Electrocatalysts and membrane for direct ethanol-oxygen fuel cell with alkaline electrolyte

Results of studies of anodic (RuNi/C) and cathodic (PtCo/C; CoN₄/C) catalysts, polybenzimidazole membrane, and membrane-electrode assemblies on their basis for alkaline ethanol-oxygen fuel cell are presented. It is shown that the anodic catalyst RuNi/C optimized in its composition (Ru: Ni = 68: 32 in atomic percent) and the metal mass on carbonaceous support (15–20%) is sufficiently effective with respect to ethanol oxidation; it is well superior to commercial Pt/C- and RuPt/C-catalysts when calculated per unit mass of the precious metal. The effect of electrolyte composition, electrode potential, and temperature on the CO₂ yield is studied by chromatographic analysis of the ethanol oxidation products. It is shown that the highest CO₂ yield (the process involves the C-C bond break) is achieved at low electrolysis overvoltage and elevated temperature. The mean number of electrons given up by C₂H₅OH molecule approaches 10 at temperatures over 60°C. The studied cathodic catalysts form the following series of their specific activity in the oxygen reduction reaction: (20 wt % Pt) E-TEK ≥ (7.3 wt % Pt) PtCo/C > CoN₄/C; however, in the presence of alcohol the activity series is reversed. On this reason fuel cell cathodes were prepared by using synthesized CoN₄/C-catalyst. For the alkali-doped polybenzimidazole membrane the conductivity and ethanol crossover were determined. A membrane-electrode assembly for platinum-free alkaline ethanol-oxygen fuel cell is designed. It comprised anodic (RuNi/C) and cathodic (CoN₄/C) catalysts and polybenzimidazole membrane. The period of service of the fuel cell exceeded 100 h at a voltage of 0.5 V and current of 100 mA/cm².     

Total harmonic distortion analysis for direct methanol fuel cell anode

In this study, total harmonic distortion (THD) analysis is put forward to illustrate nonlinear behavior of direct methanol fuel cell (DMFC) anode. THD simulations by means of different methanol oxidation kinetics as well as its experimental validation are both carried out. It is shown that the THD model adopting a three-step methanol oxidation mechanism with Kauranen–Frumkin/Temkin kinetics can be used to illustrate the THD variation for DMFC anode qualitatively. The experimental THD response at the frequency range from 0.063 Hz to 0.4 Hz is identified as the reflection of the nonlinearity variation of those kinetic steps involving intermediates in the methanol oxidation. In such a frequency domain, THD value decrease monotonously with decreasing methanol concentration, which notices its accessibility on methanol concentration detection.     

Polymer electrolyte membranes for the direct methanol fuel cell: A review

The direct methanol fuel cell (DMFC) has the potential to replace lithium‐ion rechargeable batteries in portable electronic devices, but currently experiences significant power density and efficiency losses due to high methanol crossover through polymer electrolyte membranes (PEMs). Numerous publications document the synthesis and characterization of new PEMs for the DMFC. This article reviews this research, transport phenomena in PEMs, and experimental techniques used to evaluate new PEMs for the DMFC. Although many PEMs do not show significant improvements over Nafion®, the benchmark PEM in DMFCs, experimental results show that several new PEMs exhibit lower methanol crossover at similar proton conductivities and/or higher DMFC power densities. These results and recommendations for future research are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Parts B: Polym Phys 44: 2201–2225, 2006     

Tolerant cathode catalysts for direct methanol fuel cell

Effect of methanol on the reduction kinetics of oxygen on highly dispersed catalysts 60Pt/C (HiSPEC 9100), 40Pt/carbon nanotubes, and CoFe/carbon nanotubes for the cathode of a direct methanol-oxygen fuel cell was studied. It was shown that the CoFe/carbon nanotubes catalyst surpasses the platinum systems in tolerance to the alcohol. It was found that the tolerance of the cathode catalyst strongly affects the current–voltage characteristics of the fuel cell, which is the principal result of the study and constitutes its scientific novelty. The maximum power density of an alkaline methanol-oxygen fuel cell with nonplatinum cathode (260 mW cm^–2) exceeds the characteristics of similar fuel cells with platinum cathode catalysts, both obtained in the present study and described in the literature, which points to the practical importance of the study.     

Novel fluoropolymer anion exchange membranes for alkaline direct methanol fuel cells

A series of novel fluoropolymer anion exchange membranes based on the copolymer of vinylbenzyl chloride, butyl methacrylate, and hexafluorobutyl methacrylate has been prepared. Fourier transform infrared (FT-IR) spectroscopy and elemental analysis techniques are used to study the chemical structure and chemical composition of the membranes. The water uptake, ion-exchange capacity (IEC), conductivity, methanol permeability, and chemical stability of the membranes are also determined. The membranes exhibit high anionic conductivity in deionized water at 65 °C ranging from 3.86×10(-2) S cm(-1) to 4.36×10(-2) S cm(-1). The methanol permeability coefficients of the membranes are in the range of 4.21-5.80×10(-8) cm(2) s(-1) at 65 °C. The novel membranes also show good chemical and thermal stability. An open-circuit voltage of 0.7 V and a maximum power density of 53.2 mW cm(-2) of alkaline direct methanol fuel cell (ADMFC) with the membrane C, 1 M methanol, 1 M NaOH, and humidified oxygen are achieved at 65 °C. Therefore, these membranes have great potential for applications in fuel cell systems.     

Recent development of methanol electrooxidation catalysts for direct methanol fuel cell

Direct methanol fuel cells(DMFCs) are very promising power source for stationary and portable miniature electric appliances due to its high efficiency and low emissions of pollutants. As the key material, catalysts for both cathode and anode face several problems which hinder the commercialization of DMFCs.In this review, we mainly focus on anode catalysts of DMFCs. The process and mechanism of methanol electrooxidation on Pt and Pt-based catalysts in acidic medium have been introduced. The influences of size effect and morphology on electrocatalytic activity are discussed though whether there is a size effect in MOR catalyst is under debate. Besides, the non Pt catalysts are also listed to emphasize though Pt is still deemed as the indispensable element in anode catalyst of DMFCs in acidic medium. Different catalyst systems are compared to illustrate the level of research at present. Some debates need to be verified with experimental evidences.     

A novel single electrode supported direct methanol fuel cell

In this paper a single electrode supported direct methanol fuel cell (DMFC) is fabricated and tested. The novel architecture combines the elimination of the polymer electrolyte membrane (PEM) and the integration of the anode and cathode into one component. The thin film fabrication involves a sequential deposition of an anode catalyst layer, a cellulose acetate electronic insulating layer and a cathode catalyst layer onto a single carbon fibre paper substrate. The single electrode supported DMFC has a total thickness of 3.88 × 10^?2 cm and showed a 104% improvement in volumetric specific power density over a two electrode DMFC configuration under passive conditions at ambient temperature and pressure (1 atm, 25 °C).     

Composite Nafion membrane embedded with hybrid nanofillers for promoting direct methanol fuel cell performance

A special type of hybrid nano-particles was incorporated into the Nafion^® matrix to form a composite membrane. These nano-particles possessed a core–shell structure consisting of silica core (<10 nm) and a densely grafted oligomeric ionmer layer, which was synthesized via atom transfer radical polymerization (ATRP) on the particles’ surface. Besides considerable improvement in the proton conductivity of the membrane, the presence of these hybrid nano-particles in the Nafion^® matrix also repressed its methanol permeability by almost four times. The composite membrane also demonstrated superior performance when tested in a single cell membrane-electrolyte assembly (MEA) under direct methanol fuel cell (DMFC) operating condition. It was found that the composite membrane enabled a power density output that was 1.5 times greater than that of pristine Nafion^®.     

Composite anode catalyst layer for direct methanol fuel cell

A novel composite anode catalyst layer for direct methanol fuel cell is reported in this paper. The dual-layer anode, which is based on the catalyst coated membrane technique, characterizes a morphological variety of the catalyst layer. The inner sub-layer with a dense morphology can effectively suppress methanol crossover. On the other hand, the outer sub-layer modified by the pore-forming agent, NH₄HCO₃ and the carbon nanotubes can enhance the electrochemical surface area and increase the catalyst utilization. The structural improvement of anode catalyst layer results in a 40% increment in maximum power density during the single cell test at 30 °C.     

Sulfonated polyethersulfone Cardo membranes for direct methanol fuel cell

Novel proton conducting membranes, sulfonated polyethersulfone Cardo (SPES-C), were prepared with concentrated sulfonic acid at room temperature. The degree of sulfonation was controlled by reaction time. Their proton conductivity and methanol permeability as a function of temperature were investigated. The SPES-C membranes with 70% DS were still not water soluble and had low degree of swelling. With the level of 70% sulfonation, proton conductivity was 0.011 S/cm at 80 °C, 0.0338 S/cm at 110 °C, which approached that of Nafion^® 115 membrane at the same conditions. Methanol permeability of SPES-C membranes was considerably smaller than that of Nafion^® 115 membrane over the temperature 25–80 °C.     

Compact bipolar plate-free direct methanol fuel cell stacks

Fuel cells with a PtAu/C anode and a Pr-doped Mn(2)O(3)/C cathode were stacked without using a bipolar plate, and their discharge properties were investigated in a methanol aqueous solution bubbled with air. A three-cell stack exhibited a stack voltage of 2330 mV and a power output of 21 mW.     

Preparation and characterization of CPPO/BPPO blend membranes for potential application in alkaline direct methanol fuel cell

A series of hydroxyl-conducting anion-exchange membranes were prepared by blending chloroacetylated poly(2,6-dimethyl-1,4-phenylene oxide) (CPPO) with bromomethylated poly(2,6-dimethyl-1,4-phenylene oxide) (BPPO), and their fuel cell-related performances were evaluated. The resulting membranes exhibited high hydroxyl conductivities (0.022–0.032 S cm⁻¹ at 25 °C) and low methanol permeability (1.35 × 10⁻⁷ to 1.46 × 10⁻⁷ cm² s⁻¹). All the blend membranes proved to be miscible or partially miscible under the investigations of scanning electron microscopy (SEM) and differential scanning calorimeters (DSC). By condition optimization, the blend membranes with 30–40 wt% CPPO are recommended for application in direct methanol alkaline fuel cells because they showed low methanol permeability, excellent mechanical properties and comparatively high hydroxyl conductivity.     

Microwave synthesis of polymer-embedded Pt-Ru catalyst for direct methanol fuel cell

Platinum-ruthenium nanoparticles stabilized within a conductive polymer matrix are prepared using microwave heating. Polypyrrole di(2-ethylhexyl) sulfosuccinate, or PPyDEHS, has been chosen for its known electrical conductivity, thermal stability, and solubility in polar organic solvents. A scalable and quick two-step process is proposed to fabricate alloyed nanoparticles dispersed in PPyDEHS. First a mixture of PPyDEHS and metallic precursors is heated in a microwave under reflux conditions. Then the nanoparticles are extracted by centrifugation. Physical characterization by TEM shows that crystalline and monodisperse alloyed nanoparticles with an average size of 2.8 nm are obtained. Diffraction data show that crystallite size is around 2.0 nm. Methanol electro-oxidation data allow us to propose these novel materials as potential candidates for direct methanol fuel cells (DMFC) application. The observed decrease in sulfur content in the polymer upon incorporation of PtRu nanoparticles may have adversely affected the measured catalytic activity by decreasing the conductivity of PPyDEHS. Higher concentration of polymer leads to lower catalyst activity. Design and synthesis of novel conductive polymers is needed at this point to enhance the catalytic properties of these hybrid materials.     

Proton exchange membrane using partially sulfonated polystyrene-b-poly(dimethylsiloxane) for direct methanol fuel cell

A diblock copolymer ionomer containing a rubbery poly(dimethylsiloxane) block has been developed as a proton exchange membrane for direct methanol fuel cell (DMFC). The partially sulfonated polystyrene-b-poly(dimethylsiloxane) (sPS-b-PDMS) membrane with 38% sulfonation degree exhibited 3 times lower methanol permeability and 2.6 times higher membrane selectivity (proton conductivity/methanol permeability) compared to Nafion^® 115 at 25 °C. Coexistence of microphase domains and ionic clusters was confirmed from the morphological studies by small-angle X-ray scattering and tapping-mode atomic force microscopy. Gas chromatographic analysis revealed that water/methanol selectivity of sPS-b-PDMS was 20 times higher than that of Nafion^® 115. Such a high water/methanol selectivity can be attributed to the existence of PDMS microdomains minimizing methanol permeation through hydrophilic ion channels. sPS-b-PDMS membranes were fabricated into membrane electrode assembly (MEA), and air-breathing DMFC test for these MEAs showed a better performance compared to the MEA composed of Nafion^® 115.     

Analyzing leakage current in a direct methanol fuel cell

Journal of Solid State Electrochemistry - A mathematical model is developed to study the transient leakage current in a direct methanol fuel cell (DMFC) system. The DMFC is divided into five...     

Poly(3,4-ethylenedioxythiophene)-modified nafion membrane for direct methanol fuel cells

Membranes Nafion 117 are modified with poly(3,4-ethylenedioxythiophene) (PEDT) by chemical polymerization of EDT with H₂O₂ or FeCl₃ as the oxidants in a two-compartment cell. Depending on the oxidant and polymerization conditions, PEDT is deposited either as a thin film on the membrane surface or inside the Nafion membrane depending on whether FeCl₃ or H₂O₂ is used as the oxidant. The decrease in the ionic conductivity and methanol permeability is studied as a function of the polymerization time. A linear dependence is found with H₂O₂ and a t ^−1/2 dependence, with FeCl₃. The contributions of PEDT and Nafion to the overall conductivity of the composite membranes are separated by impedance measurements. The modified membranes (FeCl₃) are also tested in direct methanol fuel cells (DMFC). The methanol permeation through the membranes is measured by operating the fuel cell in an electrolysis mode. The influence of the modified membranes on the DMFC current-voltage characteristics is studied with 2 M CH₃OH and O₂ at 1.2 bar_abs and 80°C. Membrane electrode assemblies (MEAs) are prepared by hot pressing the modified membrane between two commercial gas diffusion electrodes with 1 mg cm⁻² of Pt loading. A decrease of the methanol permeation of 25% is observed at MEA with the modified membrane (1 h polymerization time), compared with that of MEA with a Nafion membrane. However, the overall DMFC performance decreases in the same relation: a maximal power density of 36 W cm⁻² is measured at MEA with a PEDT-modified membrane compared with 45 W cm⁻² for MEA with a Nafion membrane. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 11, pp. 1330–1339. Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22, 2005, Moscow. The text was submitted by the authors in English.     

甲醇浓度对被动式自呼吸直接甲醇燃料电池性能的影响

依据单电池测试结果和甲醇传质理论考察了甲醇溶液的浓度对被动式自呼吸直接甲醇燃料电池（DMFC）性能的影响.研究结果表明,电池的法拉第效率和能量转化效率会随着浓度的增大而降低,采用4mol/L的甲醇溶液实现了最大的放电功率13.9mW/cm^2,并能在60mA下稳定放电长达20h.这取决于电池运行过程中电极内部的甲醇传质和甲醇透过的共同作用.     

A novel electrode architecture for passive direct methanol fuel cells

The supply of cathode reactants in a passive direct methanol fuel cell (DMFC) relies on naturally breathing oxygen from ambient air. The successful operation of this type of passive fuel cell requires the overall mass transfer resistance of oxygen through the layered fuel cell structure to be minimized such that the voltage loss due to the oxygen concentration polarization can be reduced. In this work, we propose a new membrane electrode assembly (MEA), in which the conventional cathode gas diffusion layer (GDL) is eliminated while utilizing a porous metal structure for transporting oxygen and collecting current. We show theoretically that the new MEA enables a higher mass transfer rate of oxygen and thus better performance. The measured polarization and constant-current discharging behavior showed that the passive DMFC with the new MEA yielded better and much more stable performance than did the cell having the conventional MEA. The EIS spectrum analysis further demonstrated that the improved performance with the new MEA was attributed to the enhanced transport of oxygen as a result of the reduced mass transfer resistance in the fuel cell system.