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.     

Poly(vinyl alcohol)–polyacrylamide blends with cesium salts of heteropolyacid as a polymer electrolyte for direct methanol fuel cell applications

A class of inorganic–organic hybrid membranes with low methanol permeability characteristics for possible direct methanol fuel cell (DMFC) applications was architected, formulated, and fabricated through the blending of poly(vinyl alcohol) (PVA) and polyacrylamide (PAM) followed by crosslinking with glutaraldehyde (Glu). Cesium salts of different heteropolyacids, including phosphomolybdic acid (PMA), phosphotungstic acid (PWA), and silicotungstic acid (SWA), were incorporated into the polymer network to form corresponding hybrid membrane materials, namely, PVA–PAM–CsPMA–Glu, PVA–PAM–CsPWA–Glu, and PVA–PAM–CsSWA–Glu, respectively (where “Cs” together with a heteropolyacid abbreviation indicates the cesium salt of that acid). All the three hybrid polymer membranes fabricated exhibited excellent swelling, thermal, oxidative, and additive stability properties with desired proton conductivities in the range 10^?2 S/cm at 50% relative humidity. A dense network formation was achieved through the blending of PVA and PAM and by crosslinking with Glu, which led to an order of magnitude decrease in the methanol permeability compared to the state‐of‐the‐art commercial Nafion 115 membrane. The hybrid membrane containing CsSWA exhibited a very low methanol permeability (1.4 × 10^?8 cm²/s) compared to other membranes containing cesium salt of heteropolyacids such as PMA and PWA. The feasibility of these hybrid membranes as proton‐conducting electrolytes in DMFC was investigated, and the preliminary results were compared with those of Nafion 115. The results illustrate the attractive features and suitability of the fabricated hybrid membranes as an electrolyte for DMFC applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Current Status of and Recent Developments in the Direct Methanol Fuel Cell

The direct methanol fuel cell (DMFC) has been discussed recently as an interesting option for a fuel‐cell‐based mobile power supply system in the power range from a few watts to several hundred kilowatts. In contrast to the favoured hydrogen‐fed fuel cell systems (e.g. the polymer electrolyte membrane fuel cell, PEMFC), the DMFC has some significant advantages. It uses a fuel which is, compared to hydrogen, easy to handle and to distribute. It also comprises a fairly simple system design compared to systems utilising liquid fuels (like methanol) to produce hydrogen from them by steam reforming or partial oxidation to finally feed a standard PEMFC. Nevertheless, many severe problems still exist for the DMFC, hindering its competitiveness as an option to hydrogen‐fed fuel cells. This work reviews the major research activities concerned with the DMFC by highlighting the problems (slow kinetics of the anodic methanol oxidation, methanol permeation through the membrane, carbon dioxide evolution at the anode) and their possible solutions. Special attention is devoted to the steady state and dynamic simulation of these fuel cell systems.     

废旧锂离子电池制备锂离子筛及其应用研究进展

锂离子电池报废量爆发式增长,预计到2023年,废旧锂离子电池回收利用将是一个超过300亿元产值的新兴市场,其中,锂资源占可回收金属价值的一半。为探索锂资源高效回收技术,基于现阶段研究热点,讨论了以废旧锰酸锂电池正极材料、废旧三元锂电池正极材料、废旧锰系锂离子电池负极材料为原料制备锂离子筛的方法;探讨了废旧锂离子电池中各类杂质成分对锂离子筛性能的影响;阐述了锰系锂离子筛技术在废旧锂离子电池的锂回收、盐湖卤水提锂和化工制药废水提锂等领域的应用。通过分析得出,锂离子筛的应用能够增加锂盐回收率与回收纯度,降低技术成本,应用前景广阔。     

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.     

密封双极性MH/Ni电池的研制及性能研究

报道了密封双极性MH/Ni电池的设计与开发。考察了电极厚度、密封技术及电解液用量等工艺条件对单体电池性能的影响,解决了双极性电池设计中的主要问题。研制开发了由4个单体电池组成的4.8V,2.8A·h密封双极性MH/Ni电池。测试结果表明,电池具有较低的内阻和良好的高倍率充放电性能。在模拟混合动力车工作环境实验中,电池的性能稳定,经过多次循环后性能没有明显衰减。这种密封双极性MH/Ni电池非常可能成为性能优异的电动车及混合动力车用电源。     

Chitosan/titanate Nanotube Hybrid Membrane with Low Methanol Crossover for Direct Methanol Fuel Cells

Titanate nanotubes (TNTs) about 10 nm in diameter and 200–600 nm in length were hydrothermally synthesized, and then incorporated into a chitosan (CS) matrix to fabricate chitosan/titanate nanotube (CS/TNT) hybrid membranes for a direct methanol fuel cell (DMFC). These hybrid membranes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray powder diffraction (XRD), thermogravimetry (TG), and positron annihilation lifetime spectroscopy (PALS). Moreover, their performances, including mechanical strength, water and methanol uptake, methanol permeability, and proton conductivity were determined. SEM results demonstrated that TNTs dispersed homogeneously in the hybrid membranes. Mechanical strength and TG measurements demonstrated that the mechanical and thermal stability of CS/TNT hybrid membranes were much higher than those of pure chitosan membranes. PALS analysis revealed that the fractional free volume (FFV) of CS/TNT hybrid membranes increased with the incorporation of TNTs and, thus, resulting in the reduction of methanol crossover. In all as‐prepared membranes, the hybrid membrane containing 15 wt % TNTs exhibited the highest mechanical strength of 85.0 MPa, low methanol permeability of 0.497 · 10^–6 cm²·s^–1, and proton conductivity of 0.0151 S·cm^–1, which had the potential for DMFC applications.     

Functionalization of polymeric materials as a high performance membrane for direct methanol fuel cell: A review

A coherent review on the advanced proton exchange membranes (PEMs) for direct methanol fuel cell (DMFC) application and the future direction in the development of a high performance polymeric membrane for DMFC were discussed in this paper. PEMs have a profound influence on performance of DMFC. The PEMs are categorized into five groups which are partially fluorinated, perfluorinated ionomers, acid–base complexes, non-fluorinated ionomers, hydro carbon and aromatic polymers. Many researchers have investigated the functionalization methods on the PEMs to solve methanol crossover problem while obtaining low electronic conductivity, high proton conductivity, low electro osmotic drag coefficient, high mechanical properties and good chemical and thermal stability. Including in this review, fabrication of PEM using electrospinning process coupled with the promising functionalized polymeric materials which were known to be the most important initiatives at present in order to further expand the full potential of DMFC performance.     

Non-Fluorinated Membranes Thickness Effect on the DMFC Performance

Abstract

In order to study the influence of the proton exchange membrane thickness on the direct methanol fuel cell (DMFC) performance, sulfonated poly (ether ether ketone) (sPEEK) membranes with a sulfonation degree (SD) of 42% and thicknesses of 25, 40, and 55 µm were prepared, characterized, and tested in a DMFC. These polymeric membranes were tested in a DMFC at several temperatures by evaluating the current-voltage polarization curve, the open circuit voltage (OCV) and the constant voltage current (CV, 35 mV). The CO₂ concentration at the cathode outlet was also measured. The thinnest sPEEK membrane proved to have the best DMFC performance, although having lower Faraday efficiency (lower ohmic losses but higher methanol permeation). In contrast, the thickest membrane presented improved properties in terms of methanol permeation (lower methanol crossover). DMFC tests results for this membrane showed 30% global efficiency, obtained with pure oxygen at the cathode feed.     

Capacity Fade Analysis of a Battery/Super Capacitor Hybrid and a Battery under Pulse Loads – Full Cell Studies

A detailed analysis of the capacity fade of a battery/supercapacitor hybrid and a battery alone has been carried out at 55 °C by discharging them at three different pulse rates. The applied peak current amplitudes were 5C (7 A), 3C (4.2 A), and 1C (1.4 A), respectively. The results indicated that for hybrids the pulse discharge run time was extended for all pulse discharge rates. The ohmic resistances estimated as a function of the pulse discharge rates were smaller for hybrids when compared with those for batteries. The variation of the ohmic resistance under pulse discharge with cycling, irrespective of the pulse discharge rate was smaller for hybrids than that for the batteries. The batteries and hybrids cycled at the lowest pulse discharge rate (high pulse discharge time) have larger capacity fade when compared with the capacity fade of the batteries and the hybrids discharged using higher discharge rates (low pulse discharge time). Impedance, cyclic voltammogram, and the rate capability studies were carried out on batteries cycled alone and on batteries cycled as part of the hybrid. The battery showed larger increase in the interfacial impedance with cycling when compared with the hybrid system.     

考虑周期划分特性和储能电池生命周期费用的混合供电系统优化

在风/柴/储混合供电系统中,风力发电的不确定性和用户负载的波动性对混合供电系统及其储能电池系统的优化设计和运行具有重要影响。针对混合供电系统,采用k-均值周期划分法考虑风力发电和用户负载的波动性,建立了混合供电系统及其储能电池系统的优化模型。在优化模型中将储能电池生命周期费用作为惩罚函数,将循环次数作为约束,以标准化能源费用为目标对混合供电系统进行优化,分析了风力发电不确定性对混合供电系统优化设计的影响。以能量需求为793 kW·h·d^-1的风/柴/储混合供电系统为例,研究了混合供电系统优化设计方法。研究表明,考虑风力发电和用户负载的周期划分后,储能电池系统循环次数显著降低,有利于储能电池使用寿命的延长。按风速特性划分周期时,储能电池系统的年循环次数最少,混合供电系统的标准化能源费用最低。当储能电池在其生命周期内的最大循环次数由2000次提升到10000次时,混合供电系统的标准化能源费用降低幅度可达8.3%~16.6%。     

Effect of operating conditions on energy efficiency for a small passive direct methanol fuel cell

Energy conversion efficiency was studied in a direct methanol fuel cell (DMFC) with an air-breathing cathode using Nafion 117 as electrolyte membrane. The effect of operating conditions, such as methanol concentration, discharge voltage and temperature, on Faradic and energy conversion efficiencies was analyzed under constant voltage discharge with quantitative amount of fuel. Both of Faradic and energy conversion efficiencies decrease significantly with increasing methanol concentration and environmental temperature. The Faradic conversion efficiency can be as high as 94.8%, and the energy conversion efficiency can be as high as 23.9% if the environmental temperature is low enough (10 °C) under constant voltage discharge at 0.6 V with 3 M methanol for a DMFC bi-cell. Although higher temperature and higher methanol concentration can achieve higher discharge power, it will result in considerable losses of Faradic and energy conversion efficiencies for using Nafion electrolyte membrane. Development of alternative highly conductive membranes with significantly lower methanol crossover is necessary to avoid loss of Faradic conversion efficiency with temperature and with fuel concentration.     

Comparative study of lead-acid batteries for photovoltaic stand-alone lighting systems

The lead-acid battery is often the weakest link in photovoltaic (PV) installations. Accordingly, various versions of lead-acid batteries, namely flooded, gelled, absorbent glass-mat and hybrid, have been assembled and performance tested for a PV stand-alone lighting system. The study suggests the hybrid VRLA batteries, which exhibit both the high power density of absorbent glass-mat design and the improved thermal properties of the gel design, to be appropriate for such an application. Among the VRLA-type batteries studied here water loss for the hybrid VRLA batteries is minimal and charge-acceptance during the service at high temperatures is better in relation to their AGM counterparts.     

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.     

AC‐Impedance Investigation of Different MEA Configurations for Passive‐Mode DMFC Mini‐Stack Applications

Membrane‐electrode assemblies (MEAs) characterised by different hydrophobic–hydrophilic properties were investigated in a passive Direct methanol fuel cell (DMFC) monopolar mini‐stack at room temperature. These properties were modulated by varying the amount of Nafion or replacing the ionomer in the catalytic layer with polytetrafluoroethylene (PTFE). Impedance spectroscopy provided valuable information with respect to the limiting processes occurring during fuel cell operation. Methanol crossover, especially in the presence of high methanol concentration, played a major role in determining the overall performance. The development of a methanol impermeable membrane appears crucial for increasing the performance of DMFC devices for portable applications.     

Development of a Self‐Adaptive Direct Methanol Fuel Cell Fed with 20 M Methanol

A passive and self‐adaptive direct methanol fuel cell (DMFC) directly fed with 20 M of methanol is developed for a high energy density of the cell. By using a polypropylene based pervaporation film, methanol is supplied into the DMFC's anode in vapor form. The mass transport of methanol from the cartridge to the anodic catalyst layer can be controlled by varying the open ratio of the anodic bipolar plate and by tuning the hydrophobicity of anodic diffusion layer. An effective back diffusion of water from the cathode to the anode through Nafion film is carried out by using an additive microporous layer in the cathode that consists of 50 wt.% Teflon and KB‐600 carbon. Accordingly, the water back diffusion not only ensures the water requirement for the methanol oxidation reaction but also reduces water accumulation in the cathode and then avoids serious water flooding, thus improving the adaptability of the passive DMFC. Based on the optimized DMFC structure, a passive DMFC fed with 20 M methanol exhibits a peak power density of 42 mW cm^–2 at 25 °C, and no obvious performance degradation after over 90 h continuous operation at a constant current density of 40 mA cm^–2.     

热管散热装置对车用锂离子电池组内温度分布影响数值模拟

电动汽车锂离子电池温度过高会降低电池的放电效率,加速电池寿命的衰减。为了降低电池组温度,设计了热管内插于电池组的散热系统。以电动汽车实际行驶过程中的速度为依据,对不同放电电流下电池组的温度场分布进行了数值计算。结果表明：随着车速的提高,电池的放电电流、产热量急剧增加,当车速达到120 km·h^-1时,放电电流高达143 A,电池放电截止时,电池组温度达到56℃;与自然对流冷却方式相比,热管冷却可以将电池组的平均温度降低4.6℃,电池组温差降低2.2℃;热管冷凝段长度的增长可以有效地降低电池组的温度,热管冷凝段长度为50 mm时,可以基本上满足电池组的散热需求。     

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.     

A Sulfophenylated Polysulfone as the DMFC Electrolyte Membrane – an Evaluation of Methanol Permeability and Cell Performance

A sulfophenylated polysulfone (PSU‐sph), carrying 0.8 sulfonic acid units per repeating unit of the polymer, is evaluated as a membrane electrolyte for DMFC applications. The liquid uptake, methanol transport characteristics, electrolyte conductivity, and fuel cell performance are investigated. The methanol transport and DMFC performance results are compared to those of Nafion® 117. The PSU‐sph membrane investigated shows superior qualities with regard to methanol crossover, with a methanol permeability of approximately 25% compared to that of Nafion®. The conductivity was measured to be 15% compared to that of Nafion®. However, this could not fully account for the internal resistance of the cell, implying that the contact resistance between the electrodes and electrolyte is higher when PSU‐sph is used, probably because the electrodes are developed for use with Nafion® membranes. The stability of the PSU‐sph membrane seems promising, with very low degradation observed over a period of 72 hours. It was concluded that although the mass transport properties of the PSU‐sph membrane sample investigated were superior, it could not match the performance of Nafion® 117 in a DMFC application. However, a higher degree of sulfonation may have a significant positive effect on cell performance. The results also showed that a fully intergrated MEA is needed to fully assess new menbrane materials.     

Improvement of the Nafion–polytetrafluoroethylene membranes for potential direct methanol fuel cell use by reduction of the methanol crossover

The possibility of ultrathin Nafion/expanded polytetrafluoroethylene (ePTFE) membranes used as proton‐exchange membranes (PEMs) for direct methanol fuel cells (DMFCs) was investigated in this study. Nafion/ePTFE membranes with a thickness of ～ 14 μm were promoted by self‐assembling Pd nanoparticles on the surface to reduce the methanol crossover. The loading of the Pd nanoparticles assembled on the membranes was 1.6–1.8 μg/cm² and had little effect on the high conductivity of the Nafion membranes. With the self‐assembly of Pd nanoparticles, the methanol permeation noticeably decreased from 340 to 28 mA/cm². As a result, the open‐ circuit voltage of the Nafion/ePTFE membranes that were self‐assembled for 48 h had a more significant increase from 0.55 to 0.73 V. The reduction of methanol crossover significantly increased the DMFC voltage‐current performance, and this means that self‐assembled Nafion/polytetrafluoroethylene PEMs have promise in DMFCs. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008