车用燃料电池启停工况性能衰减

车用燃料电池(质子交换膜燃料电池)技术经过二十余年的持续研发和不断突破,使得燃料电池汽车性能基本满足了商业化指标,并成为当前备受瞩目的新能源汽车。然而,质子交换膜燃料电池伴随实际车况变化会经历燃料供应、湿度、温度、电流、电压等复杂循环过程,造成燃料电池的关键材料衰减加速,并且车用燃料电池的耐久性问题棘手且涉及面广。本文针对车用燃料电池的启停工况,归纳分析了启停工况下燃料电池的研究过程、衰减机理、实验论证、建模分析,并从燃料电池系统管理角度分析了启停衰减的缓解策略。通过对已有启停工况下质子交换膜燃料电池性能衰减失效的梳理,提出了本文的观点、分析和解释。     

Hygrothermal aging of Nafion

The membrane durability is a critical issue for the development of Proton Exchange Membrane Fuel Cells (PEMFC). Since PEMFC in situ tests were not conclusive to determine Nafion^® membrane degradation mechanism, ex situ aging tests were performed on Nafion^® 112 in practical fuel cell usage conditions. The polymer chemical structure evolution was investigated by infrared spectroscopy (IR) and Nuclear Magnetic Resonance (NMR) while its hydrophilicity, directly linked to its protonic conductivity, is established through sorption isotherms by Dynamical Vapour Sorption (DVS). Durability studies over a period of 400 days revealed membrane degradation through a modification of sulfonic acid end-groups. Formation of sulfonic anhydride (from the condensation of sulfonic acids) was strongly demonstrated by IR spectroscopy and, indirectly, by NMR. The substitution of ionic end-groups by less hydrophilic anhydrides leads to a significant decrease of water uptake and thus of its hydrophilicity. Surprisingly, kinetic study reveals that the hygrometric level accelerates this condensation reaction.     

Recent developments in catalyst-related PEM fuel cell durability

Cost and durability remain the two major barriers to the widespread commercialization of polymer electrolyte membrane fuel cell (PEMFC)-based power systems, especially for the most impactful but challenging fuel cell electric vehicle (FCEV) application. Commercial FCEVs are now on the road; however, their PEMFC systems do not meet the cost targets established by the U.S. Department of Energy, primarily due to the high platinum loading needed on the cathode to achieve the requisite performance and lifetime. While the activities of a number of commercial Pt-based alloy cathode catalysts exceed the beginning-of-life (BOL) targets, these activities, and the overall cathode performance, degrade via a variety of mechanisms described herein. Degradation is mitigated in current FCEVs by utilizing a cathode catalyst with a lower BOL activity (e.g., much lower transition metal alloy content and larger BOL nanoparticle size), necessitating higher catalyst loadings, and through the utilization of system controls that avoid conditions known to exacerbate degradation processes, such as limiting the fuel cell stack voltage range. The design and development of active and robust materials and eliminating the need for vehicle mitigation strategies would greatly simplify the operating system, allowing for greater transient operation, avoiding large hybridization, and curtailing of fuel cell power. Although system mitigation strategies have provided the near-term pathway for FCEV commercialization, material-specific solutions are required to further reduce costs and improve operability and efficiency. Future material developments should focus on stabilization of the electrode structure and minimization of the catalyst particle susceptibility to dissolution caused by oxide formation and reduction over PEMFC cathode-relevant operating potentials plus minimization of support corrosion. Ex situ accelerated stress tests have provided insight into the processes responsible for material and performance degradation and will continue to provide useful information on the relative stability of materials and benchmarks for robust and stable materials-based solutions not requiring system mitigation strategies to achieve adequate lifetime.     

质子交换膜燃料电池铂电催化剂稳定策略

质子交换膜燃料电池使用寿命低是制约其商业化应用的主要瓶颈. 其中,影响质子交换膜燃料电池寿命的一个主要因素是其所广泛使用的贵金属铂基电催化剂在燃料电池苛刻的运行环境下（如可变电压、强酸性、气液两相流等）容易发生降解,导致电催化剂性能衰减,从而降低了质子交换膜燃料电池的使用寿命. 因此,如何保持铂基电催化剂的电化学稳定性已成为质子交换膜燃料电池稳定性研究中的重大科学问题. 本论文基于作者在该领域的长期研究成果,评述了应用于质子交换膜燃料电池的铂电催化剂稳定性的研究进展. 重点关注了能够大幅改善铂催化剂电化学稳定性的策略,包括聚合物稳定策略、多孔碳封装/限域稳定策略以及载体稳定策略,并对这些铂催化剂稳定策略所面临的挑战进行了展望.     

质子交换膜燃料电池Pt纳米线电催化剂研究现状

质子交换膜燃料电池(PEMFC)能直接将化学能转换为电能,具有能量转换效率高、环境友好、启动快等优点.其中电催化剂是决定PEMFC性能、寿命及成本的关键材料之一.目前所采用的Pt催化剂成本较高,是阻碍其商业化的主要因素.而Pt纳米线电催化剂的Pt利用率和催化剂活性高,抗CO毒性以及耐久性好.本文综述了Pt纳米线电催化剂的制备及其电化学催化性能的研究现状.     

Stabilization Strategies of Pt Catalysts for Proton Exchange Membrane Fuel Cells北大核心CSCD

The low service lifetime of proton exchange membrane fuel cells (PEMFCs) is the main bottleneck for their commercial applications.One of the main factors is that the expensive metal Pt catalyst is easy to degradation under the harsh working environment of PEMFC (such as variable voltage, strong acidity, gas-liquid two-phase flow), which leads to the inevitable decay of the catalytic performance, thus, seriously restricting the lifetime of PEMFC.Therefore, the electrochemical stability of Pt-based electrocatalysts has become an important and hot topic to improve the PEMFC lifetime.In this paper, we review the recent development in enhancing the stability of Pt electrocatalysts for PEMFC, mainly focusing on the achievements obtained by our group, especially, the polymer stabilization strategy, carbon encapsulation/confinement stabilization strategy, and support stabilization strategy.In addition, the challenges in these Pt catalyst stabilization strategies are summarized, and the corresponding measures and future research trends in facing these challenges are suggested.,,,,. © 2018 Chinese Chemical Society. All rights reserved.     

低维纳米材料在质子交换膜燃料电池电催化反应中的应用

在聚合物膜燃料电池中,电催化剂决定了电池的运行寿命及性能。本文按照材料维数的不同,分别介绍了近年来零维、一维和二维材料在聚合物膜燃料电池电极反应中应用的最新研究进展;并对各类聚合物膜燃料电池电催化反应的机理和研究侧重点进行了详细的介绍。     

Investigations of the reasons for fungal durability of heat-treated beech wood

It is generally accepted that thermal treatment of wood by mild pyrolysis (retification or torrefaction) improves its durability to fungal degradation. However, this property has recently been questioned in the literature and definitely needs further investigation. The increase in durability conferred by thermal treatment is generally explained by four hypotheses: the low affinity of heat-treated wood to water; the generation of toxic compounds during heating; the chemical modification of the main wood polymers and the degradation of hemicelluloses. This study was undertaken to understand the reasons for durability of heat-treated beech wood. In order to confirm or not the above mentioned hypotheses, the durability of heat-treated beech wood towards Coriolus versicolor was evaluated according to different parameters like mass loss, wettability or chemical composition. The heat treatment was carried out in a temperature range of 20-280 °C under inert atmosphere for 10 different temperatures. The results show clearly an important correlation between the temperature of treatment and the fungal durability. At the same time, there was insufficient evidence to support the hypothesis of improved decay resistance due to generation of fungicidal compounds or due to the hydrophobic character of wood. Finally, the most plausible hypothesis to explain improvement of wood durability concerns its chemical modifications. Indeed, degradation of hemicellulose associated with other chemical modifications appearing during treatment could be the origin of improved durability. There is a good correlation between decay resistance and mass loss measurements which are directly correlated to hemicellulose degradation.     

聚芳醚醚酮的热老化寿命研究

本工作用热重法(TG)研究了聚芳醚醚酮(PEEK)在空气和氮气中的热分解反应过程;确定了PEEK在这两种气氛中的热分解反应模型均符合无规引发断裂模型;在空气中PEEK的热分解显示两个过程,由此计算其在空气中第一阶段的热分解和氮气中的热分解反应活化能分别为214.7kJ/mol和232.2kJ/mol;由热分解反应动力学参数推算出热老化寿命曲线,并讨论了实验条件对结果的影响,进而以失重5%作为材料寿终指标估算出PEEK在氮气和空气中使用10年的最高温度分别为307℃和274℃。     

Influence of accelerated aging on clay-reinforced polyamide 6

Organically modified clay-reinforced polyamide 6 was subjected to accelerated heat aging to estimate its long-term thermo-oxidative stability and useful lifetime compared to the virgin material. Changes in molecular weight, and thermal and mechanical properties were monitored and connected to the polymer modification encountered during aging. The incorporation of the clay filler was found to result in moderate polymer degradation during processing, which became more pronounced with aging time at elevated temperature, imparting discoloration. Post-crystallization was favoured by short periods of heat exposure, leading to an increase of crystalline content. Conversely, extended chain scission occurring after prolonged residence time negatively affected crystallites' size, lowering the degree of crystallinity. The aging-induced transformations of crystal structures correlated well with materials' mechanical performance, yielding initially hard and brittle specimens which gradually adopted a softening behavior. Relative to the unfilled polymer, the loss of ductility during aging was milder in the case of nanocomposite, indicating that the clay filler restricted degradation, prolonging durability.     

Pt–Ru electrocatalysts for fuel cells: developments in the last decade

Reviewed herein are recent advances in the synthesis and performance of Pt–Ru electrocatalysts, including core–shell-like, for anodes in direct methanol fuel cells (DMFC) and in polymer electrolyte fuel cells (PEMFCs) employing reformate gas. Model systems allowing for a better understanding of composition–property and structure–property relationships, in particular of their CO-tolerance and degradation mechanisms, as well as opportunities for innovative syntheses, support optimization, and durability improvements are discussed. Some other new electrocatalysts for DMFC and PEMFC anodes are compared with Pt–Ru systems.     

The effect of volatile organic compounds and hypoxia on paper degradation

The possible effects of volatile organic compounds (VOCs) and of hypoxic conditions on the durability of library and archival collections have been investigated. There is growing evidence that particularly in micro-environments, there may be an important contribution of these indoor-generated pollutants to the degradation of paper. However, since the principal source of VOCs in repositories is the collections themselves, there are also significant possibilities for less stable papers, which are net VOC emitters, to promote the degradation of more stable papers, which may be net VOC absorbers.Using a range of model and real historic papers, the influence of acetic acid, formic acid, furfural, toluene, 1,4-diethylbenzene, iso-butylbenzol, 2-pentylfuran, paraformaldehyde, hexanal and vanillin was evaluated by adding them to samples degraded in closed vessels at elevated temperature. Possible protective effects of the use of activated charcoal cloth, oxygen removal, and of various chemisorbents were also investigated.The results strongly suggest that particularly VOCs with acidic or oxidisable functions can have a strong effect on degradation of cellulose. This is less pronounced in lignin-containing and acidic papers and more pronounced in papers with a small alkaline reserve. The removal of VOCs from the immediate environment can have a pronounced beneficial effect on papers emitting VOCs more intensively, in fact, the lifetime expectancy can be doubled.The results have immediate implications for storage of paper-based heritage in enclosures, but also for initiation of long-term VOC monitoring programmes in libraries and archives, where significant development is still needed.     

Investigation of Degradation of Structural Adhesives under Influence of Chemicals

Structural adhesives are used for joining materials also under conditions, where they through the application will be influenced by many different chemicals. The adhesives can – if not protected from the chemical influence – be degradated of the chemicals. The degradation can because of the different structures of the polymers in the adhesives result in lower strength of the joining area, but can also give higher strength but brittleness. Information of the structures of the structural adhesives used in the project have been taken from the data sheets from the manufacturers and have been compared with investigation of the structures by FTIR and DSC. In the laboratory the HSP's (Hansen Solubility Parameters) of the adhesives has been determined and compared with the theoretically estimated HSP's. The estimation has mainly been done by Lydersens group contribution method. The chemical resistance of the adhesives have been foreseen by using HSP's of the adheisves and compared them with the HSP's of the chemicals. The structural adhesives were most of the epoxy types and of the polyurethane types with different curing systems. The structural adhesives should all have high strength and an opening time of more than 30 minutes. They were in the laboratory cured up after the specifications from the manufacturer and were stored one week after curing before they were influenced by hte chosen chemicals. The chemicals were chosen from their functional groups. In the laboratory the adhesives were influenced by different chemicals at room temperarture and under elevated temperature and under different periods to develope the degradation curves for the different chemicals and to foresee the degradation time of the adhesives before their properties were not acceptable any more. The structure after influence of the chemicals is studied by FTIR. The results of the investigations have been that it is possible to estimate the degradation by using the HSP's of the adhesives and the chemicals, but to estimate the time before degradation has been so serious that the properties of the adhesives are not acceptable any more, it is necessary to add laboratory investigations to the HSP comparisons of adhesives and chemicals. The comparison of the HSP and of the chemicals by which the adhesives can be in its lifetime has seen to be usefull especially if the chemicals are pesticides.     

Hydrolytic and enzymatic degradation of poly(trimethylene carbonate-co-d,l-lactide) random copolymers with shape memory behavior

A series of homo- and copolymers were synthesized by ring-opening polymerization of 1,3-trimethylene carbonate and d,l-lactide, using low toxic Zn(Lac)₂ as catalyst. The hydrolytic and enzymatic degradation of PTMC homopolymer and PTDLA copolymers was performed at 37 °C in pH 7.4 phosphate buffered saline or in pH 8.5 Tris buffer using proteinase K. Degradation was followed by using various analytical techniques such as NMR, GPC, DSC and ESEM. PTMC degrades extremely slowly by pure hydrolysis or in the presence of proteinase K. In contrast, PTDLA copolymers with different compositions degrade at various rates both in PBS and in enzyme solutions. The higher the LA content, the faster the degradation. LA units are preferentially degraded during hydrolytic degradation, indicating that ester bonds are more susceptible to hydrolytic cleavage than carbonate ones. Changes in surface morphology are observed during enzymatic degradation, in agreement with surface erosion process. The PTDLA11 copolymer with equivalent TMC/LA contents is highly elastic. Its residual strain is approximately 4% after the first cycle at a strain of 50%. The shape recovery ratio is up to 83%. Therefore, it is concluded that high molecular weight PTDLA copolymers are promising candidates for clinical applications in minimally invasive surgery.     

Degradation of poly(vinyl chloride) and nitrocellulose in XPS

Measurements have been made of the degradation rates for poly(vinyl chloride) (PVC) and nitrocellulose with cellulose acetate (NC) in x‐ray photoelectron spectroscopy. These materials form part of earlier studies published by others to evaluate instrumental degradation factors. In the earlier studies, results showed significant scatter such that the relative rates varied significantly from instrument to instrument. It is shown here that this variation could arise from different levels of adventitious electrons in the different instruments as well as different layer thicknesses exhibiting the degradation in PVC and NC. The former depends on electrodes in the system and the neutralizing parameters, whereas the latter causes the relative degradation rates to depend on the angle of emission of the detected electrons. These will have varied from laboratory to laboratory in the earlier study. The present study leads to simple recommendations for operating conditions to reduce the degradation effects observed. Copyright © 2003 John Wiley & Sons, Ltd.     

Durable High-Temperature Proton Exchange Membrane Fuel Cells Enabled by the Working-Temperature-Matching Palladium-Hydrogen Buffer Layer

The durability degradation during stack-operating conditions seriously deteriorates the lifetime and performance of the fuel cell. To alleviate the rapid potential rise and performance degradation, an anode design is proposed to match the working temperature of high-temperature proton exchange membrane fuel cells (HT-PEMFCs) with the release temperature of hydrogen from palladium. The result is significantly enhanced hydrogen oxidation reaction (HOR) activity of Pd and superior performance of the Pd anode. Furthermore, Pd as hydrogen buffer and oxygen absorbent layer in the anode can provide additional in situ hydrogen and absorb infiltrated oxygen during local fuel starvation to maintain HOR and suppress reverse-current degradation. Compared with the traditional Pt/C anode, the Pd/C also greatly improved HT-PEMFCs durability during start-up/shut-down and current mutation. The storage/release of hydrogen provides innovative guidance for improving the durability of PEMFCs.     

About Durability of Biodegradable Polymers: Structure/Degradability Relationships

Up to now materials were chosen to satisfy specific property(ies) in relation with the required application. Nowadays, a specific attention has to be devoted to the durability of this property regarding to the lifetime duration. It is the reason why, we paid attention about degradability. Thus, a screening of bio- and photodegradability of various selected (co)polyesters has been achieved in order to get better insights about structure / durability relationships. We developed tools allowing the prediction of the behavior of materials upon ageing and the evolution of their properties, regarding to their initial chemical structures. Hence, we could be able to design (co)polyesters characterized by well-adapted physical, thermal and mechanical properties, but also, with high photostability and/or high biodegradability.     

静电纺丝制备质子交换膜燃料电池催化剂层综述

质子交换膜燃料电池催化剂层在成本、耐久性以及性能上的局限是制约燃料电池汽车商业化的瓶颈. 已有文献证明静电纺丝技术制备的纳米纤维催化剂层能提高催化剂利用率、增加三相界面和三相通道以及提高耐久性. 作者结合所在课题组的工作综述了静电纺丝技术制备质子交换膜燃料电池催化剂层的研究进展. 首先,介绍了质子交换膜燃料电池催化剂层的发展历程,并从制备方式和结构两个方面对其进行分类和总结;接下来,从静电纺丝纳米纤维催化剂层的制备、物理特性表征、电化学性能分析及耐久性表征等方面进行了总结;最后,从三相界面、三相通道以及量产适用性的视点比较了三种结构的催化剂层,介绍了质子交换膜燃料电池催化剂层的发展趋势,并梳理了静电纺丝法制备质子交换膜燃料电池催化剂层领域待研的问题.     

Application of electrospinning for the fabrication of proton-exchange membrane fuel cell electrodes

Electrospun materials have been gaining great interest in the energy sector. Their tunability and robustness make them highly attractive, particularly for proton-exchange membrane fuel cell (PEMFC) electrodes. Conventional PEMFC electrodes, prepared by either spraying, painting, or slot-die coating, have not yet met the needs of large-scale PEMFC use. Electrospinning of fibrous materials has already shown great promise as an alternative methodology for electrode fabrication. Electrospinning has been used in fuel cell electrodes through two primary means: (1) segmented carbon or inorganic fibers to serve as precious metal catalyst support, and (2) high aspect ratio polymer/particle fibers to serve directly as the electrode. The use of electrospun fibrous electrodes has led to improved PEMFC durability and increased power output at low catalyst loadings, both of which are of paramount importance to large-scale commercialization of PEMFC electric vehicles.     

聚羟基烷酸酯酶降解动力学研究

研究了羟基丁酸 羟基戊酸共聚物 (PHBV)在脂肪酶中的降解行为 ,用滴定法测定降解速度并进行酶促反应动力学研究 .探讨了降解速度与酶浓度和底物浓度的数学关系和Michaelis Menten常数 ,从实验上和理论上证实了PHBV的物理形态和几何尺寸对酶降解过程的影响 ,以及实验数据与非均相动力学模型的拟合