操作条件对DMFC阴极电化学阻抗谱参数的影响

通过降低阴极催化剂载量强化了阴极氧还原反应的电化学极化, 测量了不同操作条件下直接甲醇燃料电池(DMFC)的极化曲线和交流阻抗谱,并提出了改进的等效电路模型LR(CR)(QR(LR))用以分析温度、空气流量和甲醇流量对DMFC阴极电化学反应和传质极化过程的影响. 研究结果表明, 提高工作温度会导致更多的甲醇渗透到阴极, 加大阴极氧气还原反应的电荷转移电阻; 只有采用大的空气流量,才会有效地防止水淹, 加大氧气向催化剂层的传质, 促进阴极反应的进行; 适当提高甲醇的流量可以促进阳极和阴极电化学反应的进行, 但是过高的甲醇流速可能会降低电极表面的温度, 加剧甲醇的渗透.     

A new flow field design for polymer electrolyte-based fuel cells

We present a new flow field design, termed convection-enhanced serpentine flow field (CESFF), for polymer electrolyte-based fuel cells, which was obtained by re-patterning conventional single serpentine flow fields. We show theoretically that the CESFF induces larger pressure differences between adjacent flow channels over the entire electrode surface than does the conventional flow field, thereby enhancing in-plane forced flow through the electrode porous layer. This characteristic increases mass transport rates of reactants and products to and from the catalyst layer and reduces the amount of liquid water that is entrapped in the porous electrode, thereby minimizing electrode flooding over the entire electrode surface. We applied this new flow field to a single direct methanol fuel cell and demonstrated experimentally that the new flow field resulted in substantial improvements in both cell performance and operating stability as opposed to the conventional serpentine flow field design.     

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.     

Effect of convective channel-to-channel mass flow in a polymer electrolyte fuel cell

The effect of convective channel-to-channel mass flow on the local performance of a polymer electrolyte fuel cell (PEFC) air cathode is determined experimentally by using submillimeter resolved current density distribution measurements in channel and land areas. A special cell is employed, where the two parallel channels of the cathode flow field can be operated at different pressure. For isobaric operation of the channels (Δp = 0 mbar), the lateral current density distribution shows a distinct minimum in the land area between the channels as diffusive mass transport becomes limiting at a higher cell polarization. Toward higher Δp, the local cell performance in the land area improves initially as a result of an improving convective channel-to-channel mass flow. However, as the pressure difference exceeds a value of 10 mbar, no noteworthy additional benefit is observed with further increasing Δp. Under these conditions, the convective mass flow provides an abundant reactant supply in the land area and, since reactant depletion is no longer limiting, the lateral current density distribution is primarily governed by the local ohmic resistance. As a result, the current density exhibits a maximum in the land area, where the local ohmic resistance shows a minimum.     

Numerical simulation of a new operational regime for a polymer electrolyte fuel cell

A quasi-3D (Q3D) numerical simulation of a gas feed direct methanol fuel cell is performed. On both sides of the cell the flow field is formed by three parallel meander-like channels. It is shown that reduction of pressure in the middle channel on the cathode side leads to significant flux of water vapor to this channel without degradation of cell performance. At high current densities the channel with reduced pressure serves as collector of excessive water, which may prevent cell flooding.     

直接甲醇燃料电池电催化机理及多孔电极传质过程研究

直接甲醇燃料电池以其独特的优势被业界人士视为本世纪最有可能实现商业化的燃料电池. 因此,众多研究院所和公司展开了深入研究,取得了瞩目的成就. 本文分析了膜电极结构的电催化和多孔电极传质过程的机制,并结合制备工艺、有序多层结构以及电池内部传输过程,讨论了近年来膜电极在直接甲醇燃料电池相关的研究进展.     

Massenspektrometrische untersuchungen des ionenstromes an der kathode anomaler glimmentladungen

A method for measuring the mass and energy distribution of the ion current at the cathode of anomalous glow discharges is described. A commercial hf time-of-flight mass spectrometer for residual gas analysis is combined with a newly developed energy analyzer. The method is used to analyse the mass distribution of ions of both high and low energy at the cathode of discharges in nitrogen and argon and to measure the energy distribution of the Ar⁺ ions in discharges in argon. By applying the theory of Davis and Vanderslice to this energy distribution the cross section for resonant charge transfer of Ar⁺ ions was determined. The results lie well within the range of values reported in the literature.     

The problem of Ru dissolution from Pt–Ru catalysts during fuel cell operation: analysis and solutions

Platinum–ruthenium catalysts are widely used as anode materials in polymer electrolyte fuel cells (PEMFCs) operating with reformate gas and in direct methanol fuel cells (DMFCs). Ruthenium dissolution from the Pt–Ru anode catalyst at potentials higher than 0.5?V vs. DHE, followed by migration and deposition to the Pt cathode can give rise to a decrease of the activity of both anode and cathode catalysts and to a worsening of cell performance. A major challenge for a suitable application of Pt–Ru catalysts in PEMFC and DMFC is to improve their stability against Ru dissolution. The purpose of this paper is to provide a better knowledge of the problem of Ru dissolution from Pt–Ru catalysts and its effect on fuel cell performance. The different ways to resolve this problem are discussed.     

Optimization of an rf-powered magnetron glow discharge for the trace analysis of glasses and ceramics

A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure.     

Optimization of an rf-powered magnetron glow discharge for the trace analysis of glasses and ceramics

A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure.     

Combined local current distribution measurements and high resolution neutron radiography of operating Direct Methanol Fuel Cells

The current and fluid distribution in Direct Methanol Fuel Cells (DMFCs) was investigated in situ by means of combined high resolution neutron radiography and locally resolved current distribution measurements. The used neutron radiography set-up allows high spatial resolutions down to 70 μm at the full test cell area. A local formation of water droplets in the cathode flow field channels could be observed. Strongly inhomogeneous current distributions during cathodic flooding processes result in a performance loss of up to 30% of the initial value. Single CO₂ bubbles can be observed at low current densities. The water and current distribution during bi-functional operation of a DMFC was measured for the first time.     

质子交换膜燃料电池输出性能的数值模拟

运用COMSOL软件模拟分析3种流道下的质子交换膜燃料电池输出性能. 在相同的操作条件下,比较了单蛇形流道、交指流道以及混合流道之间的性能差异,详细说明了3种流道下质子交换膜燃料电池输出性能差异的原因. 由模拟结果分析得出,混合流道输出性能最好,交指流道输出性能其次,单蛇形流道输出性能最差;混合流道的排水能力最好,氧气浓度分布的最均匀;混合流道阴极进出口氧气浓度差最小. 模拟结果对质子交换膜燃料电池结构的优化和设计具有重要的指导意义.     

SU-8 flow field plates for a micro PEMFC

A SU-8 photoresist microfabrication process was developed for micro proton exchange membrane fuel cell flow structures for both anode and cathode flow field plates with a cross section of 5 cm² (22.5 mm×22.5 mm) and thickness (for a single cell) of about 750 µm. The new design for flow field plates would have SU-8 used as not only a photoresist but also as a microstructure material. A thickness of 30 nm Pt sputter loading deposited onto a Nafion 117 for membrane electrode assembly was made, with both scanning electron microscopy and atomic force microscopy characterization. Air flows were completed in hydrogen fuel cells with air breathing and forced air flows of low input pressure as well as low velocity. Performance tests of polarization curves and power density distribution as well as impendence measurements were conducted and discussed to examine the effects of orientation of the cathode surface with five hydrogen feeding rates as well as different airflow feeding modes.     

直接甲醇燃料电池的甲醇浓度控制方法

直接甲醇燃料电池(DMFC)直接以甲醇为阳极燃料,具有系统结构简单、体积能量密度高、燃料补充方便等特点,非常适合用于小型移动电源。甲醇浓度对DMFC性能和燃料利用效率的影响非常大,甲醇浓度高低直接决定DMFC输出性能的好坏,控制好DMFC中的甲醇浓度,对其寿命长短起着至关重要的作用。本文将目前已有的甲醇浓度控制方法分为有甲醇浓度传感器和无甲醇浓度传感器两大类,评述了这些浓度控制方法的研究现状和优缺点,并展望了甲醇浓度控制方法的趋势。     

Effects of microporous layer preparation on the performance of a direct methanol fuel cell

The effects of two different microporous layer (MPL) preparation methods, including a heated-spraying method and a scraping method, on the performance of a direct methanol fuel cell (DMFC) were investigated. The experimental results indicated the cell with the new MPL had a higher mass transfer rate of oxygen and better performance than that of the conventional MPL. Scanning electron microscopy (SEM) images showed that there were more cracks and voids on the surface of the new MPL than that of the conventional MPL. The cathode and anode polarization curves exhibited that the cell with conventional MPL decreased the cell performance due to the difficulty for mass transport. Electrochemical impedance spectra (EIS) analysis further demonstrated that the improved performance of the cell with new MPL was attributed to the enhanced oxygen transport as the result of the reduced mass transfer resistance in the fuel cell system.     

A novel MEA architecture for improving the performance of a DMFC

Direct methanol fuel cell (DMFC) consisting of a double-catalytic layered membrane electrode assembly (MEA) provide higher performance than that with the traditional MEA. This novel structured MEA includes a hydrophilic inner catalyst layer and a traditional electrode with an outer catalyst layer, which was made using both catalyst coated membrane (CCM) and gas diffusion electrode (GDE) methods. The inner catalyst was PtRu black on anode and Pt black on cathode. The outer catalyst was carbon supported Pt–Ru/Pt on anode and cathode, respectively. Thus in the double-catalytic layered electrodes three gradients were formed: catalyst concentration gradient, hydrophilicity gradient and porosity gradient, resulting in good mass transfer, proton and electron conducting and low methanol crossover. The peak density of DMFC with such MEA was 19 mW cm⁻², operated at 2 M CH₃OH, 2 atm oxygen at room temperature, which was much higher than DMFC with traditional MEA.     

Modeling the effect of the cathode geometry in a DC glow discharge ion source for mass spectrometry

A self-consistent, two-dimensional hybrid fluid-particle model is used to study the effect of cathode geometry on the plasma produced in an argon glow discharge for conditions typically of the commercially available glow discharge mass spectrometer system (VG9000 spectrometer and Megacell source). For a given power supply voltage and gas pressure, we show that the spatial distribution of the plasma in the discharge volume is strongly dependent on the cathode geometry. The plasma created in a discharge with a pin cathode tends to form a ring around the cathode, while the plasma in a discharge with a larger diameter, disk cathode is centered on-axis between the cathode face and the anode. The ion current arriving at the entry plane of the mass spectrometer thus depends strongly on the cathode geometry. This suggests that analytical performance can be enhanced by optimization of the cathode (sample) geometry.     

阳极支撑层憎水性对被动式直接甲醇燃料电池传质性能的影响

通过测定甲醇渗透率,详细研究了阳极支撑层的聚四氟乙烯（PTFE）含量对全被动式直接甲醇燃料电池（DMFC）甲醇传质和电池性能的影响。 膜电极集合体均使用相同的阳极催化层,膜和阴极。 实验结果表明,随着阳极支撑层PTFE含量的提高,甲醇渗透速率明显减小。 其含量较高时,甲醇传质阻力较大,会导致电池在很低的电流密度下就出现传质控制区。 采用PTFE质量分数为40%的支撑层时,DMFC以9 mol/L甲醇为燃料最大功率密度可达32×10-3 W/cm2,也进一步证明了适当提高阳极支撑层的憎水性,既有助于减少甲醇的渗透,又缓解了阴极的“水淹”问题。     

The influence of cathode flow field surface properties on the local and time-dependent performance of direct methanol fuel cells

The influence of cathode flow field wettability on the local and time-dependent performance of DMFCs was investigated by galvanostatic measurements of local current distribution, cell voltage and pressure drop along the cathode channels. The cathode flow fields made of graphite were either untreated, hydrophobic or hydrophilic. Drop shape analysis yielded contact angles in the descending order hydrophobic (126.8°), untreated (115.9°) and hydrophilic (26.2°). Especially at low air stoichiometry (λ_air = 2), hydrophilic cathode flow fields are advantageous with regard to higher power densities, suppression of local current fluctuations and substantial reduction of pressure drop along the cathode channels.     

Calibrant delivery for mass spectrometry

This article describes a means of sampling ions that are created at a location remote from the primary ion source used for mass spectral analysis. Such a source can be used for delivery of calibrant ions on demand. Calibrant ions are sprayed into an atmospheric pressure chamber, at a position substantially removed from the sampling inlet. A gas flow sweeps the calibrants towards the sampling inlet, and a new means for toggling the second ion beam into the instrument can be achieved with the use of a repelling field established by an electrode in front of the sampling inlet. The physical separation of two or more sources of ions eliminates detrimental interactions due to gas flows or fields. When using a nanoflow electrospray tip as the primary ion source, the potential applied to the tip completely repels calibrant ions and there is no compromise in terms of electrospray performance. When calibrant ions are desired, the potential applied to the nanoflow electrospray tip is lowered for a short period of time to allow calibrant ions to be sampled into the instrument, thus providing a means for external calibration that avoids the typical complications and compromises associated with dual spray sources. It is also possible to simultaneously sample ions from multiple ion beams if necessary for internal mass calibration purposes. This method of transporting additional ion beams to a sampling inlet can also be used with different types of atmospheric pressure sources such as AP MALDI, as well as sources configured to deliver ions of different polarity.