交流阻抗法在质子交换膜燃料电池中的运用

介绍了交流阻抗谱法在质子交换膜燃料电池中的运用，为质子交换膜燃料电池的优化设计提供参考。     

质子交换膜燃料电池膜电极组件温度分布的神经网络预测模型

质子交换膜燃料电池膜电极组件表面的温度分布会影响质子交换膜燃料电池的性能、寿命和可靠性.为探究质子交换膜燃料电池传热规律,本文提出了一种基于神经网络的质子交换膜燃料电池膜电极组件温度分布的预测模型.本研究选取径向基函数神经网络(RBF)和广义回归神经网络(GRNN)两种神经网络,以电流密度、温度点的位置作为网络输入,不同位置的温度作为网络输出,对平行流道质子交换膜燃料电池、蛇形流道质子交换膜燃料电池分别建立了神经网络预测模型.结果显示,RBF神经网络预测的均方根误差平均为0.464、平均绝对百分误差为1.179％,GRNN神经网络预测的均方根误差平均为0.7155、平均绝对百分误差为2.27％;相较于GRNN神经网络,RBF神经网络精度更高;基于RBF神经网络的平行流道质子交换膜燃料电池膜电极组件温度分布预测模型预测值与96％的实验值的相对误差在5％以内.基于RBF神经网络的蛇形流道质子交换膜燃料电池膜电极组件温度分布预测模型预测值与95％的实验值的相对误差在5％以内.     

固体聚合物电解质水电解膜电极的电化学阻抗谱研究

测量了不同电解温度、电解电压等操作条件下固体聚合物电解质水电解膜电极的电化学阻抗谱,采用ZSimpWin软件对阻抗谱进行了拟合和分析。结果表明,提高电解温度,可减小电极的电化学反应电阻以及固体聚合物电解质膜的电阻;提高电解电压,电极的电化学反应电阻降低,但是电压过高,受气泡效应显著影响,电极反应电阻反而增加,阻抗谱中出现散乱的点;与质子交换膜燃料电池不同,SPE水电解过程中膜电极的阻抗谱出现"弥散效应",拟合时采用的等效电路也不同。     

不同流道质子交换膜燃料电池内传质过程的数值模拟

对采用交指型流场的质子交换膜燃料电池阴极建立了二维数学模型,利用计算流体力学的方法,模拟和研究了质子交换膜燃料电池阴极内的流动和传质过程.分别探讨了采用交指型流场和平行流场时气体在阴极扩散层中的传递机制及各组分浓度分布的特性,为燃料电池流场的设计与分析提供了参考依据.     

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。     

质子交换膜燃料电池自增湿研究进展

概述了质子交换膜燃料电池自增湿研究状况，指出自增湿的出发点是有效利用电池阴极过程生成水。综述了薄电解质膜、新型自增湿膜、自增湿流场结构三种方法的研究进展及适用空间。对自增湿技术发展前景进行了探讨。     

集胞藻PCC-6803催化的光合微生物燃料电池性能研究

以集胞藻PCC-6803(Synechocystis PCC-6803)为阳极催化剂搭建直接利用太阳能的双室H-型光合微生物燃料电池(PMFC),通过极化曲线法、交流阻抗法、循环伏安法等电化学方法,开展电极面积比、质子交换膜、内阻等因素对光合微生物燃料电池产电的影响研究。试验结果显示:在PMFC运转过程中,其输出功率稳定,且达到的最大功率密度为72.3 mW/m2;阴阳极面积大小对PMFC产电性能没有显著影响,说明双室光合微生物燃料电池中,质子交换膜传递质子的速率较慢,限制了PMFC发电效能的提高。PMFC启动后,随着生物膜的增长,其欧姆内阻、极化内阻、总内阻都呈现下降的趋势,且欧姆内阻下降的速率小于极化内阻,从而使欧姆内阻占总内阻的比率变大,进一步说明质子交换膜传递质子的速率是限制PMFC发电的关键因素。     

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。     

基于可拓控制的质子交换膜燃料电池动态特性研究

针对质子交换膜燃料电池在启动和负载变化时,输出响应速度较慢和稳定性较差的问题,提出了一种基于可拓控制的质子交换膜燃料电池动态特性优化方案。基于质子交换膜燃料电池动态模型,结合可拓控制参数整定简单、响应快速、稳定性好的特点,以质子交换膜燃料电池输入端氢气进气量作为参考控制量,设计了可拓控制器,以提高质子交换膜燃料电池的响应速度及输出稳定性。将可拓控制与经典PID的控制效果进行了对比,结果表明,在燃料电池启动和负载变化过程中,可拓控制在燃料电池输出动态稳定性及克服燃料电池响应滞后等方面均优于PID的控制效果。     

甲醇质子交换膜燃料电池的水和热管理

甲醇质了换燃料电是未来最有希望获得工程应用的燃料电池，文章简述了燃料电的发电原理及其分类。对多孔电极，直接甲醇质子交换膜燃料电及甲醇改质质子交换膜燃料电作了分析和讨论，指出了对质子交换膜燃料电池系统进行水管理和热管理的重要性和必要性。     

Performance of high temperature fuel cells with different types of PBI membranes as analysed by impedance spectroscopy

In order to study how PBI membranes influence the operation of HT-PEFC cathode we analyse the performance of HT-PEFC based on three different PBI membrane types (meta-PBI, ABPBI and PBI-O-PhT) by means of stationary voltamperometry and impedance spectroscopy. For impedance spectra interpretation we use an equivalent circuit containing transmission line distributed element. This approach allows us to measure the distributed ohmic resistance of proton transport inside cathode catalyst layer. It is shown that this resistance depends on the membrane type used and has even more pronounced influence on the FC performance than ohmic resistance of the membrane itself.     

Decay of material properties of degraded MEA caused by repeated cold starts under subzero conditions in polymer electrolyte fuel cells

This study investigated the characteristics of cell performance degradation, decline of component performance, and changes in the properties of membrane electrode assembly materials caused by repeated cold starts under a subzero condition of ?30 °C. It was made clear that functional decay appeared mainly at the cathode due to increased proton conductive impedance and reduction of reactivity of the electrode catalyst. Among the cathode components, an increase in proton conductive impedance in the cathode electrolyte was dominant. Furthermore, the application of ion chromatography and a newly developed proton‐induced gamma‐ray emission method to measure fluorine in the off‐gas drain revealed that decomposition of the electrolyte was dominant in the cathode catalyst layer. A decrease in fluorine in the cathode electrolyte measured by fluorine‐19 nuclear magnetic resonance confirmed this decomposition. A hypothesis is also presented concerning the cause of the performance degradation. © 2012 Wiley Periodicals, Inc. Heat Trans Asian Res; Published online in Wiley Online Library ( wileyonlinelibrary.com/journal/htj ). DOI 10.1002/htj.20394     

Effect of operational parameters on the performance of PEMFC assembled with Au-coated Ni-foam

An innovative proton exchange membrane fuel cell was assembled using Au-coated nickel foam instead of the conventional flow field (carbon plate). The effect of operational parameters on the performance of this cell was investigated by DC polarization and electrochemical impedance spectroscopy techniques. Parameters such as cell operating temperature, cathode humidification temperature, and cathode-gas stoichiometry were of concern.     

Diagnosis of hydrogen crossover and emission in proton exchange membrane fuel cells

When hydrogen leaks through holes in membrane-electrode assemblies (MEAs) in proton exchange membrane (PEM) fuel cells, it recombines directly with air. This recombination results in a reduction in oxygen concentration on the cathode side of the MEA. In this paper, the signatures of electrochemical impedance spectroscopy (EIS) are analyzed in different multi-cell stack configurations to show the relation between hydrogen leak rate and reduced oxygen concentrations. The reduction in concentration was made by mixing oxygen with nitrogen at different rates, and the increase in hydrogen leak rate was made by controlling the differential pressure (dP) between anode and cathode. To analyze the impedance signatures, we fit the data of oxygen concentration and dP with the parameters of a Randles circuit. The correlation between the parameters of the two data sets allows us to understand the change in impedance signatures with respect to reduction of oxygen in the cathode side. To have a better insight on the effect of insufficient oxygen at the cathode, a model that establishes a relationship between impedance and voltage was considered. Using this model along with the impedance signatures we were able to detect the reduction of oxygen concentrations at the cathode with the help of fuzzy rule-base. However, resolution of detection was reduced with the reduction of leak rate and/or increases in the stack cell count.     

Effect of catalyst layer with zeolite on the performance of a proton exchange membrane fuel cell operated under low-humidity conditions

Proton exchange membrane fuel cells (PEMFCs) employ a proton conductive membrane as the separator to transport a hydrogen proton from the anode to the cathode. The membrane's proton conductivity depends on the water content in the membrane, which is affected by the operating conditions. A membrane electrode assembly (MEA) that can self-sustain water is the key component for developing a light-weight and compact PEMFC system without humidifiers. Hence, zeolite is employed to the anode catalyst layer in this study. The effect of the gas diffusion layer (GDL) materials, catalyst loading, binder loading, and zeolite loading on the MEA performance is investigated. The MEA durability is also investigated through the electrochemical impedance spectroscopy (EIS) method. The results suggest that the MEA with the SGL28BCE carbon paper, Pt loadings of 0.1 and 0.7 mg cm^?2 in the anode and cathode, respectively, Nafion-to-carbon weight ratio of 0.5, and zeolite-to-carbon weight ratio of 0.3 showed the best performance when the cell temperature is 60 °C and supplies with dry hydrogen and air from the environment. According to the impedance variation measured by EIS, the MEA with zeolite in the anode catalyst layer shows higher and more stable performance than those without zeolite.     

Effect of primary parameters on the performance of PEM fuel cell

A one-dimensional, steady-state and isothermal model for a proton exchange membrane (PEM) fuel cell has been developed to investigate the effects of various parameters such as the molar fraction of nitrogen gas, relative humidity, temperature, pressure, membrane thickness, anode and cathode stoichiometric flow ratio and the distribution of oxygen in the cathode catalyst while water transfer in membrane is produced by diffusion, pressure gradient and electro-osmotic drag. The most critical problems to overcome in the proton exchange membrane (PEM) fuel cell technology are the water and thermal management. The results show that the cell performance increases as operating pressure and temperature are increased. The performance of cell can decrease by decreasing the relative humidity of inlet gases and increasing the membrane thickness. Increasing the anode and cathode stoichiometric flow ratio can also improve the cell performance. As the oxygen concentration becomes zero in about 8 percent depth of cathode catalyst layer, the thickness of cathode catalyst layer can be reduced 92 percent without any potential loss in output voltage. The cathode activation loss also becomes high by increasing the molar fraction of nitrogen gas. The modeling results agree very well with experimental results.     

Parameter optimization of PEMFC stack under steady working condition using orthogonal experimental design

Operating parameters have a huge impact on the output characteristics of a proton exchange membrane fuel cell stack. In this study, to optimize the performance of proton exchange membrane fuel cell stack, 4 sets of operating parameters, which include working temperature, cathode stoichiometric, relative humidity, and backpressure, were optimized by means of the orthogonal experimental design. The experiment was developed with the help of 4‐factor and 3‐level orthogonal table. Nine orthogonal experiments were performed, and the polarization curve, local current density distribution, and electrochemical impedance spectroscopy of each experiment were obtained. It is observed that cathode stoichiometric and working temperature have much stronger effects on the output voltage and output consistency of stack than that of relative humidity and backpressure. Using comprehensive equilibrium method, the optimized combination of each parameter was achieved as follows: the working temperature was 75°C, cathode stoichiometric was 2.5, relative humidity was 50%, and backpressure was 1 bar. The on‐site test result showed that when the cathode stoichiometric was low, and some part of the stack would be in a starvation condition and when the temperature was low, it might cause mass transfer problems.     

A simple transient model for a high temperature PEM fuel cell impedance

We develop a pseudo two-dimensional, isothermal transient model for a high temperature proton exchange membrane fuel cell. It takes into account the dynamic change of oxygen concentration in the cathode gas diffusion layer and in the cathode channel. The model can be used to simulate and analyze electrochemical impedance spectra of the cell in both potentiostatic and galvanostatic modes, current interrupt results and step changes in the cell current or potential. The model is validated by fitting experimental data.     

Catalyst degradation diagnostics of proton exchange membrane fuel cells using electrochemical impedance spectroscopy

A previously validated equivalent circuit model, in which two resonant circuits were inserted to represent the processes in the catalyst layers, is applied to fit the electrochemical impedance spectroscopy results of a single proton exchange membrane fuel cell exposed to accelerated stress test targeting catalyst degradation. The simulation results of the applied equivalent circuit model show very good agreement with the experimental data. The applied model is able to extract contributions of each of the model elements to the cell degradation. The obtained results indicate that the cathode catalyst layer resonant loop parameters, together with the cathode charge transfer resistance and cathode double-layer capacitance, change the most during the accelerated stress test. If each of the elements of the cathode resonant loop can be associated with physical processes inside the catalyst layer, the model may be used to give more insight into the degradation effects on functioning of the catalyst layer. From the conducted electrochemical impedance spectroscopy analysis, it seems that the low-frequency intercept in Nyquist plot shows the most significant change with degradation, so it may be used directly as a sufficient indicator of fuel cell performance degradation due to catalyst layer degradation.