Aspects of fatigue failure mechanisms in polymer fuel cell membranes

The swelling‐driven fatigue behavior of polymer fuel cell membranes during relative humidity (RH) cycling is investigated. In particular, swelling‐induced membrane stresses are obtained from a numerical model simulating fuel cell RH cycle tests, and compared to the lifetimes obtained experimentally from tests conducted in the absence of electrochemical effects. A strong correlation between the lifetimes of the membranes in the actual tests and model results is obtained. In general, higher RH (or swelling) amplitude results in larger stress amplitudes and shorter lifetime, that is, fewer cycles to failure. Tensile stresses are needed for forming local cavities in the membrane, which may eventually lead to craze formation. Cavitation is less likely to occur in compressed membrane at high humidities. The stress–lifetime plots for polymer fuel cell membranes exhibit similar features to those observed for other polymers. The crazing criterion for polymers suggests that craze initiation during RH cycling is more likely to occur in the low compression regions, such as under the channels, which is in agreement with experimental observations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1506–1517, 2011     

含氧燃料燃烧中燃料氧迁移路径及含氧中间体生成特性

与碳氢燃料相比, 含氧燃料在燃烧过程中容易生成醛类等非常规污染物, 这些含氧中间体的生成与燃料中氧的释放密切相关. 本文从燃料氧迁移路径的角度来研究含氧中间体的生成特性及规律. 并采用分子束质谱结合真空紫外同步辐射光电离技术(SVUV-PIMS)探测了丙烷、二甲醚、乙醇三种低压预混火焰中的主要含氧中间体, 并获得了其摩尔分数分布. 结果表明: 与外部氧相比, 燃料氧更易形成含氧中间体. 生成的最主要的含氧中间体取决于燃料氧在分子中的结构. 二甲醚火焰中甲醛为最主要的含氧中间体; 乙醇火焰中乙醛为最主要的含氧中间体; 丙烷火焰中, 甲醛和乙醛的含量均很小, 但碳氢中间体乙烯、乙炔和丙烯的含量较高.     

燃料电池技术在电催化反应领域的应用

燃料电池反应器是一种既能生产有价值化学品,又能同时发电的新型单元操作装置.由于其安全、反应易受控制、无污染,且能源资源利用率高的特点,日益受到各国工业部门的重视.本文评述了几类燃料电池反应器如酸性燃料电池、质子交换膜燃料电池和固体氧化物燃料电池的用途、工作原理及其实现工业化所面临的几个主要问题。     

Polymer blend for fuel cells based on SPEKK: Effect of cocontinuous morphology on water sorption and proton conductivity

Proton‐exchange membranes (PEM), suitable for micro and small sized fuel cells, were obtained by blending sulfonated poly(ether ketone ketone) (SPEKK) polymers with different ionic exchange capacity (IEC). This approach was used to limit the amount of swelling caused by water sorption without significantly decreasing the proton conductivity of the membrane. In particular a membrane with a cocontinuous biphasic morphology was obtained by blending two SPEKKs, with respectively, an IEC equal to 1.2 and 2.08 in the weight ratio 60/40, casted from 5% (w/v) solutions in dimethylacetamide. The effect of a cocontinuous morphology on water sorption and proton conductivity in comparison to neat SPEKK was investigated. In the range of temperatures between 40 and 70 °C, which is typical for small and micro fuel cells conditions, it was found that the ratio of proton conductivity to water sorption could be maximized. This has been attributed to the presence of percolative pathways for proton transport provided by the cocontinuous morphology along with the constraint effect of the less sulfonated component on the overall capacity of swelling of the membrane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 395–404, 2007     

Mechanism of pellet coat rupture and its effect on drug release.

In the formation of a coated controlled release preparation with functional coat layers, hydroxypropyl-methylcellulose was used to form a diffusion layer which swelled immediately upon wetting. Eudragit RS30D was used to form the outer retention layer. The rupture of pellet coat occurred when the Eudragit RS30D was unable to withstand the expansion in volume due to the influx of water and swelling of the hydroxypropylmethylcellulose diffusion layer. The sucrose core was able to contribute an osmotic effect. The hydrostatic pressure built up within the pellet can cause the pellet coat to rupture. Sodium chloride deposited in the diffusion coat was able to delay the bursting of the pellet coat. This was due to the competition for the imbibed water between sodium chloride and hydroxypropylmethylcellulose. The rupture of the pellet coat did not result in a total failure of the controlled drug delivery mechanism. Similar drug release rates were obtained irrespective whether there was a puncture in the pellet coat or not. Pressure built-up in the region away from the puncture pushed the core material towards the point of puncture and sealed the puncture point. In addition, the swelling of polymer around the point of rupture ensured continuity in the drug diffusion barrier.     

钙钛矿材料在固体氧化物燃料电池燃料重整中的应用

固体氧化物燃料电池（solid oxide fuel cell,SOFC）是通过电化学反应将化石燃料（煤、石油和天然气等）、生物质燃料或其它碳氢燃料中的化学能直接转换为电能的发电装置,能量转换效率更高、污染更低,被公认为21世纪高效绿色能源技术. 但直接以碳氢化合物为燃料时,镍基阳极中容易产生积碳,从而失去电化学催化活性. 在阳极外侧进行一次燃料的预重整是一种行之有效的解决办法,其中高效稳定的重整催化剂至关重要. 本文将结合本课题组的研究进展对钙钛矿催化剂在燃料重整中的应用进行概述,并提出自己相应的观点和展望.     

Pingba RP-3喷气燃料中有色组分的鉴定及其特性研究

用中性氧化铝吸附、无水乙酸脱附的方法，对储存中变色的Pingba RP-3喷气燃料中的有色组分进行分离制备。应用有机元素分析、红外光谱、色质联用和裂解色质联用等分析法对富集有色组分的吸附胶质进行了分析鉴定，对燃料的储存特性和有色组分的化学特性进行了考察。结果表明，Pingba RP-3喷气燃料中的有色组分全部集中在吸附胶质中，吸附胶质以含氧化合物为主，其主要成分为烷基苯酚类（及其多聚体）化合物，含氮化合物质量分数极少，未检出含硫化合物。Pingba RP-3在储存中颜色变深的主要原因是胶质中的烷基苯酚类化合物氧化和缩聚。储存过程中喷气燃料的吸附胶质和颜色增加显著，与燃料在一定条件下的氧化反应有关。     

聚苯胺修饰Pt/C催化剂对质子交换膜燃料电池动态响应的促进作用

将超级电容器材料聚苯胺引入电极催化剂中以缓冲燃料电池负载的变化.以硫酸为掺杂剂,将化学法合成的聚苯胺(PANI)与Pt/C超声分散混合,制成PANI-Pt/C催化剂.PANI-Pt/C的循环伏安测试和作为质子交换膜燃料电池阴极电催化剂的电池性能测试表明,PANI含量为10%时能够提高Pt/C催化剂对氧的还原动力学速度和燃料电池放电性能.电池在不同电流负载下的电压动态响应和对电池脉冲电流的动态响应以及PANI-Pt/C催化剂多电位电势阶跃计时电流测试显示,聚苯胺在催化剂中具有在瞬间电流负载时缓冲电池电压和电池大电流放电时平稳电压的作用.     

F-T柴油在直喷式柴油机中燃烧与排放特性的研究

煤通过Fischer-Tropsch (F-T)合成可得到十六烷值高、硫和芳香烃质量分数极低的F-T柴油。研究分析了未作改动的单缸直喷式柴油机燃用F-T柴油时的燃烧和排放特性。结果表明,与燃用0号柴油相比,燃用F-T柴油时的滞燃期平均缩短18.7%,预混燃烧放热峰值降低26.8%,扩散燃烧放热峰值较高,燃烧持续期相当。燃用F-T柴油时的最高燃烧压力略低,最大压力升高率显著下降,机械损失和燃烧噪音较小,燃油消耗率和热效率都得到显著改善。燃用F-T柴油可同时降低CO、HC、NOx和炭烟排放,其中NOx和炭烟分别平均降低16.7%和40.3%。研究表明,F-T柴油是柴油机良好的清洁代用燃料。     

Evaluation of the Performance of a Mediatorless Microbial Fuel Cell by Electrochemical Impedance Spectroscopy

A mediatorless microbial fuel cell was developed using Escherichia coli bacteria and platinised titanium mesh as electrodes, producing a maximum power density of 627 mW m^?2. The performance characteristics of the fuel cell were evaluated using both electrochemical and optical techniques. Cyclic Voltammetry showed that an anaerobically grown cell suspension of E. coli was electrochemically active, and is consistent with a role for E. coli‐secreted mediators in the functioning of the cell, after the formation of a biofilm on the surface of the electrode. Electrochemical impedance spectroscopy (EIS) data show a variation in the internal resistance during bacterial growth. EIS analysis based on an equivalent circuit revealed that the initial internal resistance of the cell (5.6 MΩ) initially reduces by around 50 % over an 8 hour period; more or less the same time where the fuel cell reaches its maximum potential of 860 mV, whereupon the resistance begins to increase resulting in the corresponding fall in potential; this trend was reversible upon the introduction of further nutrients into the cell.     

直接碳氢化合物固体氧化物燃料电池

直接碳氢化合物固体氧化物燃料电池(D-HC SOFC)具有能量密度高和运行成本低等特点,可望在便携式电源等方面得到广泛应用,已成为国际上SOFC领域的研究热点。本文对D-HC SOFC进行了热力学分析,综述了目前国际上在D-HC SOFC研究方面的现状,指出现有的D-HC SOFC研究工作绝大多数都是围绕着如何避免积碳进行。围绕着避免积碳的3条途径即降低工作温度、采用合适的催化剂和促进电化学氧化,对D-HC SOFC研究进行了阐述和讨论。文中还提到一些阳极反应机理方面的研究,并对今后的D-HC SOFC工作提出了作者的观点,认为应该在D-HC SOFC电池组方面和涉及到气体分布的阳极反应机理方面做更多工作。     

燃料电池用磺化聚酰亚胺质子交换膜材料的制备与性质

以联萘二酐、磺化二胺和含咪唑基团的非磺化二胺单体为原料,制备了一系列高相对分子质量的磺化聚酰亚胺,该类聚合物具有优异的溶解性和良好的成膜性.得到的质子交换膜具有优异的水解稳定性.苯并咪唑碱性基团的存在提高了磺化聚酰亚胺质子交换膜膜的溶胀稳定性和热稳定性、降低了膜的甲醇透过率.质子导电率测试结果表明,IEC值为2.55mequiv·g-1的膜室温条件下的质子导电率为0.121 S·cm-1,高于在相同测试条件下Nafion 117膜的质子导电率(0.09 S·cm-1).     

微波裂解硬脂酸钠脱羧成烃机理研究

可再生烃类燃料相对于脂肪酸甲酯(生物柴油)有显著优势. 本研究以硬脂酸钠为研究对象, 采用微波裂解技术开展脂肪酸盐脱羧成烃机理的研究, 通过气质联用等手段对裂解产物进行分析, 研究结果表明微波能选择性作用于硬脂酸钠羧基端, 导致其在微波场中发生偶极转向极化和界面极化. 离子或极性分子的Lorentz 力按照电磁波作用的方式运动, 有助于碳负离子的形成, 有效推动了脱羧反应的进行; 添加于反应体系中的甘油具有很高的介电常数, 在微波场中形成“高热位点”, 降低了脱羧反应活化能并为硬脂酸钠脱羧起到了供氢体的作用. 液体产物中端烯烃和正构烷烃系列从C₈～C₂₀有规律的分布, 符合烃类裂解的规律. 研究结果证实了由脂肪酸盐在微波作用和甘油做为供氢体的条件下, 脱羧裂解生产优质替代性烃类燃料和绿色化学品的可行性.     

Mechanical endurance of polymer electrolyte membrane and PEM fuel cell durability

The life of proton exchange membrane fuel cells (PEMFC) is currently limited by the mechanical endurance of polymer electrolyte membranes and membrane electrode assemblies (MEAs). In this paper, the authors report recent experimental and modeling work toward understanding the mechanisms of delayed mechanical failures of polymer electrolyte membranes and MEAs under relevant PEMFC operating conditions. Mechanical breach of membranes/MEAs in the form of pinholes and tears has been frequently observed after long‐term or accelerated testing of PEMFC cells/stacks. Catastrophic failure of cell/stack due to rapid gas crossover shortly follows the mechanical breach. Ex situ mechanical characterizations were performed on MEAs after being subjected to the accelerated chemical aging and relative humidity (RH) cycling tests. The results showed significant reduction of MEA ductility manifested as drastically reduced strain‐to‐failure of the chemically aged and RH‐cycled MEAs. Postmortem analysis revealed the formation and growth of mechanical defects such as cracks and crazing in the membranes and MEAs. A finite element model was used to estimate stress/strain states of an edge‐constrained MEA under rapid RH variations. Damage metrics for accelerated testing and life prediction of PEMFCs are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2346–2357, 2006     

微生物燃料电池中生物膜成长对电池电化学性能的影响

以大肠杆菌为接种体,葡萄糖为基质,在1 000 Ω恒外阻下生成电活性生物膜,研究了生物膜的形成对电池电化学行为的影响。应用循环伏安、阻抗测试、极化分析、输出功率和阳极电势来考察其电化学表现。研究结果表明,随着生物膜完全成熟,阳极极化电阻减小66.5%,阳极电势逐渐降低,最大输出功率密度增加260%。     

Direct methanol fuel cells for vehicular applications

Dramatic technological advances for the proton exchange membrane fuel cell have focused attention on this technology for motor vehicles. The fuel cell vehicles (FCVs) have the potential to compete with the petroleum-fueled internal combustion engine vehicles (ICEVs) in cost and performance while effectively addressing air quality, energy insecurity, and global warming concerns. Methanol being a liquid can be easily transported and can be supplied from the existing network of oil company distribution sites. Recently, combining improved catalysts with fuel cell engineering, it has been possible to overcome some of the difficulties that have frustrated previous research and development efforts in realizing a commercially viable direct methanol fuel cell. Direct methanol fuel cells (DMFCs) with power densities between 0.2 and 0.4 W/cm² at operational temperatures in the range 95–130 °C have been developed. These power densities are sufficient to suggest that stack construction is well worth while. This paper reviews recent advances and technical challenges in the field of DMFCs. Received: 27 May 1997 / Accepted: 25 November 1997     

On the development of proton conducting polymer membranes for hydrogen and methanol fuel cells

The transport properties and the swelling behaviour of NAFION and different sulfonated polyetherketones are explained in terms of distinct differences on the microstructures and in the pK_a of the acidic functional groups. The less pronounced hydrophobic/hydrophilic separation of sulfonated polyetherketones compared to NAFION corresponds to narrower, less connected hydrophilic channels and to larger separations between less acidic sulfonic acid functional groups. At high water contents, this is shown to significantly reduce electroosmotic drag and water permeation whilst maintaining high proton conductivity. Blending of sulfonated polyetherketones with other polyaryls even further reduces the solvent permeation (a factor of 20 compared to NAFION), increases the membrane flexibility in the dry state and leads to an improved swelling behaviour. Therefore, polymers based on sulfonated polyetherketones are not only interesting low-cost alternative membrane material for hydrogen fuel cell applications, they may also help to reduce the problems associated with high water drag and high methanol cross-over in direct liquid methanol fuel cells (DMFC). The relatively high conductivities observed for oligomers containing imidazole as functional groups may be exploited in fully polymeric proton conducting systems with no volatile proton solvent operating at temperatures significantly beyond 100°C, where methanol vapour may be used as a fuel in DMFCs.     

Synthesis and Ex-situ Characterization of Nafion/TiO2 Composite Membranes for Direct Ethanol Fuel Cell

Nafion/TiO₂ composite membranes for different loadings of TiO₂ were prepared by casting method for the possible application in direct ethanol fuel cell (DEFC). The properties of the composite membranes were investigated by scanning electron microscopy (SEM), x-ray diffraction (XRD), thermogravimetric analyser (TGA), ion exchange capacity, water and alcohol uptake, swelling ratio, proton conductivity, and ethanol crossover. The observed characteristics of the membranes were evaluated for DEFC and compared with the direct methanol fuel cell (DMFC) membrane. The analysis reveales a significant influence on the TiO₂ surface characteristics, water and alcohol uptake, and swelling of the membrane. The TiO₂ composite membranes exhibited a sharp decrease in methanol and ethanol crossover for 5% TiO₂ and the proton conductivity was heighest for 1% TiO₂ loading. The best compromise between proton conductivity and crossover has been found out with the help of the characteristic factor ϕ. The optimum loading of 5% TiO₂ composite membrane has shown the maximum characteristic factor.     

我国燃料乙醇生产技术的现状与展望

概述了目前国内外燃料乙醇产业现状。结合我国中粮生化能源(肇东)有限公司燃料乙醇装置,重点介绍了我国目前的燃料乙醇生产工艺技术水平、特点以及与国外的差距。本文从提高燃料乙醇生产技术水平、降低生产成本、寻找廉价非粮原料和开发新生产工艺等几个方面,对燃料乙醇生产技术的发展作了展望。