质子交换膜燃料电池双极板的设计与模拟分析

质子交换膜燃料电池是直接将化学能转换为电能的装置,双极板上的流道结构对燃料电池的工作性能具有较大的影响。根据应用要求设计了具有平行流道、蛇形流道及希尔伯特分形流道的双极板结构,模拟计算了氢气在不同类型的流道和气体扩散层中的分布状态,分析了燃料电池的输出电流密度和功率密度随电极间电压的变化特点,比较了不同的流道结构对燃料电池输出电流密度的影响,以及不同的工作温度及气体压强的情况下,燃料电池输出电流密度随温度及压强的变化规律。     

四流道蛇形结构质子交换膜燃料电池温度分布数值模拟

为研究温度对质子交换膜燃料电池性能的影响,运用多物理场直接耦合分析软件COMSOL Multiphysics,对不同电池温度的四流道蛇形流场质子交换膜燃料电池进行了数值模拟。模拟得到了不同电池温度下垂直膜电极平面以及电池中心处从阳极流道到膜,再到到阴极流道的温度变化情况;还得到了电池温度为353K时,电池入口处、中心处和出口处从阳极流道到阴极流道相应位置点的温差变化。对模拟结果进行分析和比较后发现:电池内部温度的升高与电池本身的原始温度存在线性变化关系;电池入口处、中心处和出口处的温度变化趋势存在差异,且电池入口处温升最大,中心处次之,出口处温升最小;随着电池温度的升高,电池因内部反应所产生的热量减少。模拟结果对质子交换膜燃料电池的性能优化有重要意义。     

蛇形流场结构质子交换膜燃料电池的性能研究

建立包括催化层、扩散层、质子膜在内的三维质子交换膜燃料电池模型,通过Fluent软件模拟4种不同结构的蛇形流场,通过对速度、膜中水含量以及功率密度等分析得出蛇形流场的最优结构,并对最优结构进行参数优化。研究表明,4种不同蛇形流场结构中,Multi-serpentine II为最优,随着温度、压强的增加,这种流场结构的燃料电池呈现出良好的性能,从而为质子交换膜燃料电池双极板的设计提供依据。     

PEMFC翅脉流道传质及输出性能分析

为研究流道结构对质子交换膜燃料电池（PEMFC）反应气体质量传输及输出性能的影响,建立翅脉流道、叶脉流道及蛇形流道的三维PEMFC几何模型,并对比3种流道的反应气体浓度分布、压力分布及电流密度分布,最后对翅脉流道结构参数进行优化。结果表明,与蛇形流道、叶脉流道相比,翅脉流道能明显改善流道和扩散层内反应气体浓度分布的均匀性,有利于强化反应气体向催化层的质量传递;翅脉流道能减小气体压力分布梯度,使反应气体扩散更加充分;翅脉流道的平均膜电流密度更大,有利于促进电化学反应稳定进行;翅脉流道能改善PEMFC的输出性能,翅脉流道峰值功率密度比蛇形流道、叶脉流道分别提高7.72%和6.25%;减小翅脉流道的直流道长度或圆弧流道圆心角,可提升翅脉流道输出性能。     

基于不同人工神经网络的CNG发动机排气温度预测模型研究

为了提高CNG发动机排气温度预测精度,基于BP、RBF和GRNN神经网络建立了3种排气温度的预测模型。开展了CNG发动机台架实验,测量了不同工况条件下发动机的排气温度,利用实验值对模型进行训练,并预测了不同发动机转速、空气进气量、点火提前角等条件下的排气温度,将预测值与实验值进行了对比分析,评估了不同预测模型的准确性。结果表明:BP、RBF和GRNN 3种神经网络的误差分别为3.5%、2.8%和3.1%。RBF神经网络的预测误差比BP和GRNN神经网络的误差小,稳定性强,更适合CNG发动机的排气温度预测。     

质子交换膜燃料电池传输现象的数值分析

建立了一个具有蛇形通道,采用Nafion117膜单体质子交换膜燃料电池的三维数学模型,该模型同时考虑了流动、传热、传质、电化学动力学和多组分传输现象。通过求解传输方程组,并耦合电化学动力学方程,获得了电池的极化性能曲线和电池内部的反应物浓度、温度、速度分布。计算结果表明,增加电极孔隙率、提高电池运行温度和压力有助于改善电池性能。估算的极化性能与献中的实验数据基本符合。分析了运行条件对电池性能的影响。     

基于神经元的PEMFC仿生流道性能模拟研究

质子交换膜燃料电池的流道结构对反应气体的流动和压降等具有重要影响。受神经元结构启发,提出一种兼顾径向流道和仿生流道在压降和气体分布均匀性优点的新型仿生流道结构。通过COMSOL软件模拟研究该新型流道的分支数（2~9）对质子交换膜燃料电池的性能曲线、阴极氧浓度分布、水浓度分布及压降的影响。结果表明：增加流道分支数可提高质子交换膜燃料电池的输出性能,其中9分支流道的峰值功率密度最大,为0.32 W/cm²,相比于2分支流道增加了的146.15%;分支数的增加也会提高氧浓度分布的均匀性,阴极气体扩散层与催化层交界面处的平均氧浓度从0.44 mol/m³提高到1.42 mol/m³,氧气不均匀度从2.13降低至0.90;分支数的增加也明显改善了弧形流道内的水浓度分布。此外,随着流道分支数从2增加到9,流道压降从38.57 Pa递减至4.47 Pa,质子交换膜燃料电池的输出功率从0.40 W递增到1.56 W。     

质子交换膜燃料电池内电荷传递的数值模拟

为深入研究质子交换膜燃料电池内电荷传递的规律,发展了一个三维的单相流、非等温数学模型,模型考虑了电子在催化层和扩散层、质子在催化层和质子交换膜中的传递。通过计算得到了电池内电位和电流密度的空间分布,分析了不同电极结构参数下电流密度的分布和最终造成的性能差异。结果表明,欧姆电位的下降主要发生在膜相电位,而碳相电位的下降几乎可以忽略不计;电流密度在流道与集电极交界处出现＂火焰形＂累积效应;改变电池的结构对电池性能影响不大,应结合加工成本和电流密度分布综合考虑。     

质子交换膜燃料电池内部传热传质三维模拟

针对常规流场质子交换膜燃料电池提出了三维非等温数学模型。模型考虑了电化学反应动力学以及反应气体在流道和多孔介质内的流动和传递过程,详细研究了水在质子膜内的电渗和扩散作用。计算结果表明,反应气体传质的限制和质子膜内的水含量直接决定了电极局部电流密度的分布和电池输出性能;在电流密度大于0.3~0.4A/cm2时开始出现水从阳极到阴极侧的净迁移;高电流密度时膜厚度方向存在很大的温度梯度,这对膜内传递过程有较大影响。     

直接液体甲醇燃料电池流场组织行为研究(Ⅰ) 传统对称流道电池的模型建立

建立了直接甲醇燃料电池垂直流道方向电池单元的二维稳态数学模型,考虑了电化学动力学、多组分传递和甲醇渗透影响.计算了流道布置密度、扩散层、催化层和质子交换膜等组件尺度对电池内物料传质特性、化学反应组织和电池输出性能的影响.研究发现,增加流道布置密度、增加催化层厚度能有效提高电极反应均匀性和电池性能.其中催化层和质子膜的厚度影响最为显著,在该文研究范围内分别可提高电池的平均电流密度131.0%和17.8%.而扩散层和质子交换膜厚度都存在一个最佳值,需要与以上流场板设计尺寸和膜电极尺寸匹配.     

Low temperature decal transfer method for hydrocarbon membrane based membrane electrode assemblies in polymer electrolyte membrane fuel cells

Decal transfer is an effective membrane electrode assembly (MEA) fabrication method known for its low interfacial resistance and suitability for mass processing. Previously decal transfer for hydrocarbon membranes was performed at temperatures above 200 °C. Here a novel low temperature decal transfer (LTD) method for hydrocarbon membranes is introduced. The new method applies a small amount (2.2 mg cm⁻²) of liquid (1-pentanol) onto the membrane separator before decal transfer to lower the T_g of the membrane and achieves complete decal transfer at 110 °C and 6 MPa. Nafion binder amount in the catalyst layer and catalyst layer annealing temperature is controlled to optimize the fuel cell performance. Compared to conventional decal transfer (CDT), the novel LTD method shows enhancement in energy efficiency, simplicity in the process scheme, and improvement in fuel cell performance.     

Reinforced short-side-chain Aquivion® membrane for proton exchange membrane water electrolysis

A reinforced short-side-chain per?uorosulfonic acid (PFSA) Aquivion® membrane with equivalent weight (EW) of 980 g/eq and 50 μm thickness produced by Solvay Specialty Polymers was investigated for operation in polymer electrolyte membrane (PEM) water electrolysis. The membrane produced by a dispersion casting process was reinforced by introducing polytetrafluoroethylene (PTFE) fibres in order to enhance mechanical and dimensional stability properties while keeping high conductivity and decreased ohmic drop for operation at high current density. A conventional extruded PFSA Aquivion® membrane with similar EW and thickness was investigated for comparison under similar operating conditions. Membrane-electrode assemblies (MEAs) made of reinforced membranes were tested in a single cell and compared to extruded membranes bared MEAs. All MEAs consisted of home-made unsupported IrRuOx anode and carbon-supported Pt (40%) cathode electrocatalysts. Electrochemical tests showed better water splitting performance for the reinforced Aquivion® based membrane-electrode assembly as compared to the benchmark based MEA. At 90 °C, a current density of 5 Acm^?2 was recorded at 1.8 V (～80% voltage efficiency vs. Higher Heating Value (HHV) with the reinforced Aquivion® membrane. The cell voltage for the reinforced membrane-based cell was about 50 mV lower than the extruded one during a 3500 h durability test. Moreover, lower recoverable losses were observed for the reinforced membrane based MEA during steady-state durability tests and no membrane thinning appeared after prolonged operation.     

New process for high temperature polybenzimidazole membrane production and its impact on the membrane and the membrane electrode assembly

Water addition is a key step in the new process developed at BASF Fuel Cell Inc. (BFC) for polybenzimidazole (PBI) membrane production. The added water prevents further polymerization and controls the solution viscosity for easier membrane casting. For large-scale PBI membrane production, a certain amount of tension is necessary during membrane upwinding. The applied tension could affect the polymer orientation and result in anisotropic membrane mechanical properties and proton conductivity. The membrane prepared with tension shows higher elastic modulus and proton conductivity in machine direction, which might suggest some degree of polymer chain orientation. However, the membrane electrode assembly (MEA) performance is not affected by the membrane's apparent anisotropic character. However, we observed performance variation as a function of MEA break-in condition, which might be explained by the formation of a phosphate anion concentration gradient during MEA operation.     

Characterization of nitrogen gas crossover through the membrane in proton-exchange membrane fuel cells

Gas crossover phenomenon through a membrane is inevitable in a proton-exchange membrane fuel cell (PEMFC). For nitrogen, the concentration at the cathode side is usually higher than that at the anode side, so N₂ permeates to the anode side. Nitrogen gas crossover (NGC) may cause fuel starvation, if N₂ gas accumulates in the hydrogen recirculation loop. Thus, it is important to determine the NGC under various PEMFC operating conditions. In this study, characterization of NGC under both open circuit voltage (OCV) and power generation conditions is investigated using a mass spectrometer. Under OCV conditions with the PEMFC membrane fully hydrated, N₂ concentration in the anode exit stream increases as cell temperature increases. Nitrogen permeability coefficients (NPC) are calculated based on the obtained N₂ concentration data. The results show that NPC exhibits an Arrhenius type relationship. Under OCV conditions, the maximum NPC is 5.14 × 10^?13 mol m^?1 s^?1 Pa^?1 with an N₂ activation energy of 19.83 kJ. Under power generation conditions, the NGC increases with increasing current density, which is the result of elevated membrane temperature and increased water content. When the anode stoichiometric ratio (SR_A) is lowered, the N₂ concentration increases under all tested current densities. A low hydrogen flow rate, along with a low SR_A at low current density, significantly increases N₂ concentration at the anode outlet.     

Impedance study of membrane dehydration and compression in proton exchange membrane fuel cells

Electrochemical impedance spectroscopy (EIS) is used to measure drying and rehydration in proton exchange membrane fuel cells running under load. The hysteresis between forward and backward acquisition of polarization curves is shown to be largely due to changes in the membrane resistance. Drying tests are carried out with hydrogen and simulated reformate (hydrogen and carbon dioxide), and quasi-periodic drying and rehydration conditions are studied. The membrane hydration state is clearly linked to the high-frequency arc in the impedance spectrum, which increases in size for dry conditions indicating an increase in membrane resistance. Changes in impedance spectra as external compression is applied to the cell assembly show that EIS can separate membrane and interfacial effects, and that changes in membrane resistance dominate. Reasons for the presence of a capacitance in parallel with the membrane resistance are discussed.     

Performance improvement induced by membrane treatment in proton exchange membrane water electrolysis cells

Hydrogen has been widely accepted as the best alternative energy carrier to store intermittent renewable energies. Proton exchange membrane water electrolysis (PEMWE) represents a promising technology to produce highly pure hydrogen with high efficiency and low footprint. While great progress has been made on components, materials and even fabrication processes, new materials or complicated processes still require refinement in the process of continuously improving PEMWE performance and durability. In this study, we demonstrate a facile treatment on membranes, aiming at improving cell performance at low costs. By adopting the hydration in DI water or 0.5 M H₂SO₄, or by varying the treatment sequence with the catalyst layer deposition, the PEMWE performance was tuned with the overpotential improvement as high as 50 mV at 2.0 A cm^?2. The PEMWE cells after different treatments were characterized both ex-situ and in-situ, and the mechanism was also proposed. The H₂SO₄ treatment swelled the micro micelle structure of the Nafion membranes, resulting in a higher proton conductivity and better cell performance compared with those from DI water treatment. In addition, the treatment sequence also had great impact, and the treatment after the catalyst layer deposition would result in better performance due to the reduced resistance and better kinetics. Not only the types of membrane, but also the thickness should be measured and reported when tested, which is more critical when compared across the published works from different groups. This work could also provide a guideline for future membrane treatment and PEMWE cell testing.     

Sputtered Pt loadings of membrane electrode assemblies in proton exchange membrane fuel cells

The fabrication of electrodes use in proton exchange membrane fuel cells (PEMFCs) by Pt sputter deposition has great potential to increase Pt utilization and reduce Pt loading without loss of cell performance. A radio frequency (RF) magnetron sputter deposition process (RF power = 100 W and argon pressure = 10^?3 Torr) was adopted to prepare Pt catalyst layers of PEMFC electrodes. The effects of cathode Pt and Nafion loadings on membrane electrode assembly (MEA)/cell performance were investigated using cell polarization, cyclic voltammetry, AC impedance, and microstructure analysis. Among the tested MEAs with various cathode Pt loadings (0.02–0.4 mg cm^?2), the one with 0.1 mg‐Pt cm^?2 (grain size = 3.90 nm, mainly Pt(111)) exhibited the best cell performance (320 and 285 mW cm^?2 at 0.44 and 0.60 V, respectively), which was similar to or better than those of some commercial nonsputtered/sputtered electrodes with the same or higher Pt loadings. The electrode Pt utilization efficiency increased as the Pt loading decreased. A Pt loading of greater than or lower than 0.1 mg cm^?2 yielded a lower electrode electrochemical active surface (EAS) area but a higher charge transfer and diffusion resistance. Nafion impregnation (0.1 to 0.3 mg cm^?2) into the sputtered Pt layer (Pt = 0.1 mg cm^?2) noticeably increased the EAS area, consistent with the decrease of the capacitance of the electrode double layer, but did not improve MEA/cell performance, mainly because of the increase in the kinetic and mass transfer resistances associated with oxygen reduction on the cathode. Copyright © 2011 John Wiley & Sons, Ltd.     

Operation of a proton exchange membrane fuel cell under non-humidified conditions using a membrane–electrode assemblies with composite membrane and electrode

Composite membranes with hydrophilic substances can retain water and allow the operation of proton exchange membrane fuel cells (PEMFCs) under non-humidified conditions. In this work, thin Nafion composite membranes with silica are prepared to operate a PEMFC with dry fuel and oxidant. In addition, the role of silica in the catalyst layer as a water retainer is studied. In particular, the anode and the cathode are modified separately to elucidate the effect of silica. The incorporation of silica in the membrane and the catalyst layer enhances single-cell performance under non-humidified operation. The cell performance of membrane–electrode assemblies using the composite membrane and electrode is higher than that of a MEA using commercial Nafion 111 membrane under non-humidified conditions.     

Experimental study on water transport in membrane humidifiers for polymer electrolyte membrane fuel cells

This paper presents an experimental setup for the measurement of water transfer in membrane humidifiers for automotive polymer electrolyte membrane (PEM) fuel cells at different process conditions. This setup was used to determine steady-state water permeation through perfluorinated sulfonic acid (PFSA)-based polymer membranes. The process conditions were varied within a relative humidity in the feed stream of RH = 30–90 %, absolute pressures of p = 1.25–2.5 bar, and temperatures of T = 320–360 K. The examined membranes are Nafion® membranes of different thicknesses (Nafion® 211, 212 and 115) and an experimental composite membrane manufactured by W. L. Gore & Associates. It was found that the overall water permeance is affected by both the mass transfer resistance of the membrane and the resistances in the boundary layers of the adjacent gas streams. The overall permeance is a strong function of water activity, with high levels of relative humidity showing the highest overall permeance. The absolute pressure only affects the overall permeance by affecting the diffusion in the boundary layers. Lower pressures are preferable for high overall water permeances. Increasing temperatures favor diffusion in the membrane and the boundary layers but lead to lower sorption into the membrane. The thicker Nafion® membranes show lower overall permeance at higher temperatures, while the overall permeance of the composite membrane shows no dependency on the temperature. Investigation of membrane humidifiers in counter-, co-, and cross-flow shows that the flow configuration in our setup has very little impact on the water flux in the humidifier.