Pt nanowires prepared via a polymer template method: Its promise toward high Pt-loaded electrocatalysts for methanol oxidation

Platinum nanowires were prepared via a template-synthesis method by electrodeposition of platinum within pores of a track-etched polycarbonate (PCTE) membrane, followed by chemical etching to separate the Pt nanowires from the polymer. The structure and morphology of the Pt nanowires were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM), revealing a polycrystalline phase with nanowire dimension up to 6 μm long and ca. 47 ± 9.8 nm of diameter. The unsupported Pt nanowires showed the better electrochemical mass activities over the methanol electro-oxidation than supported or unsupported Pt nanoparticles under the high Pt content-loaded conditions that is typically required for direct methanol fuel cells. This enhancement could be rationalized by its unique physicochemical and electrical properties arising from the inherent anisotropic one-dimensional (1D) nanostructure, such as charge transfer facilitation by reducing number of particle interfaces and more efficient use of Pt by alleviating fraction of embedded catalysts.     

直接甲醇燃料电池

介绍了直接甲醇燃料电池的原理、结构,并与发展较早的氢气燃料电池进行优劣比较。针对近期商业化便携式燃料电池的技术指标,主要讨论了直接甲醇燃料电池在性能和成本上的现状和问题,并着重阐述了阳极催化剂和电解质膜(决定其性能的两个关键因素)的研发进展。     

聚合物溶液的弹性对残余油滴变形的影响

针对亲油岩石水驱后残余油膜的存在形式及聚合物溶液的粘弹特性,选取上随体Maxwell本构方程。使用计算流体软件Polyflow对模型进行数值分析,分析聚合物溶液弹性对残余油滴的变形影响。     

电流中断法在线测定直接甲醇燃料电池的欧姆阻抗

Electrochemical impedance spectroscopy (EIS) is widely used in fuel cell impedance analysis. However, for ohmic resistance (RΩ), EIS has some disadvantages such as long test period and complex data analysis with equivalent circuits. Therefore, the current interruption method is explored to measure the value of RΩ in direct methanol fuel cells (DMFC) at different temperatures and current densities. It is found that RΩ decreases as temperature increase, and decreases initially and then increases as current density increases. These results are consistent with those measured by the EIS technique. In most cases, the ohmic resistances with current interruption (RiR) are larger than those with EIS (REIS), but the difference is small, in the range from –0.848% to 5.337%. The errors of RiR at high current densities are less than those of REIS. Our results show that the RiR data are reliable and easy to obtain in the measurement of ohmic resistance in DMFC.     

Sulfonated polyether sulfone‐poly(vinylidene fluoride) blend membrane for DMFC applications

Direct methanol fuel cell (DMFC) proton exchange membranes were prepared by blending poly (vinylidene fluoride) (PVDF) with sulfonated poly(ether sulfone) (SPES). Using a diffusion cell and gas chromatographic technique, the effects of PVDF content on methanol permeability in the blended membranes were investigated. The thermal resistance and proton conductivity of the membranes were also determined by using a thermal gravimetric analysis (TGA) and an impedance analysis technique respectively. The presence of sulfonic acid groups in SPES was confirmed by Fourier transform infrared (FTIR). It was found that the methanol permeability in the blended membranes decreased with PVDF content at the expense of proton conductivity. Blended membranes show methanol permeability values much lower than that of Nafion 115, whereas the proton conductivities of the membranes are comparable with that of Nafion. The thermal stability of these blended membranes is above 250°C, which is sufficiently high for use in DMFC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A novel nanocomposite catalytic cathode for direct methanol fuel cells

We report a new nanocomposite catalytic cathode composed of iron phthalocyanine, platinum, carbon black and Nafion^® (FePc-Pt/C-Nafion^®) which exhibited enhanced catalytic activity for the oxygen reduction reaction (ORR) in the presence of methanol compared with usual Pt/C based electrodes. The catalytic cathode was prepared by depositing Pt colloidal nanoparticles (d_av = 2.2 nm) on a FePc/C support to form a FePc-Pt/C powder and ultrasonically treating a mixture of Nafion^® and the FePc-Pt/C powder in ethanol, followed by loading the mixture on a glassy carbon electrode and drying at 120 °C. In an O₂-saturated H₂SO₄ solution (0.5 M) with methanol (0.5 M), the onset potential (0.92 V vs RHE) over the FePc-Pt/C-Nafion^® electrode shifted by more than 240 mV toward positive relative to that over an electrode prepared with a commercial Pt/C catalyst and Nafion^®. A new kind of catalytic sites constructed by FePc nanocrystals and Pt nanoparticles was found in the FePc-Pt/C-Nafion^® electrode for the first time, which exhibited higher specific activity for ORR than Pt as calculated based on the hydrogen desorption charge.     

Effect of cathode catalyst layer thickness on methanol cross-over in a DMFC

The effects of cathode catalyst layer (CCL) thickness on the detrimental effect of methanol cross-over in a direct methanol fuel cell (DMFC) under various operating conditions are studied. Three membrane electrode assemblies (MEAs) with different CCL thicknesses but identical catalyst loading and identical anode catalyst layer are used. The results show that, when a thicker CCL, approximately twice the thickness of the base case, is used, the fuel cell performance increases significantly. The increase in performance with a thicker CCL is attributed to the oxidation of the methanol crossed-over in part of the catalyst layer and leaving the rest of the catalyst layer free from methanol contamination, leading to mitigations of the effects of mixed potentials. The results of electrochemical impedance spectroscopy (EIS) show that the charge transfer resistance for the fuel cell with twice the thickness of CCL is 30% lower compared to that for the base case, indicating that the active catalyst area available for oxygen reduction reaction (ORR) is indeed greater. The results of the electrochemical active surface areas (ECA) show that without methanol contamination, the ECA of the thicker CCL is actually lower, indicating that the better performance and the lower charge transfer resistance are not caused by a higher original ECA, but a higher active area for ORR. A much thicker CCL, about 5 times of that for the base case, is also used and the cell performance is also higher than that for the base case. The experimental results show that there exists an optimum cathode catalyst layer thickness and the thickness of cathode catalyst layer has a significant effect on DMFC performance.     

DMFC阳极催化剂用GRQD-NiCo2O4复合物的制备与电催化活性分析

采用水热法制备GRQD-NiCo₂O₄复合物,利用XRD、SEM及TEM分析其微结构,并探讨其作为DMFC阳极催化剂使用时的电化学性能。微结构分析表明所得GRQD-NiCo₂O₄复合物皆为具NiCo₂O₄单一相的尖晶石结构,且GRQD质量浓度高于0.25 g/mL后表面形貌将转变GRQD与NiCo₂O₄相互结合的状态。电化学分析表明添加GRQD可有效增强NiCo₂O₄的导电性并提升其电化学稳定性,其中GRQD质量浓度为0.25 g/mL时所得样品经500次循环测试后电流密度约为77.5 A/g,与循环5次后相比其电流密度剩余量最大（约为69.7%）,该样品作为DMFC阳极催化剂使用时性价比最佳。     

Hot wire chemical vapor deposition: limits and opportunities of protecting the tungsten catalyzer from silicide with a cavity

Hot Wire Chemical Vapor Deposition (HW-CVD) is one of the most promising techniques for depositing the intrinsic microcrystalline silicon layer for the production of micro-morph solar cells. However, the silicide formation at the colder ends of the tungsten wire drastically reduces the lifetime of the catalyzer, thus limiting its industrial exploitation. A simple but interesting strategy to decrease the silicide formation is to hide the electrical contacts of the catalyzer in a long narrow cavity which reduces the probability of the silane molecules to reach the colder ends of the wire. In this paper, the working mechanism of the cavity is elucidated. Measurements of the thickness profile of the silicon deposited in the internal walls of the cavity have been compared with those predicted using a simple diffusion model based on the assumption of Knudsen flow. A lifetime study of the protected and unprotected wires has been carried out. The different mechanisms which determine the deterioration of the catalyzer have been identified and discussed.     

Analysis of the diffusive mass transport in the anode side porous backing layer of a direct methanol fuel cell

In this work we present an analysis of the mass transport in the anode side porous backing layer of a direct methanol fuel cell (DMFC). The effective transport coefficient of different backing layers at various compressions was measured and compared to two different literature models and a single particle random walk simulation which accounts for details of the geometrical fibre microstructure. Based on the measured values of the effective transport coefficient limiting current densities for diffusive transport were calculated taking into account geometric boundary conditions and anisotropic and inhomogeneous backing layer properties. Comparison with the measured values for the limiting current in fuel cell operation shows qualitative agreement. A systematic underestimation indicates that also other transport processes contribute significantly to the mass transfer at the used experimental setup.