A “proton pump” concept for the investigation of proton transport and anode kinetics in proton exchange membrane fuel cells

A novel concept for the measurement of proton transport properties and electrode kinetics in proton exchange membrane fuel cells (PEMFC) is presented. The “proton pump” is essentially a fuel cell operated with pure nitrogen or very low hydrogen partial pressure instead of oxygen-containing gas on the cathode side, avoiding the complicated electrode kinetics of oxygen reduction. In this first study using this concept, we investigated the proton transport in high temperature PEMFC based on polybenzimidazole (PBI)/phosphoric acid membranes. The impedance spectra of the proton pump allow the clear distinction between anode and cathode kinetics and proton transport in the membrane. Identifying and analyzing the contribution of the anodic processes in the impedance spectra enabled the quantitative investigation of anode kinetics based on the Butler-Volmer equation. The proton transport was investigated in more detail in the current saturation region, where proton transport turned out to be the limiting process in case of sufficient H₂ supply at the anode. The maximum proton transport capacity of the PBI/phosphoric acid membrane was found to be comparable to those of Nafion^® membranes.     

质子交换膜燃料电池两维、两相流动模型

提出了考虑电池内部两相流动的质子交换膜燃料电池数学模型,模拟了阳极、阴极两侧的流道和扩散层中同时发生两相流动时电池内部的各种传递特性,并用实验数据验证了该模型的准确性。模拟结果显示,当电池阴极扩散层中有液态水存在时会大大降低膜中的局部电流密度;质子交换膜中水的净通量方向可正、可负,因此电池的增湿策略应根据不同的运行工况而不断变化。     

质子交换膜燃料电池温度和电流分布同步测定

发展了一种新的质子交换膜燃料电池（PEMFC）局部特性测试方法,该方法实现了在不改变PEMFC膜电极和电池结构的情况下对PEMFC电流密度和局部温度分布的同步测量。对一种PEMFC在自然冷却状态下,阳极流场板背面温度分布以及阴极电流密度分布进行了实验测定。实验结果表明,阳极流场板背面最大温差小于1℃;电流密度分布主要受电极内液态水分布影响;同时,水蒸气冷凝放热导致电池局部温度升高是造成电池温度分布不均的主要因素。     

Water flooding and pressure drop characteristics in flow channels of proton exchange membrane fuel cells

Water flooding of the flow channels is one of the critical issues to the design and operation of proton exchange membrane fuel cells (PEMFCs). The liquid water and total pressure drop characteristics both in the anode and cathode parallel flow channels of an operating PEMFC were experimentally studied. The gas/liquid two-phase flow both in the anode and cathode flow channels was observed, and the total pressure drop between the inlet and outlet of the flow field was measured. The effects of cell temperature, current density and operating time on the total pressure drop were investigated. The results indicated that the total pressure drop in the flow channels mainly depends on the resistance of the liquid water in the flow channels to the gas flow, and the different flow patterns distinguish the total pressure drops in the flow field. Clogging by water columns result in a higher pressure drop in the flow channels. The total pressure drop measurement can be considered as an in situ diagnoses method to characterize the degree of the flow channels flooding. The liquid water in the cathode flow channels was much more than that in the anode flow channels. The pressure drop in the cathode flow channels was higher than that in the anode flow channels. During the fuel cell operation, the cell performance decreased gradually and the pressure drop both in the anode and the cathode flow channels increased. The rate of flooding at the cathode side reached 49.56% under experimental conditions after 78 min of operation. However, it was zero at the anode side.     

自呼吸式MEMS微燃料电池的结构及其性能

利用MEMS技术设计并制作了有效面积为1.2cm×1.2cm的不同阳极和阴极结构,将它们组成电池并进行比较。结果表明,阳极采用点-蛇形混合流场,电池峰值功率密度为比点状流场的电池可提高10.4%;阴极采用双层镂空流场,峰值功率密度比单层镂空流场电池增加15.7%。最优结构电池在30%～50%相对湿度下性能良好,200mA恒流放电近610h,电池电压比较稳定。     

质子交换膜燃料电池冷启动的数值模拟

冷启动是质子交换膜燃料电池（PEMFC）商业化所面临的挑战之一，在PEMFC冷启动实验中，通过中子成像技术已经观测到电池内部存在过冷水，因此本文模型重点考虑过冷水对电池冷启动性能的影响。通过引入结冰概率函数对过冷水结冰过程的随机性进行描述，从而建立了PEMFC冷启动的三维、瞬态和多相流动数学模型。基于该模型，研究电池阴极催化层中离子聚合物的体积分数和质子交换膜的厚度对电池冷启动性能的影响。研究结果表明，增加阴极催化层中离子聚合物的体积分数，可有效促进阴极催化层中的反应生成水向质子交换膜中进行扩散，从而充分利用膜内的储水空间；减少质子交换膜的厚度，能促进质子交换膜中的离聚物水向阳极催化层扩散，在大电流密度工况下可有效缓解阳极的“膜干”现象。     

Experimental and numerical study on improvement performance by wave parallel flow field in a proton exchange membrane fuel cell

The performance and operation stability of proton exchange membrane fuel cells (PEMFCs) are closely related to the transportation of reactants and water management in the membrane electrode assembly (MEA) and flow field. In this paper, a new three-dimensional wave parallel flow field (WPFF) in cathode was designed and analyzed throughout simulation studies and an experimental method. The experimental results show that the performance of PEMFC with WPFF outperforms that of PEMFC with straight parallel flow field (SPFF). Specifically, the peak power density increased by 13.45% for the PEMFC with WPFF as opposed to PEMFC with SPFF. In addition, the flow field with area of 11.56 cm² was formed by the assembly of transparent end plate used for cathode and the traditional graphite plate used for anode. To understand the mechanism of the novel flow field improving the performance of PEMFC, a model of PEMFC was proposed based on the geometry, operating conditions and MEA parameters. The thickness of gas diffusion layers (GDL), catalytic layers (CL) and proton exchange membrane were measured by scanning electron microscope. The simulation result shows that compared with SPFF, the WPFF based PEMFC promote the oxygen transfer from flow channel to the surface of CL through GDL, and it was beneficial to remove the liquid water in the flow channel and the MEA.     

质子交换膜燃料电池膜电极结构与设计研究进展

膜电极（MEA）为质子交换膜燃料电池（PEMFC）提供了电子、质子、反应气体和产物水等多相物质传递和电化学反应的重要场所。设计和制备具有优异特性的MEA对提高PEMFC的性能,降低制造成本,加快其商业化应用是至关重要的。本文首先对PEMFC的反应机理进行了分析,接着从气体扩散层（GDL）、催化层（CL）、质子交换膜构造（PEM）3个方面阐述各部件在MEA中的作用,归纳总结了各部件的制备方法、传热传质方式、仿真模型、构效关系以及优缺点,最后对影响MEA的各种因素进行了总结,并且结合目前涌现出的许多新兴技术对PEMFC的发展进行了展望。本综述对未来高性能、长寿命和低成本的MEA开发具有指导意义。     

质子交换膜燃料电池关键技术研究进展

简述了质子交换膜燃料电池(PEMFC)的工作原理及特点;综述了PEMFC关键技术的最新研究进展,包括质子交换膜合成、电催化剂制备、膜电极工艺及水管理和热控制;并简介了我国PEMFC的开发情况。     

Applying Shape‐Controlled Pt Nano‐dendrites Supported on Carbon for Membrane‐Electrode Assembly in a Proton Exchange Membrane Fuel Cell

Platinum nano‐dendrites of various sizes were applied as cathode catalysts in a proton exchange membrane fuel cell (PEMFC). The membrane electrode assembly (MEA) fabricated with Pt nano‐dendrites showed very high ORR activity at high potential ranges due to lower activation overpotential. But it showed the cell performance only comparable to commercial Pt/C due to Ohmic and mass transfer resistance at high current density ranges. These results demonstrate that both high intrinsic activity of the catalysts and the formation of three‐phase interface with efficient proton, electron, and mass transfer should be considered together when shape‐controlled metal nanoparticles are used as cathode catalysts in a PEMFC.     

常规流场下各向异性扩散层对质子交换膜燃料电池(PEMFC)性能影响

为了研究扩散层各向异性对电池性能的影响,以XD=Di,j ^y/Di,j ^x 为各向异性的表征,建立了使用常规流场的质子交换膜燃料电池二维传质模型.考虑了阴阳极内物质的对流和扩散、水和质子在膜内传递以及催化层的电化学反应.利用有限差分法对控制方程进行离散,采用逐次超松驰法求解得到了阴阳极反应气体和水的浓度分布以及催化层电流密度、膜中水含量、膜中电势和电流密度的分布.分析结果表明：在1≤XD≤4时增大XD有利于提高电池性能,但随着XD增大其对电池性能的影响逐渐减小;并且XD对电池性能的影响主要体现在对阴极和膜性能的影响上,其对阳极性能的影响甚微.     

质子交换膜燃料电池用催化剂及其电极的研究进展

膜电极(MEA)是质子交换膜燃料电池(PEMFC)的核心技术。膜电极包含的催化剂层、材料和结构等对PEMFC的性能影响很大。催化剂面层上供三相(质子、电子、气体)用的通道对于电池使用时的催化作用是必不可少的。介绍了近几年催化剂的研究进展,看重对三相通道进行了详细叙述。也回顾了一些用于改善催化剂活性的其他方法,如阴极催化、合金催化剂,根据这些进展,对今后的研究方向提出了建议。     

Mathematical Model of Proton Exchange Membrane Fuel Cell with Consideration of Water Management

One‐dimensional model on the membrane electrode assembly (MEA) of proton exchange membrane fuel cell is proposed, where the membrane hydration/dehydration and the possible water flooding of the respective cathode and anode gas diffusion layers are considered. A novel approach of phase‐equilibrium approximation is proposed to trace the water front and the detailed saturation profile once water emerges in either anode or cathode gas diffusion layer. The approach is validated by a semi‐analytical method published earlier. The novel approach is applicable to the polarization regime from open circuit voltage to the limiting current density under practical operation conditions. Oxygen diffusion is limited by water accumulation in the cathode gas diffusion layer as current increases, caused by excessive water generation at the cathode catalyst layer and the electro‐osmotic drag across the membrane. The existence of liquid water in the anode gas diffusion layer is predicted at low current densities if high degrees of humidification in both anode and cathode feeds are employed. The influences of inlet relative humidity, imposed pressure drop, and cell temperature are correlated well with the cell performance. In addition, the overpotentials attributed from individual components of the MEA are delineated against the cell current densities.     

质子交换膜燃料电池的研究进展

质子交换膜燃料电池（PEMFC）是一种高效节能、工作稳定、环境友好的理想发电装置。质子交换膜是PEMFC的核心组成,是一种选择透过性膜,主要起传导质子、分割氧化剂与还原剂的作用。PEMFC用电催化剂主要为铂系电催化剂,为降低成本,提高铂的利用率和开发非铂系催化剂是今后催化剂研究的主要方向之一。对PEMFC电极的工作原理,关键组件及电池的水管理、热管理方法等作了综述。     

Water transport through a PEM fuel cell: A one-dimensional model with heat transfer effects

Models play an important role in fuel cell design/development. The most critical problems to overcome in the proton exchange membrane (PEM) fuel cell technology are the water and thermal management. In this work, a steady-state, one-dimensional model accounting for coupled heat and mass transfer in a single PEM fuel cell is presented. Special attention is devoted to the water transport through the membrane which is assumed to be a combined effect of diffusion and electro-osmotic drag. The transport of heat through the gas diffusion layers is assumed to be a conduction-predominated process and heat generation or consumption is considered in the catalyst layers. The analytical solutions for concentration and net water transport coefficient are compared with recent published experimental data. The operating conditions considered are various cathode and anode relative humidity (RH) values at and 2 atm. The studied conditions correspond to relatively low values of RH, conditions of special interest, namely, in the automotive applications. Model predictions were successfully compared to experimental and theoretical I-V polarization curves presented by Hung et al. [2007. Operation-relevant modelling of an experimental proton exchange membrane fuel cell. Journal of Power Sources 171, 728-737] and Ju et al. [2005a. A single-phase, non-isothermal model for PEM fuel cells. International Journal of Heat and Mass Transfer 48, 1303-1315]. The developed easy to implement model using low CPU consumption predicts reasonably well the influence of current density and RH on the net water transport coefficient as well as the oxygen, hydrogen and water vapour concentrations at the anode and cathode. The model can provide suitable operating ranges adequate to different applications (namely low humidity operation) for variable MEA structures.     

杂质气体对质子交换膜燃料电池性能影响的研究进展

质子交换膜燃料电池（proton exchange membrane fuel cell,PEMFC）的商业化进程受到了其耐久性的严重制约。燃料气体中含有的微量CO、CO2、H2S和NH3等杂质以及空气中含有的NOx、SOx等污染物是影响PEMFC耐久性的最主要因素之一。本文综述了燃料气体杂质和空气污染物分别对PEMFC性能的影响及其机理,其中燃料中含的CO除了能影响PEMFC的阳极性能以外,还可能通过扩散传质过程对电池阴极性能造成影响;H2S不仅能对电池阳极性能造成严重的影响,也可能对电池阴极性能造成明显的破坏;而空气中的微量NOx会对PEMFC性能造成明显的影响,但NOx对电池性能的影响是一种可逆过程。最后指出对杂质气体影响PEMFC耐久性的研究需要将计算机模型和实际试验相结合,用模型数据指导实验的进行,同时有必要考虑杂质对PEMFC电堆性能的影响。     

带增湿区的质子交换膜燃料电池

Water management is of great importance to maintain performance and durability of proton exchange membrane fuel cells. This paper presents a novel proton exchange membrane (PEM) fuel cell with a humidification zone in the membrane electrode assembly (MEA) of each cell, in which the moisture of the cathode exhaust gas could transfer through the membrane to humidify anode or cathode dry gas. With a simple model, the relative humidity (RH) of the dry air exhaust from a membrane humidifier with 100% RH stream as a counter flow is calculated to be 60.0%, which is very close to the experimental result (62.2%). Fuel cell performances with hydrogen humidifying, air humidifying and no humidifying are compared at 50, 60 and 70˚C and the results indicate that humidifying is necessary and the novel design with humidifying zone in MEA is effective to humidify dry reactants. The hydrogen humidifying shows better performance in short term, while water recovered is limited and the stability is not as good as air hu-midifying. It is recommended that both air and hydrogen should be humidified with proper design of the humidifying zones in MEA and plates.     

直通道流场PEMFC电流密度分布测定实验

大功率燃料电池研究中存在的主要问题是电池在放大过程中性能出现大幅度衰减．为提高电池和电池组性能,改善电池内部水管理,优化电极组成、电池操作参数和流场板结构,对电池内部电流密度分布进行测定很有必要．     

质子交换膜燃料电池水传递模型

提出了用于研究质子交换膜燃料电池膜中水分布、水传递量分布、电流密度分布等的二维数学模型;系统地考察了电池温度、阴阳极压力差、增湿程度、质子膜厚度等条件对水的传递和膜中水分布的影响.计算结果表明:①阳极增湿能够提高气体进口段膜阳极侧水的含量;②使用越薄的质子膜,越能提高膜中水的含量;③阳极增湿程度越大,由阳极向阴极迁移的水量越多.     

PEMFC流道横截面二维两相流数学模型(Ⅰ)模型建立

建立了质子交换膜燃料电池（PEMFC）流道和脊横截面的二维两相流数学模型（across-the-channel model）。模型描述了PEMFC主要的传递和反应过程,包括阴、阳两极反应气的质量传递、动量传递、电子和质子的传递以及电化学反应等。模型细致地描述了水（液态和气态）在扩散层、催化层以及质子交换膜中的传递过程。模型可以用来研究流场、扩散层、催化层以及膜等对电池性能的影响,进而达到优化电池结构的目的。