中低温固体氧化物燃料电池电解质材料研究进展

 固体氧化物燃料电池（SOFC）是一种全固态的电化学能量转换装置,它的能量转换效率高达70%,且其尾气中的有毒成分含量极低,是未来化石燃料发电技术的理想选择之一。SOFC 具有较宽的工作温度范围,通常在450~1000℃。高温下（800~1000℃）尽管SOFC 在燃料选择方面具有更高的灵活性,但是材料性能衰减的加快、运营成本的提高,以及系统的开关速度变慢等一系列缺点也愈加明显。因而,SOFC 主要朝着低温化的趋势发展。降低SOFC 工作温度最有效的方法是提高固体电解质的电导率,以尽量减少电池的欧姆阻抗。本文综述了萤石型、钙钛矿型和复合型3 类固体电解质材料国内外的研究进展,同时展望了未来中低温SOFC 电解质材料的研究方向。钙钛矿型电解质材料在中低温下具有较高的纯离子电导率,且具备丰富的改性空间,有望成为将来中低温SOFC 电解质材料的首选。     

Sm2O3掺杂Ce2O3的加入量对YBa2Cu3O7-δ界面性能的影响

固体氧化物燃料电池(SOFC)具有稳定性高、寿命长、污染低等优点,是二十一世纪的绿色能源之一。当前SOFC阴极通常采用掺杂的ABO3钙钛矿型材料。这类材料在高温下具有较高的导电率和催化活性,但中温化是SOFC的趋势,高温下常用的La(Sr)MnO3阴极材料在中温下性能下降,不能满足中温下电导率的要求。本论文尝试采用柠檬酸燃烧法来制备YBa2Cu3O7-δ,并在YBCO中加入一定量的Sm2O3掺杂的Ce2O3(SDC)作为SOFC的阴极材料,通过对阻抗分析,研究了SDC掺杂量、烧结温度等对该阴极材料性能的影响。实验结果表明:随着SDC的掺杂量x(0≤x≤50%)和烧结温度的升高,阴极材料的界面阻抗减小。在SDC的掺杂量为50%时,且在800℃下烧结得到的烧结体界面阻抗最小,其界面比电阻仅为0.1353ohm/cm2(800℃),这标志着掺杂SDC的YBCO作为中温固体氧化物燃料电池的阴极材料时非常具有发展前景的。     

A high-performance cathode for the next generation of solid-oxide fuel cells

Fuel cells directly and efficiently convert chemical energy to electrical energy. Of the various fuel cell types, solid-oxide fuel cells (SOFCs) combine the benefits of environmentally benign power generation with fuel flexibility. However, the necessity for high operating temperatures (800-1,000 degrees C) has resulted in high costs and materials compatibility challenges. As a consequence, significant effort has been devoted to the development of intermediate-temperature (500-700 degrees C) SOFCs. A key obstacle to reduced-temperature operation of SOFCs is the poor activity of traditional cathode materials for electrochemical reduction of oxygen in this temperature regime. Here we present Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-delta)(BSCF) as a new cathode material for reduced-temperature SOFC operation. BSCF, incorporated into a thin-film doped ceria fuel cell, exhibits high power densities (1,010 mW cm(-2) and 402 mW cm(-2) at 600 degrees C and 500 degrees C, respectively) when operated with humidified hydrogen as the fuel and air as the cathode gas. We further demonstrate that BSCF is ideally suited to 'single-chamber' fuel-cell operation, where anode and cathode reactions take place within the same physical chamber. The high power output of BSCF cathodes results from the high rate of oxygen diffusion through the material. By enabling operation at reduced temperatures, BSCF cathodes may result in widespread practical implementation of SOFCs.     

固体氧化物燃料电池致密电解质薄膜制备技术

鉴于固体氧化物燃料电池(SOFC)在高温运行时存在的种种问题,电解质薄膜的厚度,降低其运行温度,是解决这些问题的重要途径.本文分别综述了目前常用的SOFC致密电解质薄膜的制备工艺,如化学法、物理法、陶瓷粉末法等,评述了它们的优缺点,并介绍了采用上述方法制备电解质薄膜的性能和用于电池研究的实验结果.     

Review： Perspectives on the metallic interconnects for solid oxide fuel cells

The various stages and progress in the development of interconnect materials for solid oxide fuel cells (SOFCs )over the last two decades are reviewed. The criteria for the application of materials as interconnects are highlighted. Interconnects based on lanthanum chromite ceramics demonstrate many inherent drawbacks and therefore are only useful for SOFCs operating around 1000℃. The advance in the research of anode-supported flat SOFCs facilitates the replacement of ceramic interconnects with metallic ones due to their significantly lowered working temperature. Besides, interconnects made of metals or alloys offer many advantages as compared to their ceramic counterpart. The oxidation response and thermal expansion behaviors of various prospective metallic interconnects are examined and evaluated. The minimization of contact resistance to achieve desired and reliable stack performance during their projected lifetime still remains a highly challenging issue with metallic interconnects. Inexpensive coating materials and techniques may play a key role in promoting the commercialization of SOFC stack whose interconnects are constructed of some current commercially available alloys. Alternatively, development of new metallic materials that are capable of forming stable oxide scales with sluggish growth rate and sufficient electrical conductivity is called for.     

Solid Oxide Fuel Cell：Materials, Technology and Application

Solid oxide fuel cells (SOFCs) offer a clean, pollution-free technology for the electrochemical conversion of chemical energy of hydrocarbon fuels into electricity. Many programs are being initiated in the United States, Europe, Japan and so on. The funding for SOFC development worldwide has risen dramatically and this trend is expected to continue for at least the next decades. These development programs are also investigating wider applications of SOFCs in stationary, residential, transportation and military sectors. Finally, it is summarized the key materials and fabrication processes of SOFC in this paper.     

Studies on the effects of pre-firing and sintering temperature on NSDC nanocomposite electrolytes

Solid oxide fuel cells (SOFCs) technology, with fuel flexibility, is one of the most promising power generation technology. However, the high operating temperature of SOFCs has hindered their commercial applications. As a crucial requirement to enhance its performance, SOFCs electrolytes should operate at a low temperature. Carbonate/ceria composites are developed as electrolytes for low operating temperature SOFCs, and a better understanding of the mechanism of its ionic conductivity serves this purpose. In this work, ceria-carbonate composite electrolyte, Na₂CO₃/samarium doped ceria (NSDC) were synthesized by the co-precipitation method. The synthesized electrolytes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and UV–Vis spectroscopy. The XRD and SEM results showed that the sintered NSDC nanocomposite comprised a single-phase dense electrolyte structure. The crystallite size of the NSDC nanocomposite was greatly affected by the different pre-firing temperatures and different sintering temperatures. Also, the ionic conductivity of the prepared NSDC nanocomposite electrolytes was strongly dependent on the pre-firing and sintering temperatures. The NSDC nanocomposite electrolytes were pre-fired at 950 ?°C and 650 ?°C and sintered at 1200 ?°C and 900 ?°C respectively, had ionic conductivity in H₂ and air high as 0.36 ?S/cm and 0.3 ?S/cm.     

固体氧化物燃料电池电解质用离子导体

固体氧化物燃料电池以其高的能量转换效率和清洁的发电而被广泛研究.其中电解质—离子导体材料是影响固体燃料电池的效率和热力学稳定性的关键.作为所期望的电解质材料应满足以下要求(1)高的离子导电,(2)低的电子导电,(3)在使用条件一热力学稳定,(4)好的综合力学性能.在一些荧石相关结构和钙钛矿塑结构的氧化物中通过掺杂和取代形成氧空位可得到高的氧离子导电性.本文介绍了一些这类离子导体材料,并讨论了它们的特性.     

板式固体氧化物燃料电池的热应力分析

为了深入掌握固体氧化物燃料电池(SOFC)的结构性能,进而提高其可靠性,在对SOFC的内部流动和电化学特性进行数值模拟,对顺流和逆流两种流动情况下板式SOFC内温度分布、电势特征和电流密度特征进行分析的基础上,将数值计算得到的温度场作为载荷施加到SOFC的热应力模型中,建立了数值模拟SOFC的有限元热应力模型,对SOFC关键结构中的三合一电极板中的热应力分布特征进行了分析研究.研究结果表明:相对于顺流形式,逆流形式燃料入口附近的温度梯度要大得多;材料间热膨胀系数的不匹配导致了热应力的产生;热应力的大小与温度分布和温度梯度密切相关.由于过大的热应力可能会导致SOFC结构开裂甚至破坏,该研究工作为SOFC单电池和电池堆的设计优化提供了重要的理论依据.     

Electrode/electrolyte interface and interface reactions of solid oxide cells:Recent development and advances

High temperature solid oxide cells(SOCs) consisted of solid oxide fuel cells(SOFCs) and solid oxide electrolysis cells(SOECs) are considered one of the most environmentally friendly and efficient energy conversion technology to store renewal energy from sun and wind in hydrogen and generate electricity from the fuels such as hydrogen and natural gas with high efficiency and very low greenhouse gas emission. Over the last few decades, the development of SOC technologies in particularly SOFCs has ...     

高力学性能及高导电性的防冻有机水凝胶电解质

由于水凝胶电解质的力学性能差且水在低温下会结冰,限制了水凝胶电解质在储能器件和电子导体方面的应用。加入大豆分离蛋白,以丙烯酰胺和甲基丙稀酰乙基磺基甜菜碱为单体,在二甲基亚砜/H₂O的混合溶液和氯化锂的存在下,通过自由基聚合制备了高力学性能、高导电性的防冻有机水凝胶。其具有良好的电导率(最高37.5 mS/cm)、良好的力学性能(最大应力69 kPa,最大应变762.5%)、优良的韧性和抗疲劳性能,对应变和温度具有良好的响应性、宽的传感窗口及稳定性,具有应用于传感器领域的潜力。另外,所制备的超级电容器在20 ℃和-20 ℃均表现出良好的电化学性能,20 ℃时,0.2 A/g电流密度下,超级电容器的比电容为62.1 F/g,5 A/g 的高电流密度下,比电容仍有30 F/g;同时具有良好的抗冻性能和循环稳定性,-20 ℃时,0.5 A/g电流密度下,超级电容器循环10 000圈后仍能保持20 ℃下容量的92%。     

基于ABC-SVM模型的固体氧化物燃料电池预测控制仿真研究

为了满足直流负载电压的稳定性及固体氧化物燃料电池（SOFC）的耐用性和安全性的要求,设计了两个控制回路分别对SOFC的输出电压和燃料利用率进行控制。通过设计一个简单的控制回路来使燃料利用率保持在恒定值,并在此基础上开发了一个非线性模型预测控制器以控制SOFC的输出电压。该非线性模型预测控制器基于改进的支持向量机（SVM）预测模型,首先利用Lipschitz quotients准则确定SVM预测模型的结构,然后通过人工蜂群算法（ABC）优化SVM参数。仿真结果表明,所提的基于ABC-SVM模型的SOFC预测控制算法可以很好地跟踪电压设定值,证明了ABC-SVM模型在SOFC非线性动态建模中的有效性。     

SOFC/Micro-GT混合循环系统性能分析

基于总能系统概念讨论固体氧化物燃料电池/微型燃气轮机(SOFC/Micro-GT)间接混合发电系统及其特点,建立SOFC电池堆及系统的物理、数学模型,对700kW级混合系统的稳态全负荷运行工况进行分析,结果表明混合系统净发电效率可达68.3%,加上回收的余热,系统整体热效率可达82.9%。该文还探讨了燃料利用率、平均电流密度、电池温度、压力及蒸汽/碳比等主要参数对系统性能的影响规律,为SOFC/Mciro-GT混合发电系统的设计、优化提供参考依据。     

固体氧化物燃料电池电化学特性分析

对固体氧化物燃料电池的理想电势及有效电势进行理论分析,利用有关最新发表的活化超电势、欧姆超电势和传质超电势的计算公式,对有效电势和超电势进行了计算,探讨了工作温度和燃料中水蒸汽含量对有效电势的影响.研究发现,温度对SOFC有较大影响,在电流密度较高时,工作温度越高SOFC的有效电势就越高;燃料氢气中水蒸气的含量对SOFC的理想电势和超电势都有影响,共同作用下,SOFC燃料中较小的水蒸汽含量可获得较大的有效电势.     

溶胶-凝胶法制备SiO2-P2O5-TiO2电解质薄膜

溶胶-凝胶法制备的SiO2-P2O5-TiO2电解质薄膜,具有较高的质子电导率和化学稳定性。测定不同组分电解质薄膜的质子电导率,发现随着温度的上升,质子电导率呈上升趋势。其原因为随着温度的升高,附着水排出和羟基结构的缩合。     

Quantized conductance atomic switch

A large variety of nanometre-scale devices have been investigated in recent years that could overcome the physical and economic limitations of current semiconductor devices. To be of technological interest, the energy consumption and fabrication cost of these 'nanodevices' need to be low. Here we report a new type of nanodevice, a quantized conductance atomic switch (QCAS), which satisfies these requirements. The QCAS works by controlling the formation and annihilation of an atomic bridge at the crossing point between two electrodes. The wires are spaced approximately 1 nm apart, and one of the two is a solid electrolyte wire from which the atomic bridges are formed. We demonstrate that such a QCAS can switch between 'on' and 'off' states at room temperature and in air at a frequency of 1 MHz and at a small operating voltage (600 mV). Basic logic circuits are also easily fabricated by crossing solid electrolyte wires with metal electrodes.     

无机膜在脱盐应用中的研究

水资源短缺问题已成为全球共同关注的问题.无机膜化学稳定性好、耐腐蚀、较高的机械强度以及可在高温等苛刻条件下使用等优点,使其在脱盐领域具有广阔的应用前景.有机膜除了传统的陶瓷膜外,碳基材料等由于其可调的纳米结构以及优异的性能,逐渐成为无机膜领域的研究热点.为了更好地了解不同种类无机膜的特性,拓展无机膜材料在脱盐中的应用.首先对无机膜的分类、理化性质、制备方法、盐滞留机理进行阐述;其次重点对无机膜在脱盐应用中的进展进行综述;最后对其未来在水处理领域的发展趋势做了展望.     

染料敏化太阳能电池用固态电解质研究进展

染料敏化太阳能电池是近十几年来发展起来的新型高效率、低成本电池。电解质是关系到该电池稳定性的重要材料。介绍了染料敏化太阳能电池电解质的分类,讨论了准固态电解质和固态电解质的优缺点及其研究进展。使用传统的液态电解质获得的光电转换效率较高,但稳定性受到一定的影响,使用准固态电解质和固态电解质制备的染料敏化太阳能电池,稳定性有了较大的提高。重点讨论了准固态电解质以及无机p型半导体材料、有机p型半导体材料和导电高聚物等几种主要的固态电解质的特点和相应的电池稳定性。     

SBS物理和化学改性沥青混合料路用性能研究

对SBS改性沥青混合料进行了一系列室内试验研究,包括高温车辙试验、APA车辙试验、低温弯曲试验、残留稳定度和冻融劈裂试验等.研究结果表明,SBS化学改性沥青混合料的高温稳定性、低温抗裂性和水稳定性均比SBS物理改性沥青混合料好.SBS化学改性沥青混合料具有良好的路用性能,是一种值得推广的沥青路面材料.