球形团聚物模型在质子交换膜燃料电池过程模拟中的应用

在建立直通道质子交换膜燃料电池(PEMFC)的二维全电池数学模型中,将球形团聚物模型应用至两极的催化剂层。通过调节团聚物中质子传导介质的比例和催化层孔隙率,预测了基准供气状态下单电池的极化曲线,与文献报道的实验数据吻合良好。研究了电池运行过程中,膜电极内各化学组分和电流密度的分布情况及流向,比较了不同供气压力、催化剂铂颗粒尺寸等参数对电池性能的影响。计算结果表明,在阴极及时排出反应产生的水,并在阳极对燃料气进行加湿是保证单电池正常运行的前提,提高阴极的氧化剂气体压力,可显著改善PEMFC单电池性能,特别是在受浓差极化影响较大的大电流密度区;在催化剂铂载量相同的情况下,减小铂颗粒的尺寸可以提高电池的性能。     

PEM燃料电池中质子交换膜内水和质子的迁移特性

质子交换膜的水含量及水和质子的迁移对PEM燃料电池的性能具有重要影响.提出了一个稳态两相流数学模型,用以研究质子交换膜中的水迁移和水含量及其与质子传递阻力的关系.模型耦合了连续方程、动量守恒方程、物料守恒方程和水在质子交换膜中的传递方程.通过与实验数据对比,验证了模型的有效性.分析模拟结果发现,当电流密度相同时,沿气体流动方向,质子交换膜中水的电渗拉力系数、反扩散系数和水力渗透系数逐步增大,而水的净迁移系数逐步减小;同时,质子交换膜的含水量增加,质子传递阻力逐步下降;增大电池的操作压力,电渗拉力系数、反扩散系数、水力渗透系数、水净迁移系数和质子膜的含水量增加,而质子传递阻力下降,使燃料电池的性能得到了提高.     

Pt/C催化剂的制备及单电池中的性能测试

以氢气作为还原剂,XC-72炭黑为载体,H2[PtCl6]为前驱体,制备Pt含量为20%的高分散Pt/C纳米电催化剂,在质子交换膜燃料电池单电池中进行了催化剂的性能测试。结果表明,该催化剂的催化性能良好。     

乙烷质子交换膜燃料电池的研究

研究了以乙烷作为燃料、全氟磺酸高分子膜(Nafion膜)作为质子交换膜、Pt或Pt-Ru作为电极催化剂主要组分、并通过掺杂Nafion膜作为电极内的离子导体构成的燃料电池电化学性能.研究了两种电极催化剂:Pt与Pt-Ru复合催化剂的制备及构成的单电池在不同温度及运行时间下的电化学性能.温度增加,电池性能变好;运行时间增加,电池性能下降,在相同的温度与运行时间下,Pt-Ru复合催化剂构成的电池比Pt催化剂构成的电池极化小.通过分析电极反应产物,探讨了乙烷电极及电池的反应机理.结构为C2H6,( Pt-Ru+膜材料复合阳极)/Nafion膜/(Pt+膜材料复合阴极),O2 的质子交换膜燃料电池,在150℃时,电池的最大输出电流和功率密度分别高达70 mA·cm-2和22 mW·cm-2.     

高温质子交换膜燃料电池用离子液体聚合物电解质的研究进展

综述了近十几年来高温质子交换膜燃料电池用离子液体聚合物电解质的研究进展及其在高温质子交换膜燃料电池中的应用进展,指出了此类电解质目前存在的亟待解决的两个问题：咪唑类离子液体毒化Pt基催化剂和复合膜中离子液体的长期稳定性。最后对高温质子交换膜燃料电池用离子液体聚合物电解质的发展前景作了展望,即开发与Pt基催化剂相容的离子液体聚合物电解质以及预防复合膜内离子液体的流失,即提高高温质子交换膜燃料电池的性能及长期稳定性,最终提高高温燃料电池的寿命。     

质子交换膜燃料电池研究现状及发展

质子交换膜燃料电池是一种高效清洁的发电技术,具有反应动力学快、启动温度低等特点。目前质子交换膜燃料电池技术发展迅速,有望得到广泛推广和普及。本文从质子交换膜燃料电池核心组件出发,对近年来质子交换膜燃料电池的发展进行了简要概述。从材料出发,对核心组件进行分类,详细介绍了质子交换膜、催化剂以及气体扩散层的研究现状和技术特点,综述了各组件的研究方法、改进方法以及研究进展,展望了质子交换膜燃料电池的研究方向和未来发展趋势。基于高温环境下的各种优势,具有短侧链、低当量的且适用于高温低湿环境的质子交换膜仍将是重点研究对象。质子交换膜燃料电池将进一步向低Pt甚至无Pt方向发展,同时未来将实现无增湿条件下的水平衡。     

阳极进气湿度对质子交换膜水含量及电流密度分布影响

针对质子交换膜中水分布不均匀造成燃料电池性能降低的问题,将膜和催化层中水传递方程进行耦合实现水在膜和催化层之间连续传递,建立了质子交换膜燃料电池三维稳态模型。利用有限元分析软件COMSOL进行模拟计算,研究了阳极气体在不同湿度下膜电流密度分布并组装单电池进行了验证,分析实验模拟结果表明:模拟极化曲线与实验极化曲线吻合良好。湿度对电流密度分布影响很大,低湿度条件下,脊背下方电流密度大于气体流道下方;高湿度条件下,电流密度分布比较均匀;采用Nafion117较厚膜时,高电流密度下,即使阳极加湿,阳极侧也有脱水的可能。     

国外甲醇燃料电池技术开发概况

燃料电池包括碱性燃料电池、磷酸燃料电池、熔融碳酸盐燃料电池、固态氧化物燃料电池和质子交换膜燃料电池.质子交换膜燃料电池中的直接甲醇燃料电池技术获得重大突破,可望于近期进入量产和商业化应用阶段,新型膜材料的开发是目前直接甲醇燃料电池研发的关键课题,电催化剂的催化性能对其功能也起着极为重要的作用.Ball、Casio、DFMC、Giner电化学系统、NEC、Polyfuel、三星电子、东芝和Motorola等一些大公司都在积极开展直接甲醇燃料电池的研发工作,并取得很大进展.     

质子交换膜燃料电池阴极催化剂的研究进展

随着时代的发展,环境问题走进人们的视野,绿色可持续发展成了当下共同探讨的话题,而燃料电池(FC)凭借其低污染、低噪声等特点成为理想的动力源之一,质子交换膜燃料电池(PEMFC)是燃料电池的一种,具备启动速度快、电池结构简单等特点,是环保电动汽车发电技术的主要研究方向之一。其中双极板是质子交换膜燃料电池的主要部件,其上附载的催化剂决定着电池的能量转换效率、制造成本及民用价值。催化剂可分为阴极催化剂和阳极催化剂两类,本综述主要围绕阴极催化剂的开发与催化性能的研究情况,从工作原理、优缺点、催化剂及其制备、发展前景等方面进行介绍。     

质子交换膜燃料电池膜电极性能特性研究

质子交换膜燃料电池(Proton Exchange Membrane Fuel Cell,PEMFC)是一种清洁高效的发电技术,其中膜电极是PEMFC的核心部件,膜电极的材料和制备工艺对电池性能的影响明显。为了对电池性能进行优化,针对Pt/C催化剂类型、膜电极热压温度、碳粉导电层疏水特性以及催化层中Nafion质量分数等因素进行了电流-电压实验测试,获得了电池性能的影响规律。实验结果表明:Pt/C催化剂类型、碳粉导电层疏水性以及催化层Nafion质量分数对电池性能有显著影响,当碳粉导电层聚四氟乙烯质量分数为24%,催化层中Nafion质量分数为30%时,电池性能达到最优值。膜电极热压温度对电池性能影响较小,但对导电碳粉层与催化层的粘结力影响显著,过低的温度会导致膜电极出现分层。     

Performance analysis of the ordered and the conventional catalyst layers in proton exchange membrane fuel cells

Two steady-state, one-dimensional models of the cathode active layer for the proton exchange membrane fuel cell, a conventional active layer model with the agglomerate structure and an ordered active layer model, have been compared. The model equations account for the Tafel kinetics of oxygen reduction reaction, proton migration and oxygen diffusion in the polymer electrolyte and gas pores. The polarization curves simulated by the ordered active layer predict a superior performance than the conventional active layer model even with lower platinum loadings. Analysis of the overpotential contributions indicates that the better performance of the ordered catalyst layer can be attributed to the reduction of concentration polarization. Simulation results also reveal that the ordered active layer gives more uniform oxygen concentration and overpotential distributions while the conventional catalyst layer shows more evenly distributed local current source. The present results will be helpful for practical fuel cell designs.     

A thin-film/agglomerate model of a proton-exchange-membrane fuel cell cathode catalyst layer with consideration of solid-polymer-electrolyte distribution

A thin-film/agglomerate model for the cathode part of a proton-exchange-membrane fuel cell is developed. Parameter estimation is employed to determine the exchange current density in the catalyst layer, proton conductivity of the recast ionomer, and oxygen diffusivity in the solid polymer electrolyte. The effects of catalyst and polymer electrolyte loadings in the catalyst layer on the cell performance are demonstrated using this model. The influence of polymer electrolyte distribution in the catalyst layer is correlated with the oxygen diffusion and proton migration rates within the electrolyte. It is found that proton migration in the polymer electrolyte is the dominant factor for cell current density under normal operating conditions. A better cell performance is achieved by a concentrated polymer electrolyte near the catalyst layer/membrane interface.     

质子交换膜燃料电池电源系统停机特性及控制策略

质子交换膜燃料电池(PEMFC)电源系统在停机后,燃料电池开路高电压被认为是造成电池性能下降和寿命缩短的重要因素。这主要是因为PEMFC电源系统停机后,燃料电池处于开路状态,阳极侧残留的氢气和阴极侧的空气发生电化学反应,电池电压为开路高电压且维持在开路电压的时间比较长,这容易引起催化剂碳载体发生氧化,使分布在载体上的铂(Pt)颗粒脱落,造成燃料电池性能衰减以及寿命缩短。以最大程度缩短停机后开路高电压的时间和加快阳极侧残留氢气的消耗速度为目标,提出了一种PEMFC电源系统的停机策略,通过实验分别研究了直接停机和停机策略停机对PEMFC输出特性的影响。以该停机控制策略为基础,通过实验验证了该停机策略的有效性,为提出保护性的PEMFC电源系统停机控制策略提供了参考性指导。     

A Non‐isothermal Model of a Laboratory Intermediate Temperature Fuel Cell Using PBI Doped Phosphoric Acid Membranes

A two‐dimensional non‐isothermal model developed for a single intermediate temperature fuel cell with a phosphoric acid (PA) doped PBI membrane is developed. The model of the experimental cell incorporates the external heaters, and the body of the fuel cell. The catalyst layers were treated as spherical catalyst particles agglomerates with porous inter‐agglomerate space. The inter‐agglomerate space is filled with a mixture of electrolyte (hot PA) and PTFE. All the major transport phenomena are taken into account except the crossover of species through the membrane. This model was used to study the influence of two different geometries (along the channel direction and cross the channel direction) on performance. It became clear, through the performance analyses, that the predictions obtained by along the channel geometry did not represent the general performance trend, and therefore this geometry is not appropriate for fuel cell simulations. Results also indicate that the catalyst layer was not efficiently used, which leads to large temperature differences through the MEA.     

液相进样直接甲醇燃料电池性能研究

报道了用研制的Pt-Ru/C催化剂, 采用特殊工艺制备了膜电极, 并组装了直接甲醇质子交换膜单电池系统。考察了电极扩散层制备方法、催化剂层中催化剂、Teflon-C以及Nafion液的用量等电极制备工艺条件以及空气作为氧化剂对单电池性能的影响。结果表明：采用刷涂法制备电极扩散层比喷涂法好,催化剂层中催化剂的优化含量为0.6mg·cm-2,Teflon-C、Nafion液的最佳用量分别为0.3 mg·cm-2、0.5 mg·cm-2。当工作温度为80℃时,输出电压为0.3V,氧气作为阴极气体的输出电流密度为36mA·cm-2;而空气作为阴极气体的输出电流密度为22.5mA·cm-2。膜电极有效面积为9cm2的的液相进样直接甲醇/氧气燃料电池三电池电堆的最大功率为0.285W,此时输出电压为0.7V,输出电流为0.407A;而液相进样直接甲醇/空气三电池电堆的输出电压为0.635V,输出电流为0.252A时,最大功率为0.160W。     

Electrocatalytic activity mapping of model fuel cell catalyst films using scanning electrochemical microscopy

Scanning electrochemical microscopy has been employed to spatially map the electrocatalytic activity of model proton exchange membrane fuel cell (PEMFC) catalyst films towards the hydrogen oxidation reaction (the PEMFC anode reaction). The catalyst films were composed of platinum-loaded carbon nanoparticles, similar to those typically used in PEMFCs. The electrochemical characterisation was correlated with a detailed physical characterisation using dynamic light scattering, transmission electron microscopy and field-emission scanning electron microscopy. The nanoparticles were found to be reasonably mono-dispersed, with a tendency to agglomerate into porous bead-type structures when spun-cast. The number of carbon nanoparticles with little or no platinum was surprisingly higher than would be expected based on the platinum-carbon mass ratio. Furthermore, the platinum-rich carbon particles tended to agglomerate and the clusters formed were non-uniformly distributed. This morphology was reflected in a high degree of heterogeneity in the film activity towards the hydrogen oxidation reaction.     

三维石墨毡阳极自呼吸微流体燃料电池性能数值模拟

针对采用三维石墨毡可渗透阳极的空气自呼吸无膜微流体燃料电池,建立了三维等温稳态数学模型,对电池中燃料及电解液的流动和传输、电极过程动力学及电荷传递过程进行了模拟,计算获得了具有石墨毡阳极的微流体燃料电池内的传质和燃料渗透特性,研究了石墨毡厚度及反应物（燃料和电解液）流量对电池性能的影响。结果表明：当入口流量为333 μl·min^-1时,采用石墨毡可渗透阳极相比碳纸和碳布可渗透阳极,极限电流密度和极限功率密度分别提升12%和50%;电池电压为0.8 V时燃料渗透引起的寄生电流密度仅占电流密度的0.86%。电池性能随着石墨毡电极厚度增加而升高,但增幅逐渐减小;反应物流量增大,电池的性能先增加后逐渐趋于稳定。     

On the Catalytic Degradation in Fuel Cell Power Supplies for Long‐Life Mobile Field Sensors

Important tasks such as environment monitoring require field devices such as sensors that can operate for long durations. Current power supply technologies such as batteries limit many applications. Fuel cells are a promising alternative to batteries because they can have much higher energy densities. However, their lives may be short due to catalyst degradation. Here, a simplified model of proton exchange membrane (PEM) fuel cell catalyst degradation is applied to small fuel cells. The model focuses on the combined effects of catalyst dissolution and migration. The effect of migration on catalyst degradation is found to be substantial and this has not been accounted for in previous models. The model considers the effect of field conditions such as varying power demands, temperature and humidity, and predicts the catalyst life of the fuel cell and its power output. The predicted life is a proposed metric that can quantify the relative importance and effect of field conditions on the catalyst particularly for the design and control of fuel cell power supplies. Experiments are presented that support the model. This model is applied to a study on field sensors and results suggests unless PEM fuel cells are isolated from damaging field conditions, they will have short lives.     

An isothermal model of a laboratory intermediate temperature fuel cell using PBI doped phosphoric acid membranes

A two-dimensional isothermal model is described for an intermediate temperature fuel cell using a phosphoric acid doped polybenzimidazole (PBI) membrane. The model considered the membrane-electrode-assembly and gas flow channels. All the major transport phenomena were taken into account except the cross-over of species through the membrane. The catalyst layers were treated as spherical catalyst agglomerates with porous inter-agglomerate spaces. The inter-agglomerate spaces are filled with a mixture of electrolyte (hot phosphoric acid) and polytetrafluoroethylene (PTFE). The model was validated against experimental data and used to study the influence of the catalyst layer properties on performance. Through the analyses of the effectiveness factor the model showed that utilisation of catalyst particles was very low at high current densities. At these conditions, the reaction occurs mainly on the surface of the agglomerate. An optimum phosphoric acid loading was found from the model simulations. The model was also used to demonstrate the resistance of the intermediate temperature fuel cell to anode poisoning by CO.