甲醇制氢的燃料电池技术及应用

以质子交换膜燃料电池为例介绍了燃料电池的工作原理、结构、性能等，简述了甲醇蒸汽重整、甲醇分解以及甲醇部分氧化重整制氢为燃料电池提供燃料的催化反应机理、反应条件、催化剂性能等，阐明从甲醇制氢的离子变换膜燃料电池的优越性及应用前景。     

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。     

直接甲醇燃料电池钯基催化剂研究进展

直接甲醇燃料电池(DMFC)阳极催化剂是直接甲醇燃料电池的关键材料之一。由于钯的价格便宜、储量丰富、在碱性条件下活性较高,成为取代铂作为DMFC的潜在的阳极催化剂。着重介绍了近年来钯基阳极催化剂在碱性条件下对甲醇的电氧化的研究进展,展望了其发展前景。     

甲醇制氢的燃料电池技术及应用

以质子交换膜燃料电池为例 ,介绍了甲醇蒸汽重整、甲醇分解以及甲醇部分氧化重整制氢为燃料电池提供燃料的催化反应机理、反应条件、催化剂性能等 ,并提出了甲醇制氢的质子交换膜燃料电池的优越性及应用前景。     

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.     

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.     

直接甲醇燃料电池用质子交换膜的研究进展

综述了质子交换膜在直接甲醇燃料电池中的作用和要求,目前质子交换膜的研究进展,重点介绍了适用于直接甲醇燃料电池用质子交换膜的各种材料的改性方法。按照物理和化学两种方法对几类质子交换膜材料进行改性。同时对比了改性前和改性后各种聚合物膜的物性特点。     

直接尿素燃料电池研究进展

直接尿素燃料电池可同时处理含尿素废水(尿液等)并发电,且Ni基材料为阳极尿素电氧化反应的有效催化剂。然而由于尿素电氧化反应复杂且缓慢的动力学使得Ni基催化剂活性低且稳定性差,导致直接尿素燃料电池功率密度普遍较低。实现其应用的关键在于对Ni基催化剂进行改性以构建高效稳定的催化剂层及其膜电极组件。因此,详细评述了组装成直接尿素燃料电池的阳极催化剂研究进展,深入分析改性后的催化剂组成结构对系统性能的影响机制(包括载体效应和协同效应),旨在为设计高效稳定的尿素电氧化催化剂提供科学依据。此外,阐述了直接尿素燃料电池系统中膜材料的研究现状及其膜电极组件的构建。最后,总结并展望了该领域的研究重点及未来研究的发展方向,为开发高性能直接尿素燃料电池以推进其商业化进程提供借鉴。     

直接甲醇燃料电池研究取得成果

2011年5月8日,中科院长春应用化学研究所承担的国家高技术研究发展计划（863）课题一直接甲醇燃料电池技术开发通过科技部验收,为直接甲醇燃料电池实用化和产业化奠定了重要基础。     

直接甲醇燃料电池甲醇电氧化催化剂研究的新动向

概述了直接甲醇燃料电池甲醇电氧化催化剂最近的一些研究情况。电化学沉积法和采用有机金属前驱体、有机溶剂中还原金属化合物制备催化剂的方法可以有效地控制催化剂组成、分布、颗粒大小；铂—金属大环化合物对甲醇的电催化氧化具有很好的催化活性，金属碳化物和钙饮矿类氧化物是可能代替责金属铂而作为直接甲醇燃料电池阳极催化剂的非责金属材料。     

Influence of Methanol Crossover on the Fuel Utilization of Passive Direct Methanol Fuel Cell

The effect of methanol crossover on the fuel utilization of a passive direct methanol fuel cell (DMFC) was reported. The results revealed that the Faradaic efficiency decreased from 46.9 to 17.4% when methanol concentration increased from 1.0 to 8.0 mol L^–1 at the lower current density 11.1 mA cm^–2. However, the Faradaic efficiency increased from 14.7 to 31.3% when methanol concentration increased from 1.0 to 8.0 mol L^–1 at a higher current density of 44.4 mA cm^–2. On the other hand, although the amount of methanol was increased, the Faradaic efficiency did not change, obviously due to the uniform methanol crossover and methanol diffusion at the same methanol concentration and constant current.     

A Pumpless Methanol Feeding Method for Application in Direct Methanol Fuel Cell Systems

This paper presents a simple and reliable pumpless methanol feeding (PLMF) method for application in direct methanol fuel cell (DMFC) systems. The primary feature and advantage of the PLMF is as follows: it employs an approach that allows the cathode gas pressure to be connected with a fuel container for supplying the methanol fuel into the anode fuel loop, instead of using any feeding pump or other specially designed apparatuses. The PLMF has been used in a portable 25 W DMFC system and realised feeding methanol in real time for meeting the requirements of the system. The PLMF method not only is suitable for the DMFC system, but also can be used in other liquid‐feeding fuel cell systems.     

Empirical Model Equations for the Direct Methanol Fuel Cell DMFCs

Empirical model equations, proposed for polymer electrolyte fuel cells, are used to predict the cell voltage vs. current density response of a liquid feed direct methanol fuel cell. The model equations are validated against experimental data for a small-scale fuel cell over a wide range of methanol concentration and temperatures. A new empirical equation is presented which is able to predict the voltage response of liquid feed direct methanol fuel cells over a wide range of operating conditions and even in the case of very low current densities caused by, for example, the use of dilute methanol solutions or low cell temperatures.     

Modeling Methanol Crossover by Diffusion and Electro-Osmosis in a Flowing Electrolyte Direct Methanol Fuel Cell

A CFD model is created to analyze methanol transport in a flowing electrolyte direct methanol fuel cell (FE-DMFC) by solving the 3D advection-diffusion equation, with consideration of electro-osmosis. The average methanol flux at the anode and cathode surfaces is simulated and compared to equivalent direct methanol fuel cells. Methanol crossover is defined as methanol flux at the cathode surface, and the results reveal that methanol crossover can be drastically reduced by the flowing electrolyte. The performance of the FE-DMFC at peak power current density is evaluated, and diffusion is shown to be the dominant contribution, although electro-osmosis increases with current density. The power consumption of the electrolyte pump is shown to be negligible compared to the cell power output. This indicates that thin electrolyte channels with high flow rates could further improve the efficiency.     

Effect of Porosity in Catalyst Layers on Direct Methanol Fuel Cell Performances

Effects of porosity of catalyst layers (CLs) on direct methanol fuel cell (DMFC) performances are investigated using silicon dioxide (SiO₂) particles as a pore former. The pore size and volume of CLs are controlled by changing the size and content of SiO₂. As the size of pore formed by removal of SiO₂ increases, DMFC performances are enhanced. The augmentation in performances can be explained by facilitation of fuel transport to catalyst particles, increase of utilization efficiency of catalysts, diminishment in methanol crossover, reduction in activation loss and facilitation of water discharging out of CLs of cathode due to the controlled porosity in CLs. The enhanced fuel transport, accessibility of fuels to Pt catalyst surface, is proved by the active areas of Pt catalyst. In addition to the active area of Pt catalyst, porous CLs exhibit a decline in methanol crossover, leading to increase of open circuit voltage (OCV). The porous CLs also show improvements in activation loss due to high porosity, causing enhancement in DMFC performances. In aspect of pore volume contribution to cathode performance, the SiO₂ content is optimized. Based on the DMFC performances, it can be suggested that the optimum conditions of SiO₂ are 500 nm in size and 20 wt.% in content. The porosity effect on both electrodes appears as follows: the pores in cathode are more effective on DMFC performances (55.5%) than those of anodes (44.5%) based on the maximum power of DMFC, indicating that the pores in CLs facilitate removal of water from electrodes.     

Operation Characteristic Analysis of a Direct Methanol Fuel Cell System Using the Methanol Sensor‐less Control Method

The application of methanol sensor‐less control in a direct methanol fuel cell (DMFC) system eliminates most of the problems encountered when using a methanol sensor and is one of the major solutions currently used in commercial DMFCs. This study focuses on analyzing the effect of the operating characteristics of a DMFC system on its performance under the methanol sensor‐less control as developed by Institute of Nuclear Energy Research (INER). Notably, the influence of the dispersion of the methanol injected on the behavior of the system is investigated systematically. In addition, the mechanism of the methanol sensor‐less control is investigated by varying factors such as the timing of the injection of methanol, the cathode flow rate, and the anode inlet temperature. These results not only provide insight into the mechanism of methanol sensor‐less control but can also aid in the improvement and application of DMFC systems in portable and low‐power transportation.     

Model for the Degradation Performance of a Single‐Cell Direct Methanol Fuel Cell under Varying Operational Conditions

The effect of varying operating parameters on the degradation of a single‐cell direct methanol fuel cell (DMFC) with serpentine flow channels was investigated. Fuel cell internal temperature, methanol concentration, and air and methanol flow rates were varied in experimental tests and fuel cell performance was chronologically recorded. A DMFC semi‐empirical performance model was developed to predict the polarization curves of the DMFC and validated at different operating conditions. Performance degradation was observed and modeled over time by a linear regression model. Unlike previous studies, the cumulative exposure of the operating factors to the fuel cell was considered in the degradation analysis. The degradation model shows the cell voltage generation capacity does not significantly degrade. However, the Tafel slope of the cell changes with cumulative exposure to methanol concentration and air flow, and the ohmic resistance changes with cumulative exposure to temperature, methanol and air flow.     

Development of a Direct Alcohol Alkaline Fuel Cell Stack

Direct alcohol alkaline fuel cells (DAAFC) are one of the potential fuel cell types in the category of low temperature fuel cells, which could become an energy source for portable electronic equipment in future. In the present study, a simple DAAFC stack has been developed and studied to evaluate the maximum performance for a given fuel (methanol or ethanol) and electrolyte (KOH) at various concentrations and temperatures. The open circuit voltage of the stack of four cells was nearly 4.0 V. A particular combination, 2 M fuel (methanol or ethanol) and 3 M KOH, results in maximum power density of the stack. The maximum power density obtained from the DAAFC stack (25 °C) was 50 mW cm^–2 at 20 mA cm^–2 for methanol and 17 mA cm^–2 for ethanol. The stack power density corroborated with that obtained from a single cell, indicating there was no further loss in the stack.     

Operating Temperature Dependency on Performance Degradation of Direct Methanol Fuel Cells

The effect of operating temperature on performance degradation of direct methanol fuel cell (DMFCs) is examined to disclose the main parameter of the degradation mechanism and the degradation pattern in the membrane electrode assemblies (MEAs). The DMFC MEA degradation phenomenon is explained through the use of various electrochemical/physicochemical tools, such as electrochemical impedance spectroscopy, electrode polarization, methanol stripping voltametry, field emission‐scanning electron microscopy, X‐ray diffraction, inductively coupled plasma‐atomic emission spectroscopy, and X‐ray photoelectron spectroscopy analysis. The operation of DMFC under high temperature accelerates the degradation process of the DMFC. The higher degradation rate under high temperature DMFC operation is mainly attributed to the formation of membrane pinhole with interfacial delamination and cathode degradation. A high operating temperature may result in more considerable thermal and mechanical stress of the polymeric membrane continuously due to frequent dry–wet cycling mode and substantial uneven distribution of water between the anode and the cathode during a long period of DMFC operation. On the other hand, the electrochemical surface area deterioration by Pt coarsening and ionomers loss is not directly related to the larger DMFC performance decay at high temperature.