 V vs. Ag/AgCl/KCl(sat). The Pt economy of the Pt–Ru(Cu)/C system was proved for the methanol oxidation, with specific currents more than twice those obtained on the Ru-decorated commercial Pt/C catalysts.     

Characterization and performance evaluation of Pt–Ru electrocatalysts supported on different carbon materials for direct methanol fuel cells

The paper addresses the effect of the carbon support on the microstructure and performance of Pt–Ru-based anodes for direct methanol fuel cells (DMFC), based on the study of four electrodes with a carbon black functionalized with HNO₃, a mesoporous carbon (CMK-3), a physical mixture of TiO₂ and carbon black and a reference carbon thermally treated in helium atmosphere (HeTT). It is shown that CMK-3 hinders the growth of the electrocatalyst nanoparticles (2.7 nm) and improves their distribution on the support surface, whereas the oxidized surfaces of HNO₃ carbon and TiO₂+carbon lead to larger (4–4.5 nm), agglomerated particles, and the lowest electrochemical active areas (54 and 26 m² g⁻¹, in contrast with 90 m² g⁻¹ for CMK-3), as determined from CO stripping experiments. However, HNO₃ and TiO₂ are characterized by the lowest CO oxidation potential (0.4 V vs. RHE), thus suggesting higher CO tolerance for the se electrodes. Tests in DMFC configuration show that the three modified electrodes have clearly better performance than the reference HeTT. The highest power density attained with electrodes supported on carbon treated with HNO₃ (65 mW cm⁻²/300 mA cm⁻² at 90 °C) and the equally interesting performance of the TiO₂-based electrodes (53 mW cm⁻²/300 mA cm⁻²), is a strong indication of the positive effect of the presence of oxygenated groups on the methanol oxidation reaction. The results are interpreted in order to identify separate microstructural (electrocatalyst particle size, porosity) and compositional (oxygenated surface groups, presence of oxide phase) effects on the electrode performance.     

Methanol electrooxidation on synthesized PtRu nanocatalyst supported on acetylene black in half cell and in direct methanol fuel cell

We reported the direct reduction of H₂PtCl₆ and RuCl₃ solution containing acetylene black powder by Na₂S₂O₄ to make Pt–Ru (20–10 wt%) supported on acetylene black (Pt–Ru/AB) as a nanocatalyst for methanol electrooxidation in acidic media. The electrochemical activity of catalyst was studied by electrochemical impedance spectroscopy, linear sweep voltammetry, cyclic voltammetry and chronoamperometry. Structural aspects of the Pt–Ru (20–10 wt%)/AB were studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The analysis of electrochemical results indicated lower charge transfer resistance, higher peak current for Pt–Ru (20–10 wt%)/AB compared to the commercial catalyst, Pt–Ru (20–10 wt%)/carbon Vulcan. XRD spectra verified a face centered cubic structure for the synthesized Pt–Ru/AB and its particle size was mostly 10 nm according to TEM and XRD images. In DMFC, Pt–Ru/AB had superior performance compared to the commercial catalyst in all current densities, which could be attributed to enhancement of the methanol oxidation kinetics, higher conductivity, and more uniform distribution of the ionomer in anode catalyst layer.     

Methanol-tolerant cathode electrode structure composed of heterogeneous composites to overcome methanol crossover effects for direct methanol fuel cell

A methanol-tolerant cathode electrode composed of heterogeneous composites was developed to overcome CO poisoning and large O₂ mass transfer overpotential generated by methanol crossover as well as the limitation of a single alloy catalyst with methanol-tolerance in direct methanol fuel cells (DMFCs). Two additives, PtRu black and PTFE particles, were well distributed in the Pt/C matrix of the cathode electrode, and had significant effects upon open circuit voltage (OCV) and performance. A small amount of PtRu black protected the Pt surface during the oxygen reduction reaction (ORR) by decreasing CO poisoning. In addition, hydrophobic PTFE particles reduced the O₂ mass transfer overpotential induced by water and permeated methanol in the cathode. Despite only 0.5 mg cm⁻² of metal catalysts in the cathode, the membrane electrode assembly (MEA) with 3 M methanol showed high performance (0.117 W cm⁻²), which was larger than that of the traditional MEA (0.067 W cm⁻²).     

Silicotungstic acid stabilized Pt–Ru nanoparticles supported on carbon nanofibers electrodes for methanol oxidation

Silicotungstic acid stabilized Pt–Ru nanoparticles supported on Functionalized Carbon Nanofibers have been prepared by a microwave-assisted polyol process. The samples were characterized by XRD, SEM and TEM analysis. The electro-catalytic activities of the prepared composites (20% Pt–Ru/STA–CNF) were examined by using Cyclic Voltammetry (CV) for oxidation of methanol. The electro-catalytic activity of the carbon nanofiber based composite (20% Pt–Ru/STA–CNF) electrode for methanol oxidation showed better performance than that of commercially available Johnson Mathey 20% Pt–Ru/C and 20% Pt–Ru/STA–C catalyst. The results imply that carbon nanofiber based STA composite electrodes are excellent potential candidates for application in direct methanol fuel cells.     

Effect of carbon substrate materials as a Pt–Ru catalyst support on the performance of direct methanol fuel cells

The support effect of carbon nanotubes (CNTs) for direct methanol fuel cell (DMFC) was studied using CNTs with and without defect preparation, carbon black, and fishbone-type CNTs. The Pt–Ru/defect-free CNTs afforded the highest catalytic activity of methanol oxidation reaction (MOR) in rotating disk electrode experiments and the highest performance as the anode catalysts in DMFC single cell tests with the one-half platinum loading compared to Pt–Ru/VulcanXC-72R. CO stripping voltammograms with Pt–Ru/defect-free CNTs also revealed the lowest CO oxidation potential among other Pt–Ru catalysts using different carbon support. It is thus considered that the carbon substrates significantly affect the CO oxidation activity of anode electrocatalysts in DMFC. This is ascribed to the geometrical effect that the flat interface between CNTs and metal catalysts has a unique feature, at which the electron transfer occurs, and this interface would modify the catalytic properties of Pt–Ru particles.     

Effects of the microstructure and powder compositions of a micro-porous layer for the anode on the performance of high concentration methanol fuel cell

To investigate the effects of the microstructure and powder compositions for the micro-porous layer (MPL) of an anode on the cell performance of a direct methanol fuel cell (DMFC) using a highly concentrated methanol solution up to 7 M, various powders and their compositions were applied as a filler of the MPL in the membrane electrode assembly (MEA). Several nano- and microstructured carbons such as commercial carbon black (CB), spherical activated carbon (AC), multi-walled carbon nanotube (MWCNT), and platelet carbon nanofiber (PCNF) were selected with different morphology and surface properties, and a meso-porous silica (one of SBA series) was also included for its porous and hydrophilic properties. The coating morphology and physical properties such as porosity and gas permeability were measured, and electrochemical properties of MEA with the MPL were examined by using current–voltage polarization, electrochemical impedance spectroscopy, and voltammetric analyses. A mixture of different carbons was found to be effective for lowering methanol crossover with sustaining electrical conductivity and gas permeability. A MEA with modified-anode MPLs made of CB (50 vol%) and PCNF (50 vol%) powders showed a maximum power density of 67.7 mW cm⁻² under operation with a 7 M concentration of methanol.     

Inkjet printing of carbon supported platinum 3-D catalyst layers for use in fuel cells

We present a method of using inkjet printing (IJP) to deposit catalyst materials onto gas diffusion layers (GDLs) that are made into membrane electrode assemblies (MEAs) for polymer electrolyte fuel cell (PEMFC). Existing ink deposition methods such as spray painting or screen printing are not well suited for ultra low (<0.5 mg Pt cm⁻²) loadings. The IJP method can be used to deposit smaller volumes of water based catalyst ink solutions with picoliter precision provided the solution properties are compatible with the cartridge design. By optimizing the dispersion of the ink solution we have shown that this technique can be successfully used with catalysts supported on different carbon black (i.e. XC-72R, Monarch 700, Black Pearls 2000, etc.). Our ink jet printed MEAs with catalyst loadings of 0.020 mg Pt cm⁻² have shown Pt utilizations in excess of 16,000 mW mg⁻¹ Pt which is higher than our traditional screen printed MEAs (800 mW mg⁻¹ Pt). As a further demonstration of IJP versatility, we present results of a graded distribution of Pt/C catalyst structure using standard Johnson Matthey (JM) catalyst. Compared to a continuous catalyst layer of JM Pt/C (20% Pt), the graded catalyst structure showed enhanced performance.     

Improved fuel use efficiency in microchannel direct methanol fuel cells using a hydrophilic macroporous layer

We demonstrate state-of-the-art room temperature operation of silicon microchannel-based micro-direct methanol fuel cells (μDMFC) having a very high fuel use efficiency of 75.4% operating at an output power density of 9.25 mW cm⁻² for an input fuel (3 M aqueous methanol solution) flow rate as low as 0.55 μL min⁻¹. In addition, an output power density of 12.7 mW cm⁻² has been observed for a fuel flow rate of 2.76 μL min⁻¹. These results were obtained via the insertion of novel hydrophilic macroporous layer between the standard hydrophobic carbon gas diffusion layer (GDL) and the anode catalyst layer of a μDMFC; the hydrophilic macroporous layer acts to improve mass transport, as a wicking layer for the fuel, enhancing fuel supply to the anode at low flow rates. The results were obtained with the fuel being supplied to the anode catalyst layer via a network of microscopic microchannels etched in a silicon wafer.     

Suppressing methanol crossover with a deposited quaternary Pt-based catalyst on the Nafion surface

A Pt₄₉–Ru₃₅–Ir₆–Os₁₀ alloy layer is deposited on the Nafion membrane surface using the impregnation-reduction (IR) method to mitigate methanol crossover. The methanol crossover in a membrane electrode assembly (MEA) with a deposited Pt–Ru–Ir–Os layer is compared with a MEA without any layer on the proton exchange membrane (PEM). The deposited Pt₄₉–Ru₃₅–Ir₆–Os₁₀ layer functions like a catalytically active layer, a methanol barrier, and an electrode all at the same time. This layer yields up to a 30% suppression of methanol crossover and a 15% improvement in fuel cell voltage performance (@170 mA cm⁻²) at 80 °C. The porous metal alloy layer with a high surface area of the Pt–Ru layer suppresses methanol crossover by the catalytic activity of the deposited layer. The presence of the solid Pt₄₉–Ru₃₅–Ir₆–Os₁₀ layer on the Nafion membrane surface reduces the proton conductivity of the PEM (from 10.75 to 4.22 mS cm⁻¹), and degrades the output of the cell voltage performance (from 0.350 to 0.335 V at 90 mA cm⁻² of current density) at 60 °C, even though methanol crossover is reduced (from 6928 ppm to 4415 ppm (CO₂ concentration at cathode exhaust is proportional to methanol crossover)).     

Performance of PVDF supported silica immobilized phosphotungstic acid membrane (Si-PWA/PVDF) in direct methanol fuel cell

PVDF supported silica-immobilized phosphotungstic acid membrane (Si-PWA/PVDF) was synthesized by impregnation of silica immobilized phosphotungstic acid particles in porous PVDF film. Pore size distribution as well as stability of membrane in oxidative environment was determined using Fenton's reagent test. Stability of membrane against leaching of PWA which provides ion exchanging capacity was also determined and found to be adequate. Properties which affect performance of membrane in DMFC like water uptake, methanol cross-over and proton conductivity were measured. Water uptake of the membrane increased from 30.3% to 37.9% as the temperature was increased from 25 °C to 80 °C. The proton conductivity of the membrane increased from 4.3 mS cm⁻¹ to 20 mS cm⁻¹ with increase in the temperature from 25 °C to 80 °C. Methanol uptake of the Si-PWA/PVDF membrane was low compared to Nafion membrane and changed by very small amount with increase in temperature. Effect of operating parameters on performance of direct methanol fuel cell (DMFC) with the synthesized Si-PWA/PVDF was determined. DMFC performance improved on increasing temperature. As the temperature was increased from 25 °C to 60 °C, open circuit voltage (OCV) increased from 0.685 V at 0.815 V and the peak power density increased from 21.4 mW cm⁻² to 44.0 mW cm⁻². Maximum peak power density was obtained with 1 M methanol concentration and 60% relative humidity. Peak power density decreased with further increase in both methanol concentration and relative humidity.     

Polymer electrolytes based on sulfonated polysulfone for direct methanol fuel cells

This paper reports the development and characterization of sulfonated polysulfone (SPSf) polymer electrolytes for direct methanol fuel cells. The synthesis of sulfonated polysulfone was performed by a post sulfonation method using trimethyl silyl chlorosulfonate as a mild sulfonating agent. Bare polysulfone membranes were prepared with two different sulfonation levels (60%, SPSf-60 and 70%, SPSf-70), whereas, a composite membrane of SPSf-60 was prepared with 5 wt% silica filler. These membranes were investigated in direct methanol fuel cells (DMFCs) operating at low (30–40 °C) and high temperatures (100–120 °C). DMFC power densities were about 140 mW cm⁻² at 100 °C with the bare SPSf-60 membrane and 180 mW cm⁻² at 120 °C with the SPSf-60-SiO2 composite membrane. The best performance achieved at ambient temperature using a membrane with high degree of sulfonation (70%, SPSf-70) was 20 mW cm⁻² at atmospheric pressure. This makes the polysulfone-based DMFC suitable for application in portable devices.     

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.