Numerical simulation of enhancement of mass transfer in the cathode electrode of a PEM fuel cell by magnet particles deposited in the cathode-side catalyst layer

Recent experimental results show that performance of a proton exchange membrane (PEM) fuel cell is improved when small particles of permanent magnet are deposited in the catalyst layer on the cathode side. In this study, the mechanism of this phenomenon was clarified by using numerical simulation. Permanent magnet particles induce a Kelvin (magnetic) repulsive force against liquid water and an attractive force towards oxygen gas. To precisely study the behavior of oxygen and liquid water flows near the interface between the catalyst layer and gas diffuser, the simulation domain included the catalyst layer and gas diffuser. The simulation results revealed the following. The Kelvin repulsive force against liquid water mainly “manages” the liquid water flow and improves the performance of the fuel cell, especially in the current-limited region. In the presence of Kelvin forces, the liquid water saturation near the interface between the catalyst layer and gas diffuser decreases, thus making more pore space available for transport of oxygen gas. Furthermore, the water velocity moving from the interface increases in the upstream region. The gas velocity near the interface also increases, and thus more oxygen is supplied to the reaction sites. In summary, the Kelvin force promotes removal of liquid water from the catalyst layer, thus providing more oxygen to the catalyst and improving the performance of the fuel cell.     

Oxygen mass transport limitations at the cathode of polymer electrolyte membrane fuel cells

Oxygen transport across the cathode gas diffusion layer (GDL) in polymer electrolyte membrane (PEM) fuel cells was examined by varying the O₂/N₂ ratio and by varying the area of the GDL extending laterally from the gas flow channel under the bipolar plate (under the land). As the cathode is depleted of oxygen, the current density becomes limited by oxygen transport across the GDL. Oxygen depletion from O₂/N₂ mixtures limits catalyst utilization, especially under the land.The local current density with air fed PEM fuel cells falls to practically zero at lateral distances under the land more than 3 times the GDL thickness; on the other hand, catalyst utilization was not limited when the fuel cell cathode was fed with 100% oxygen. The ratio of GDL thickness to the extent of the land is thus critical to the effective utilization of the catalyst in an air fed PEM fuel cell. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Effects of hydrophobicity of the cathode catalyst layer on the performance of a PEM fuel cell

The effects of hydrophobicity of the cathode catalyst layer on the performance of a PEM fuel cell are studied. The surface contact angle is measured to understand the changes of the hydrophobicity of the cathode catalyst layer upon the addition of hydrophobic dimethyl silicone oil (DSO). The results show that the contact angle increases with the DSO loadings in the cathode catalyst layer ranging from 0 to 0.65 mg/cm². The subsequent electrochemical measurements of the fuel cells with various cathodes reveal that the addition of DSO in the cathode catalyst layer can effectively prevent the cathode flooding at high current density, thus leading to a much higher limiting current density and the maximum power density when compared to the fuel cell with a normal cathode. An optimal DSO loading in the cathode catalyst layer is found to be around 0.5 mg/cm² under the testing conditions in this work. The fuel cell with cathode loaded with 0.5 mg/cm² can reach the maximum power density of 356 mW/cm² in H₂/air (or 709 mW/cm² in H₂/O₂) at room temperature, which is around 2.5 times in H₂/air (or 1.8 times in H₂/O₂) of that with normal cathode. All of the results indicate that the hydrophobicity of the cathode catalyst layer plays a crucial role in the water management of the fuel cell. The possible function of the DSO on improved oxygen solubility for the oxygen starved cathode during flooding warrants some further investigation.     

A three-dimensional numerical simulation of the transport phenomena in the cathodic side of a PEMFC

A three-dimensional numerical model is developed to simulate the transport phenomena on the cathodic side of a polymer electrolyte membrane fuel cell (PEMFC) that is in contact with parallel and interdigitated gas distributors. The computational domain consists of a flow channel together with a gas diffusion layer on the cathode of a PEMFC. The effective diffusivities according to the Bruggman correlation and Darcy's law for porous media are used for the gas diffusion layer. In addition, the Tafel equation is used to describe the oxygen reduction reaction (ORR) on the catalyst layer surface. Three-dimensional transport equations for the channel flow and the gas diffusion layer are solved numerically using a finite-volume-based numerical technique. The nature of the multi-dimensional transport in the cathode side of a PEMFC is illustrated by the fluid flow, mass fraction and current density distribution. The interdigitated gas distributor gives a higher average current density on the catalyst layer surface than that with the parallel gas distributor under the same mass flow rate and cathode overpotential. Moreover, the limiting current density increased by 40% by using the interdigitated flow field design instead of the parallel one.     

Optimization of cathode catalyst layer for direct methanol fuel cells: Part II: Computational modeling and design

The cathode catalyst layer in direct methanol fuel cells (DMFCs) features a large thickness and mass transport loss due to higher Pt loading, and therefore must be carefully designed to increase the performance. In this work, the effects of Nafion loading, porosity distribution, and macro-pores on electrochemical characteristics of a DMFC cathode CL have been studied with a macro-homogeneous model, to theoretically interpret the related experimental results. Transport properties in the cathode catalyst layers are correlated to both the composition and microstructure. The optimized ionomer weight fraction (22%) is found to be much smaller than that in H₂ polymer electrolyte fuel cells, as a result of an optimum balance of proton transport and oxygen diffusion. Different porosity distributions in the cathode CLs are investigated and a stepwise distribution is found to give the best performance and oxygen concentration profile. Influence of pore defects in the CLs is discussed and the location of macro-pores is found to play a dual role in affecting both oxygen transport and proton conduction, hence the performance. The reaction zone is extended toward the membrane side and the proton conduction is facilitated when the macro-pores are near the gas diffusion layer.     

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.     

Physical and electrochemical characterization of catalysts for oxygen reduction in fuel cells

The cathode catalysts in low temperature fuel cells are associated with major cell efficiency losses, because of kinetic limitations of the oxygen reduction reaction. Additionally, methanol oxidation at the cathode leads to significant lowering of the efficiency in direct methanol fuel cells, which can be alleviated by use of methanol-tolerant catalysts. In this work, alternative carbon-supported platinum-alloy catalysts were investigated by physical methods. Second, methanol-tolerant ruthenium-selenide catalysts were characterized by physical and electrochemical methods. Besides V–i characteristics and electrochemical impedance spectroscopy as electrochemical methods, physical methods such as X-ray photoelectron spectroscopy, nitrogen adsorption, porosimetry by mercury intrusion and temperature programmed reduction are used to characterize the catalysts. The electrochemical characterization yields information about properties and behavior of the catalyst. In contrast to platinum a significantly different hydrophobic behavior of the RuSe/C catalysts is found. Low open circuit voltage values measured for RuSe/C indicate an effect on both electrodes. The anode reaction was also influenced by the different cathode catalysts. As a result of the formation of H₂O₂ at the cathode, which passes through the membrane from cathode to anode side, a mixed anode potential is formed. By comparing RuSe/C catalysts before and after electrochemical stressing, changes of the catalysts are determined. Postmortem surface analysis (by X-ray photoelectron spectroscopy) revealed that catalyst composition and MEA structure changed during electrochemical stressing. During fuel cell operation selenium oxide is removed from the surface of the catalysts to a large extent. Additionally, a segregation effect of selenium in RuSe to the surface is identified.     

Studies of the performance of PEM fuel cell cathodes with the catalyst layer directly applied on Nafion membranes

The performance of a proton exchange membrane fuel cell (PEMFC) with gas diffusion cathodes having the catalyst layer applied directly onto Nafion membranes is investigated with the aim at characterizing the effects of the Nafion content, the catalyst loading in the electrode and also of the membrane thickness and gases pressures. At high current densities the best fuel cell performance was found for the electrode with 0.35 mg Nafion cm⁻² (15 wt.%), while at low current densities the cell performance is better for higher Nafion contents. It is also observed that a decrease of the usual Pt loading in the catalyst layer from 0.4 to ca. 0.1 mg Pt cm⁻² is possible, without introducing serious problems to the fuel cell performance. A decrease of the membrane thickness favors the fuel cell performance at all ranges of current densities. When pure oxygen is supplied to the cathode and for the thinner membranes there is a positive effect of the increase of the O₂ pressure, which raises the fuel cell current densities to very high values (>4.0A cm⁻², for Nafion 112—50 μm). This trend is not apparent for thicker membranes, for which there is a negligible effect of pressure at high current densities. For H₂/air PEMFCs, the positive effect of pressure is seen even for thick membranes.     

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.     

采用常规条形流场的质子交换膜燃料电池阴极数值模拟(Ⅰ)模型建立

对采用常规条形流场的H₂-Air PEMFCs阴极建立了二维数学模型,模型的控制方程耦合了连续性方程、Darcy方程、电传导方程以及O₂和H₂O的对流-扩散方程,对氧的电化学还原反应过程采用Butler-Volmer方程描述.利用模型计算了阴极扩散层中电流密度、O₂和H₂O浓度、催化层界面上局部电流密度的分布,分析了采用常规条形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点.     

PEMFC流道截面对气体浓度在催化层分布影响的数值分析

以蛇形流场质子交换膜燃料电池阴极为研究对象,取其中一部分建立三维、稳态的数学计算模型,利用CFD（计算流体动力学）方法研究了质子交换膜燃料电池阴极内的流动和传质过程,得到了阴极内氧气和水蒸气的质量分数的分布情况,探讨了流道宽度和深度对气体在催化层空间分布的影响,为燃料电池流场的设计和改进提供了参考依据。     

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。     

Electrochemical Evaluation of Porous Non‐Platinum Oxygen Reduction Catalysts for Polymer Electrolyte Fuel Cells

A porous non‐platinum electrocatalyst for the oxygen reduction reaction (ORR), obtained by pyrolysing a cobalt porphyrin precursor, was evaluated by electrochemical means. The reactivity of the non‐platinum ORR catalyst was investigated with a rotating disc electrode (RDE) experimental set up. RDE data were collected in an acidic electrolyte containing N₂, O₂, CO and under mixed reactant O₂/methanol conditions. The electrochemical performance of such‐obtained non‐platinum catalyst is discussed and compared to platinum‐based ORR catalysts. Based on the results collected here, we are able to propose and test possible proton exchange fuel cell (PEFC) operating conditions where non‐platinum ORR catalysts can be utilised. Direct methanol fuel cell (DMFC) data demonstrating a superior performance of the non‐platinum catalyst relative to platinum black, often perceived as the state‐of‐the‐art oxygen–reduction catalyst for the DMFC cathode is presented.     

质子交换膜燃料电池阴极催化剂的位置效应

考虑局部几何效应,通过二维稳态数学模型研究了质子交换膜燃料电池阴极催化剂的位置与其表面传质和反应能力的关系。模型方程涉及氧气在催化层气孔的传输,氧气在气相和电解质相界面的分配以及氧气和质子在电解质中的传递和电化学反应过程。计算结果表明,催化剂表面的氧气扩散能力对催化剂的位置变化非常敏感,随催化剂深入电解质内部,其表面的氧气扩散能力经短暂上升后迅速下降。催化剂位置对质子传递阻力的影响与氧气扩散类似,但位置效应要弱些。性能比较确定最优的催化剂位置是恰好处于刚被电解质膜完全覆盖的位置。     

Effect of cathode GDL characteristics on mass transport in PEM fuel cells

The effect of the content of the hydrophobic agent in the cathode gas diffusion layer (GDL) on the mass transport in the proton exchange membrane fuel cells (PEMFCs) was studied using mercury porosimetry, scanning electron microscopy, and electrochemical polarization techniques. The mercury intrusion data and SEM micrograph indicated that the hydrophobic agent alters the surface and bulk structure of the GDL, thereby controlling gas-phase void volume and liquid water transport. The electrochemical polarization curves were measured and quantitatively analyzed to determine the oxygen transport limitation both in the catalyst layer and the GDL. Evaluation of the parameter ζ, which represents the cathode GDL characteristics for liquid water transport, indicated that the optimized content of the hydrophobic agent and effective water management results from a trade-off between the hydrophobicity and the absolute permeability for faster water drainage.     

Carbon corrosion characteristics of CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanostructures in acidic media and implications for ORR performance

Accelerated electrochemical corrosion of nitrogen-containing carbon (CN _x ) oxygen reduction catalysts was performed by a chronoamperometric hold at 1.2 V versus NHE in acidic electrolyte using a rotating disk electrode system. Cyclic voltammograms were used to measure the electrochemically active quinone/hydroquinone redox reaction couple indicating the degree of carbon corrosion. Half-cell testing of CN _x oxygen reduction catalyst materials showed superior carbon corrosion resistance compared to Vulcan carbon, the most ubiquitous cathode catalyst support. When oxygen reduction activity was measured before and after carbon corrosion, carbon corrosion resilience trended with the oxygen reduction activity. CN _x catalysts subjected to carbon corrosion testing did not show a change in the onset of oxygen reduction reaction (ORR) activity potentials with only a slight reduction in current density, but showed improved ORR selectivity to the complete reduction of dioxygen to water.     

Electrodics at the gas diffusion platinum electrodes-H3PW12O40 proton conducting liquid electrolyte interface

The optimization procedure of gas diffusion electrode (anode and cathode) development is described for a new type of low temperature fuel cell using as proton conducting electrolyte a concentrated aqueous solution of H₃PW₁₂O₄₀ acid. The procedure consists of full factorial design of experiments performed by varying three variables:

1. (a) content of polytetrafluoroethylene (PTFE) in the catalyst layer of electrodes;

2. (b) content of fluoroethylenepropylene (FEP) in the diffusional (supporting) layer of electrodes; and

3. (c) thickness of the diffusional layer of electrodes on three levels (low, medium and high) during the measurements of hydrogen permeability through dry electrodes, measurements of electrolyte absorption in the electrodes and during the electrochemical measurements of polarization curves for oxygen reduction, hydrogen oxidation and of the oxygen gain in a half-cell at room temperature.

The results obtained demonstrate that the electrochemical activity in the half-cell reactions is regulated by the gas permeability of diffusional layer and wettability of the catalyst layer. The strongest influence on the observables has the polymer content in the diffusional layer. However, in the case of anode optimization, a strong interaction between the polymer content in the catalytic layer and polymer content in the diffusional layer has been demonstrated.     

Mn/Co oxide on Ni foam as a bifunctional catalyst for Li–air cells

Binary Mn/Co oxide sheets with spherical flower-like hierarchical structure are grown directly on the surface of a Ni foam skeleton as a cathode for Li–O₂ batteries using a hydrothermal method. This integrated cathode architecture eliminates the negative effects of a conductive carbon additive and binder on the electrochemical performance of Li–O₂ batteries and minimizes the processing steps in fabrication of cathodes for Li–O₂ batteries. The porous Ni foam acts as a scaffold and current collector, and the highly hierarchical porous flower-like structure of the binary Mn/Co oxide sheet acts as a highly active catalyst. Together, they facilitate effective diffusion of oxygen gas as well as rapid ion and electron conduction during electrochemical reactions. When assembled in Li–O₂ cells, the prepared catalyst exhibits excellent catalytic activities, including the oxygen reduction and oxygen evolution reactions. In particular, the Li–O₂ cell using the cathode delivers an extremely high specific discharge capacity of 9690 mAh g^-1 under a applied specific current of 200 mA g^-1 and operate successfully in a long lifespan of 66 cycles even under a high specific current of 600 mA g^-1 and a limited discharge-charge capacity mode of 1000 mAh g^-1. The simultaneous effect of the fast electron transport kinetics provided by the free-standing structure and the high catalytic activity of the binary Mn/Co oxide show promise for use in air electrodes for Li–O₂ batteries.     

Oxygen reduction at Pt and Pt70Ni30 in H2SO4/CH3OH solution

The electrochemical oxygen reduction reaction (ORR) was studied at Pt and Pt alloyed with 30 atom% Ni in 1 M H₂SO₄ and in 1 M H₂SO₄/0.5 M CH₃OH by means of rotating disc electrode. In pure sulphuric acid, the overpotential of ORR at 1 mA cm⁻² is about 80 mV lower at Pt₇₀Ni₃₀ than at pure Pt. It was found that in methanol containing electrolyte solution the onset potential for oxygen reduction at PtNi is shifted to more positive potentials and the alloy catalyst has an 11 times higher limiting current density for oxygen reduction than Pt. Thus, PtNi as cathode catalyst should have a higher methanol tolerance for fuel cell applications. On the other hand, no significant differences in the methanol oxidation on both electrodes was found using cycling voltammetry, especially regarding the onset potential for methanol oxidation. During all the measurements no significant electrochemical activity loss was observed at Pt_0.7Ni_0.3. Ex-situ XPS investigations before and after the electrochemical experiments have revealed Pt enrichment in the first surface layers of the PtNi.     

Carbon nano-tube supported Pt–Pd as methanol-resistant oxygen reduction electrocatalyts for enhancing catalytic activity in DMFCs

This work tries to study the problem of methanol crossover through the polymer electrolyte in direct methanol fuel cells (DMFCs) by developing new cathode electrocatalysts. For this purpose, a series of gas diffusion electrodes (GDEs) were prepared by using single-walled carbon nanotubes (SWCNTs) supported Pt–Pd (Pt–Pd/SWCNT) with different Pd contents at the fixed metal loading of 50 wt%, as bimetallic electrocatalysts, in the catalyst layer. Pt–Pd/SWCNT was prepared by depositing the Pt and Pd nanoparticles on a SWCNTs support. The elemental compositions of bimetallic catalysts were characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES) system. The performances of the GDEs in the methanol oxidation reaction (MOR) and in the oxygen reduction reaction with/without the effect of methanol oxidation reaction were investigated by means of electrochemical techniques: cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS). The results indicated that GDEs with Pt–Pd/SWCNT possess excellent electrocatalytic properties for oxygen reduction reaction in the presence of methanol, which can originate from the presence of Pd atoms and from the composition effect.