基于非贵金属氧还原催化剂的质子交换膜燃料电池性能

质子交换膜燃料电池的成本和寿命问题是制约其商业化的主要瓶颈. 开发高效稳定的新型非铂氧还原催化剂是降低电池成本的重要途径. 过渡金属-氮-碳型非贵金属催化剂具有较高催化活性、资源丰富、价格低廉等优点, 被认为是未来最有希望替代铂的氧还原催化剂. 本综述从催化剂的设计构筑、催化层结构优化以及电池测试等方面, 对过渡金属-氮-碳型非贵金属催化剂的国内外最新研究进展进行了重点讨论, 并对未来其发展趋势提出展望.     

Polyaniline/Platinum Composite Cathode Catalysts Towards Durable Polymer Electrolyte Membrane Fuel Cells

Polymer stabilization proved to be a promising approach to increase the catalytic performance of common platinum/carbon based cathode catalysts (Pt/C) used in polymer electrolyte membrane fuel cells (PEMFCs). Platinum and polyaniline composite catalysts (Pt/C/PANI) were prepared by combining chemical polymerization reactions with anion exchange reactions. Electrochemical ex-situ characterizations of the decorated Pt/C/PANI catalysts show high catalytic activity toward the oxygen reduction reaction (ORR) and, more importantly, a significant enhanced durability compared to the undecorated Pt/C catalyst. Transmission electron microscopy (TEM) investigations reveal structural benefits of Pt/C/PANI for ORR catalysis. All studies confirm high potential of Pt/C/PANI for practical fuel cell application.     

Recent Developments in Carbon-Based Nanocomposites for Fuel Cell Applications: A Review

Carbon-based nanocomposites have developed as the most promising and emerging materials in nanoscience and technology during the last several years. They are microscopic materials that range in size from 1 to 100 nanometers. They may be distinguished from bulk materials by their size, shape, increased surface-to-volume ratio, and unique physical and chemical characteristics. Carbon nanocomposite matrixes are often created by combining more than two distinct solid phase types. The nanocomposites that were constructed exhibit unique properties, such as significantly enhanced toughness, mechanical strength, and thermal/electrochemical conductivity. As a result of these advantages, nanocomposites have been used in a variety of applications, including catalysts, electrochemical sensors, biosensors, and energy storage devices, among others. This study focuses on the usage of several forms of carbon nanomaterials, such as carbon aerogels, carbon nanofibers, graphene, carbon nanotubes, and fullerenes, in the development of hydrogen fuel cells. These fuel cells have been successfully employed in numerous commercial sectors in recent years, notably in the car industry, due to their cost-effectiveness, eco-friendliness, and long-cyclic durability. Further; we discuss the principles, reaction mechanisms, and cyclic stability of the fuel cells and also new strategies and future challenges related to the development of viable fuel cells.     

Silver Nanowires and Silanes in Hybrid Functionalization of Aramid Fabrics

New functionalization methods of meta- and para-aramid fabrics with silver nanowires (AgNWs) and two silanes (3-aminopropyltriethoxysilane (APTES)) and diethoxydimethylsilane (DEDMS) were developed: a one-step method (mixture) with AgNWs dispersed in the silane mixture and a two-step method (layer-by-layer) in which the silanes mixture was applied to the previously deposited AgNWs layer. The fabrics were pre-treated in a low-pressure air radio frequency (RF) plasma and subsequently coated with polydopamine. The modified fabrics acquired hydrophobic properties (contact angle Θ_W of 112–125°). The surface free energy for both modified fabrics was approximately 29 mJ/m², while for reference, meta- and para-aramid fabrics have a free energy of 53 mJ/m² and 40 mJ/m², respectively. The electrical surface resistance (R_s) was on the order of 10² Ω and 10⁴ Ω for the two-step and one-step method, respectively. The electrical volume resistance (R_v) for both modified fabrics was on the order of 10² Ω. After UV irradiation, the Rs did not change for the two-step method, and for the one-step method, it increased to the order of 10¹⁰ Ω. The specific strength values were higher by 71% and 63% for the meta-aramid fabric and by 102% and 110% for the para-aramid fabric for the two-step and one-step method, respectively, compared to the unmodified fabrics after UV radiation.     

Self-Compacting Alkali-Activated Materials: Progress and Perspectives

Alkali-activated materials (AAMs) are considered to be alternative cementitious materials for civil infrastructures. Nowadays, efforts have been made in developing AAMs with self-compacting ability. The obtained self-compacting AAMs (SCAAMs) accomplish superior passing and filling properties as well as excellent mechanical and environmental advantages. This work critically revisits recent progresses in SCAAMs including mixture proportions, fresh properties, mechanical strength, microstructure, acid and sulfate resistance, high temperature behaviors, impact resistance and interface shear strength. To facilitate direct comparison and interpretation of data from different publications, mixture proportions were normalized in terms of the content of key reactive components from precursors and activators, and correlation with mechanical behaviors was made. Moreover, special attention was paid to current research challenges and perspectives to promote further investigation and field application of SCAAMs as advanced construction material.     

对电极材料对非贵金属电催化剂耐久性评价的影响

质子交换膜燃料电池(PEMFCs)环境友好,具有高的能量转换效率,已受到了广泛的关注.目前,铂基电催化剂广泛使用在 PEMFCs中,但铂的储量有限,活性低,耐久性差,成本高,急需开发高性能的非贵金属电催化剂替代铂基电催化剂.非贵金属电催化剂的电化学表征基本上都沿用了铂基电催化剂的评价体系和方法,不一定适用于非贵金属电催化剂的表征.
　　本文选用铂和石墨为对电极考察其对非贵金属电催化剂在酸性电解质中耐久性测试的影响.当使用铂对电极时,商业 Pt/C电催化剂的氧还原(ORR)活性随着耐久性测试圈数的增加而降低,而非贵金属电催化剂的氧还原活性在耐久性测试过程中的变化规律与商业 Pt/C不同,呈现先降低,后升高的规律.耐久性测试前后的透射电镜(TEM)分析表明非贵金属电催化剂经过耐久性测试后,在电催化剂表面生长了铂纳米颗粒.高分辨透射电镜(HRTEM)和能量色散 X射线光谱(EDX)进一步证明以铂为对电极的三电极体系,在进行非贵金属电催化剂耐久性测试的过程中,非贵金属电催化剂表面生长了铂纳米颗粒,使得非贵金属电催化剂的 ORR活性在耐久性测试后得到显著提高.耐久性测试前后,非贵金属电催化剂氧还原过程的电子转移数由3.7变为4.0,再次证明了耐久性测试过程中铂颗粒的生成.在三电极电化学体系中,当工作电极发生阴极反应时,对电极为阳极反应,反之亦然,即在工作电极上发生的任何电化学过程,都会在对电极上完成相反的电化学过程.在循环电位扫描过程中,当铂对电极的电压高于1.0 V (vs RHE)时,开始发生铂的溶解现象,并且当电压高于1.2 V (vs RHE)时,铂的溶解量会急剧增加,部分溶解的铂会扩散到工作电极附近,并在工作电极的非贵金属电催化剂表面发生沉积作用.随着扫描圈数的增加,沉积的铂纳米颗粒的数量增加,颗粒变大,从而使非贵金属电催化剂的表观 ORR活性显著提高.该现象使得非贵金属电催化剂在酸性电解质中无法表现出其真实的耐久性.当选用石墨棒为对电极材料时,非贵金属电催化剂在酸性电解质中的 ORR活性不会受到对电极材料的影响.
　　通过考察对电极材料对非贵金属电催化剂在酸性电解质中耐久性能的影响,可以得出结论,即对非贵金属电催化剂在酸性电解质中的耐久性测试中,不宜使用铂对电极,应该使用石墨为对电极材料,以防止对电极材料干扰耐久性测试.     

燃料电池技术发展现状与展望

燃料电池是一种高效、清洁的电化学发电装置,近年来得到国内外普遍重视.本文详细阐述了燃料电池的近期研究进展与未来面临的挑战及发展方向。燃料电池在宇宙飞船、航天飞机、潜艇动力源已经得到应用;在汽车、电站及便携式电源等民用领域展现了成功的示范,但低成本、长寿命仍然是商业化面临的瓶颈问题.未来我国应大力推进燃料电池在水下潜器、航天飞行器等特殊领域的应用,解决高可靠性与安全性及环境适应性等关键问题;同时,在民用领域要实现燃料电池寿命与成本兼顾,从材料、部件及系统等3个层次深入技术改进与创新,尽快推进燃料电池的商业化.     

一种超高耐久混凝土——梯度结构混凝土

分析超高耐久混凝土的研究现状,提出了一种高耐久、低成本的超高耐久混凝土--梯度结构混凝土(Gradient Structural Concrete,简称GSC),采用电量法和氯离子扩散系数法来评价梯度结构混凝土的抗氯离子渗透性能,最后进行梯度结构混凝土的寿命预测与成本分析.结果表明,高性能混凝土(High Performance Concrete,简称HPC)、无细观界面过渡区水泥基复合材料(Meso-interfacial transition zone-free cement-based materials,简称 MIF)和梯度结构混凝土MIF-HPC的6 h导电量和氯离子扩散系数的排列顺序均为:HPC>MIF-HPC>MIF,其抗氯离子渗透性能排列顺序为:MIF>MIF-HPC>HPC.梯度结构混凝土的成本会有所增加,但由于其氯离子渗透性能大幅降低,其使用寿命得到大幅延长,使得其年损耗费用大幅下降.     

软岩力学特性研究

本文讨论了软岩的基本特性。根据软岩的膨胀崩解耐久性、冻融作用、力学性质试验结果、, 分析软岩力学特性与赋存环境(含水量、地应力、温度)和时间的关系。总结了软岩的力学性质变化特征。并提出软岩强度取值原则。     

Characterizing fracture energy of proton exchange membranes using a knife slit test

Pinhole formation in proton exchange membranes (PEM) may be caused by a process of flaw formation and crack propagation within membranes exposed to cyclic hygrothermal loading. Fracture mechanics can be used to characterize the propagation process, which is thought to occur in a slow, time‐dependent manner under cyclic loading conditions, and believed to be associated with limited plasticity. The intrinsic fracture energy has been used to characterize the fracture resistance of polymeric material with limited viscoelastic and plastic dissipation, and has been found to be associated with long‐term durability of polymeric materials. Insight into this limiting value of fracture energy may be useful in characterizing the durability of proton exchange membranes, including the formation of pinhole defects. In an effort to collect fracture data with limited plasticity, a knife slit test was adapted to measure fracture energies of PEMs, resulting in fracture energies that were two orders of magnitude smaller than those obtained with other fracture test methods. The presence of a sharp knife blade reduces crack tip plasticity, providing fracture energies that may be more representative of the intrinsic fracture energies of the thin membranes. Three commercial PEMs were tested to evaluate their fracture energies (G_c) at temperatures ranging from 40 to 90 °C and humidity levels varying from dry to 90% relative humidity (RH). Experiments were also conducted with membrane specimens immersed in water at various temperatures. The time temperature moisture superposition principle was applied to generate fracture energy master curves plotted as a function of reduced cutting rate based on the humidity and temperature conditions of the tests. The shift with respect to temperature and humidity suggests that the slitting process is viscoelastic in nature. Also such shifts were found to be consistent with those obtained from constitutive tests such as stress relaxation. The fracture energy is more sensitive to temperature than on humidity. The master curves converge at the lowest reduced cutting rates, suggesting similar intrinsic fracture energies; but diverge at higher reduced cutting rates to significantly different fracture energies. Although the relationship between G_c and ultimate mechanical durability has not been established, the test method may hold promise for investigating and comparing membrane resistance to failure in fuel cell environments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 333–343, 2010