Two-dimensional numerical modelling of a direct methanol fuel cell

The results of a numerical simulation of a direct methanol fuel cell (DMFC) with liquid methanol feed are presented. A two-dimensional numerical model of a DMFC is developed based on mass and current conservation equations. The velocity of the liquid is governed by gradients of membrane phase potential (electroosmotic effect) and pressure. The results show that, near the fuel channel, transport of methanol is determined mainly by the pressure gradient, whereas in the active layers, and in the membrane, diffusion transport dominates. Shaded zones, where there is a lack of methanol, are formed in front of the current collectors. The results reveal a strong influence of the hydraulic permeability of the backing layer K _p ^BL on methanol crossover through the membrane. If the value of K _p ^BL is comparable to that of the membrane and active layers, electroosmotic effects lead to the formation of an inverse pressure gradient. The flux of liquid driven by this pressure gradient is directed towards the anode and reduces methanol crossover.     

Material aspects of the liquid feed direct methanol fuel cell

A study of a small scale Liquid Feed Direct Methanol Fuel Cell (LFDMFC), based on solid polymer electrolyte membrane, is reported. Two flow cell designs, one with a parallel flow channel arrangement and the other with a spot design of flow bed, are used. The structure of the DMFC comprises a composite of two porous electrocatalytic electrodes; Pt–Ru–carbon catalyst anode and Pt–carbon catalyst cathode, on either side of a solid polymer electrolyte (SPE) membrane. The performance of three Pt–Ru catalysts is compared. The influence of the degree of Teflon loading on the electrode structure is also reported. The effect of the following parameters: cell temperature, oxygen gas or air pressure, methanol liquid flow rate and methanol concentration on the power performance is described.     

直接甲醇燃料电池参比电极的设计与稳定性

提出了用于原位测量直接甲醇燃料电池(DMFC)极化的参比电极的结构设计,并考察了电解质的润湿程度对参比电极的电位及其电位稳定性的影响.结果表明：在可逆氢电极(RHE)作为参比电极的DMFC中,RHE的电位随电解质润湿程度的增加而降低,其电位的稳定性主要取决于其表面状态的稳定性.提出要获得电位稳定及测量准确的极化曲线,RHE处的电解质应处于对侧液态水润湿的状态,且电极表面要有适量、稳定流速的氢气.     

直接甲醇燃料电池

介绍了直接甲醇燃料电池的原理、结构,并与发展较早的氢气燃料电池进行优劣比较。针对近期商业化便携式燃料电池的技术指标,主要讨论了直接甲醇燃料电池在性能和成本上的现状和问题,并着重阐述了阳极催化剂和电解质膜(决定其性能的两个关键因素)的研发进展。     

直接甲醇燃料电池

介绍了直接甲醇燃料电池的原理、结构,并与发展较早的氢气燃料电池进行优劣比较。针对近期商业化便携式燃料电池的技术指标,主要讨论了直接甲醇燃料电池在性能和成本上的现状和问题,并着重阐述了阳极催化剂和电解质膜（决定其性能的两个关键因素）的研发进展。     

直接甲醇燃料电池研究进展

介绍了直接甲醇燃料电池的工作原理、研究现状及最新进展,认为直接甲醇燃料电池是目前较理想的燃料电池,有广阔的发展前景。     

燃料电池用碱性膜材料的研究进展

碱性膜直接甲醇燃料电池因为结合了质子交换膜燃料电池和液体碱燃料电池的优点而产生自身独特的性质,使其可以在一定程度上弥补质子交换膜燃料电池以及液体碱燃料电池的缺点而尤其引人关注。其中碱性膜电解质为碱性膜燃料电池的核心组件,其性能直接关系到燃料电池的性能及寿命。截至目前,关于碱性膜材料的制备及应用方面的报道较多,涉及的碱性膜电解质的种类也较多。本文以燃料电池用碱性膜电解质为综述内容,对国内外关于碱性膜电解质的研究报道进行系统的梳理和介绍。     

直接甲醇燃料电池反应物浓度测量技术

直接甲醇燃料电池的阳极采用甲醇作为燃料,阴极采用纯氧或空气作为氧化剂,具有能量密度高、燃料储存方便、结构简单的优点,有望成为下一代小型电子设备的电源。反应物的浓度对直接甲醇燃料电池的性能、效率和燃料利用率等都有很大的影响,因此对燃料电池中反应物的浓度进行准确测量至关重要。本文综述了直接甲醇燃料电池中反应物浓度的测量方法,主要包括化学测量方法和物理测量方法,并对这些测量方法的优缺点、基本原理及适用范围进行了分析和评述。     

微型直接甲醇燃料电池阳极传质分析

针对微型直接甲醇燃料电池,将阳极流场板简化为规则结构的多孔介质,运用多孔介质理论建立了包括流场板在内的阳极传输模型。模型考虑了阳极流道内液体饱和度沿流动方向的变化、催化层的厚度以及甲醇渗透,计算并讨论了阳极流道内液体饱和度的分布和流量对电池电流密度的影响,分析了阳极过电位对甲醇浓度分布和电池性能的影响以及质子交换膜内的传质特性。     

直接甲醇燃料电池用阻醇质子交换膜研究进展

直接甲醇燃料电池是近十年兴起的新型燃料电池,并以其独特的优点引起了人们广泛的关注。作为其重要组成部分的质子交换膜的性质是影响电池性能的关键因素。本文在介绍近两年质子交换膜研究最新进展的基础上,综述了天然聚合物用作质子交换膜材料的研究情况,并分析了其优劣势及应用前景。     

An investigation of scale-up on the response of the direct methanol fuel cell under variable load conditions

The electrical response of the direct methanol fuel cell, based on solid polymer electrolyte, to variable load is reported. The dynamic power response of the direct methanol fuel cell is of importance particularly when the cell is used for transportation applications. The study reports the dynamic characteristics of a small-scale cell (active area 9 cm²), a large-scale cell (active area 272 cm²), and a three-cell stack. The effect of operating conditions (i.e., flow rate, cathode pressure and solution concentration) on the voltage response is described and the effect of a change of scale is discussed.     

Carbon supported and unsupported Pt–Ru anodes for liquid feed direct methanol fuel cells

A comparative study of the use of supported and unsupported catalysts for direct methanol fuel cells has been performed. The effect of catalyst loading, fuel concentration and temperature dependence on the anode, cathode and full fuel cell performance was determined in a fuel cell equipped with a reversible hydrogen reference electrode. Although the measured specific activities of supported catalysts were as much as 3-fold greater than the unsupported catalysts, membrane electrode assemblies prepared with supported catalysts showed no improvement with loadings above 0.5 mg/cm². Fuel cells utilizing 0.46 mg/cm² supported catalyst electrodes performed as well as unsupported catalyst electrodes with 2 mg/cm². The temperature dependence and methanol concentration dependence studies both suggest increased methanol permeation through the thinner supported catalyst layers relative to the unsupported catalyst layers.     

Investigation of direct methanol fuel cell performance of sulfonated polyimide membrane

Sulfonated polyimide (SPI) membranes have been evaluated as electrolyte membranes in direct methanol fuel cells (DMFCs). The membrane-electrode assembly (MEA) was made by hot-pressing the membrane, an anode and a cathode, catalyzed with PtRu/CB (PtRu dispersed on carbon black) and Pt/CB bound with Nafion^® ionomer, respectively. The performance of the cell based on SPI was compared with that of Nafion^® 112 in various operation conditions such as cell temperature (T_cell), cathode relative humidity (RH), and methanol concentration (C_MeOH). The methanol crossover at the cell based on SPI was a half of Nafion^® 112, resulting in the improved cell efficiency. Advantage of the use of SPI became much distinctive from the conventional Nafion^® 112 when the DMFC was operated at a higher T_cell or a higher C_MeOH.     

Systematic analysis of the direct methanol fuel cell

The dynamic operating behaviour of the direct methanol fuel cell (DMFC) is governed by several physico-chemical phenomena which occur simultaneously: double layer charging, electrode kinetics, mass transport inside the porous structures, reactant distributions in the anode and cathode flowbeds etc. Therefore it is essential to analyse the interactions of these phenomena in order to fully understand the DMFC. These phenomena were initially analysed independently by systematic experiments and model formulations. Electrode kinetics were determined by fitting models of varying complexity to electrochemical impedance spectroscopy (EIS) measurements. Reaction intermediates adsorbed on the catalyst seem to play a key role here. To describe mass transport across the DMFC a one-dimensional model was formulated applying the generalised Maxwell–Stefan equations for multi-component mass transport and a Flory–Huggins model for the activities of mobile species inside the membrane (PEM). Also swelling of the PEM as well as heat production and transport were considered. Finally, the anode flowbed was analysed by observing flow patterns in different flowbed designs and measuring residence time distributions (RTDs). Detailed CFD models as well as simpler CSTR network representations were used to compare to the experimental results. Even the simpler models showed good agreement with the experiments. After these investigations the results were combined: the electrode kinetics model was implemented in the mass transport model as well as in the CSTR network flowbed model. In both cases, good agreement, even to dynamic experiments, was obtained.     

Test on the degradation of direct methanol fuel cell

A 500 h life-test of direct methanol fuel cell (DMFC) was conducted in a single cell. X-ray diffraction (XRD) and transmission electron microscopy (TEM) images showed that after life-test, the particle size of electrocatalysts increased both in anode and cathode, and the degree is higher in cathode. Electrochemical areas (ECAs) of anode and cathode catalyst were evaluated by CO-stripping and hydrogen-desorption test, respectively. It was found that the ECA loss is higher than the specific surface area (SSA) loss (determined by XRD) that merely due to the sintering of the electrocatalyst particles. Energy dispersive X-ray analysis (EDX) revealed a crossover of ruthenium from the anode side to the cathode side in the cell.     

负载动态变化时直接甲醇燃料电池的响应特性

直接甲醇燃料电池动态特性的研究对于实际应用来说非常重要.实验研究了直接甲醇单体燃料电池电流动态变化时电压的响应. 基于计算机控制的负载变化,得到了各种电流变化波形及不同的加载电流、放电/开路时间、加载斜率下的电池电压动态响应.结果表明电池电压对电流动态变换变化时的响应很迅速,动态运行时电池的开路电压要比稳态时的高,加载斜率对电池动态响应特性有重要影响. 电池内部电化学反应和传热传质瞬态变化的相互作用是电池动态响应的关键.     

Proton-conducting membranes from phosphotungstic acid-doped sulfonated polyimide for direct methanol fuel cell applications

A series of novel hybrid proton conducting membranes based on sulfonated naphthalimides and phosphotungstic acid (PTA) were prepared from N-Methyl Pyrrolidone (NMP) solutions. These hybrid organic-inorganic materials, composed of two proton-conducting components, have high ionic conductivities (9.3 × 10^?2 S cm^?1 at 60 °C, 15% PTA), and show good performance in H₂|O₂ polymer electrolyte membrane fuel cells (PEMFC), previously reported by us. Moreover, they have low methanol permeability compared to Nafion^®112. In this paper we describe, for the first time, the behaviour of these hybrid membranes as electrolyte in a direct methanol fuel cell (DMFC). The maximum power densities achieved with PTA doped sulfonated naphthalimide membrane, operating with oxygen and air, were 34.0 and 12.2 mW cm^?2, respectively; about the double and triple higher than those showed by the non-doped membrane at 60 °C.     

Effects of dissolved iron and chromium on the performance of direct methanol fuel cell

Effects of Fe³⁺ and Cr³⁺ ions on the performance of direct methanol fuel cell were investigated. The results show that the cell performance decreased remarkably when the concentration of Fe³⁺ or Cr³⁺ exceeded 1 × 10⁻⁴ mol L⁻¹. Fe³⁺ displayed a strong negative effect on the catalytic oxidation of methanol, while Cr³⁺ affected the cell performance primarily by exchanging with protons of the membrane/ionomer and resulted in ionic conductivity losses. Complete recovery of the cell performance was not obtained after flushing the cell with deionized water.     

Preparation and influence of performance of anodic catalysts for direct methanol fuel cell

This research aims at increasing the utilization of platinum-ruthenium alloy (Pt-Ru) catalysts and thus lowering the catalyst loading in anodes for methanol electrooxidation. The direct methanol fuel cell’s (DMFC) anodic catalysts, Pt-Ru/C, were prepared by chemical reduction with a reducing agent added in two kinds of solutions under different circumstances. The reducing agent was added in hot solution with the protection of inert gases or just air, and in cold solution with inert gases. The catalysts were treated at different temperatures. Their performance was tested by cyclic voltammetry and potentiostatic polarization by utilizing their inherent powder microelectrode in 0.5 mol/L CH₃OH and 0.5 mol/LH₂SO₄ solution. The structures and micro-surface images of the catalysts were determined and observed by X-ray diffraction and transmission electron microscopy, respectively. The catalyst prepared in inert gases showed a better catalytic performance for methanol electrooxidation than that prepared in air. It resulted in a more homogeneous distribution of the Pt-Ru alloy in carbon. Its size is small, only about 4.5 nm. The catalytic performance is affected by the order of the reducing agent added. The performance of the catalyst prepared by adding the reductant at constant temperature of the solution is better than that prepared by adding it in the solution at 0°C and then heating it up to the reducing temperature. The structure of the catalyst was modified, and there was an increase in the conversion of ruthenium into the alloyed state and an increase in particle size with the ascension of heat treatment temperature. In addition, the stability of the catalyst was improved after heat treatment. Translated from Journal of Harbin Institute of Technology, 2006, 38 (4): 541-545 [译自: 哈尔滨工业大学学报]