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.     

Designing fast oxide-ion conductors based on La2Mo2O9

The ability of solid oxides to conduct oxide ions has been known for more than a century, and fast oxide-ion conductors (or oxide electrolytes) are now being used for applications ranging from oxide fuel cells to oxygen pumping devices. To be technologically viable, these oxide electrolytes must exhibit high oxide-ion mobility at low operating temperatures. Because of the size and interaction of oxygen ions with the cationic network, high mobility can only be achieved with classes of materials with suitable structural features. So far, high mobility has been observed in only a small number of structural families, such as fluorite, perovskites, intergrowth perovskite/Bi2O2 layers and pyrochlores. Here we report a family of solid oxides based on the parent compound La2Mo2O9 (with a different crystal structure from all known oxide electrolytes) which exhibits fast oxide-ion conducting properties. Like other ionic conductors, this material undergoes a structural transition around 580 degrees C resulting in an increase of conduction by almost two orders of magnitude. Its conductivity is about 6 x 10(-2) S cm(-1) at 800 degrees C, which is comparable to that of stabilized zirconia, the most widely used oxide electrolyte. The structural similarity of La2Mo2O9 with beta-SnWO4 (ref. 14) suggests a structural model for the origin of the oxide-ion conduction. More generally, substitution of a cation that has a lone pair of electrons by a different cation that does not have a lone pair--and which has a higher oxidation state--could be used as an original way to design other oxide-ion conductors.     

Direct oxidation of hydrocarbons in a solid-oxide fuel cell

The direct electrochemical oxidation of dry hydrocarbon fuels to generate electrical power has the potential to accelerate substantially the use of fuel cells in transportation and distributed-power applications. Most fuel-cell research has involved the use of hydrogen as the fuel, although the practical generation and storage of hydrogen remains an important technological hurdle. Methane has been successfully oxidized electrochemically, but the susceptibility to carbon formation from other hydrocarbons that may be present or poor power densities have prevented the application of this simple fuel in practical applications. Here we report the direct, electrochemical oxidation of various hydrocarbons (methane, ethane, 1-butene, n-butane and toluene) using a solid-oxide fuel cell at 973 and 1,073 K with a composite anode of copper and ceria (or samaria-doped ceria). We demonstrate that the final products of the oxidation are CO2 and water, and that reasonable power densities can be achieved. The observation that a solid-oxide fuel cell can be operated on dry hydrocarbons, including liquid fuels, without reforming, suggests that this type of fuel cell could provide an alternative to hydrogen-based fuel-cell technologies.     

BaCeO3基高温质子导体研究进展

介绍了BaCeO3基高温质子导体的晶体结构、导电机理与影响电导率的因素，评述了其研究进展和在固体氧化物燃料电池（SOFC）、气体传感器以及氢泵等方面的应用，指出其在应用中存在的问题和发展方向。     

A class of non-precious metal composite catalysts for fuel cells

Fuel cells, as devices for direct conversion of the chemical energy of a fuel into electricity by electrochemical reactions, are among the key enabling technologies for the transition to a hydrogen-based economy. Of several different types of fuel cells under development today, polymer electrolyte fuel cells (PEFCs) have been recognized as a potential future power source for zero-emission vehicles. However, to become commercially viable, PEFCs have to overcome the barrier of high catalyst cost caused by the exclusive use of platinum and platinum-based catalysts in the fuel-cell electrodes. Here we demonstrate a new class of low-cost (non-precious metal)/(heteroatomic polymer) nanocomposite catalysts for the PEFC cathode, capable of combining high oxygen-reduction activity with good performance durability. Without any optimization, the cobalt-polypyrrole composite catalyst enables power densities of about 0.15 W cm(-2) in H2-O2 fuel cells and displays no signs of performance degradation for more than 100 hours. The results of this study show that heteroatomic polymers can be used not only to stabilize the non-precious metal in the acidic environment of the PEFC cathode but also to generate active sites for oxygen reduction reaction.     

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。     

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 experienced significant progress and much of the recent research have paid great efforts in understanding the processes occurring at the electrode/electrolyte interfaces. As electrochemical reactions mainly proceed at the gas, electrode and electrolyte three phase boundaries(TPBs), the microstructure and properties of the electrode/electrolyte interfaces thus play a crucial role in determining the overall cell performance and durability. Herein, we review the progress and achievements in the fundamental researches of the electrode/electrolyte(mainly oxygen-conducting) interface evolution behavior under open circuit and polarization conditions. Studies involving interfacial phenomena such as interface formation and reactions, element segregation and diffusion, micropore formation and delamination are summarized and discussed in detail. Besides, the state of the art characterization techniques that have been employed to examine the interface behavior are reviewed. Finally, the challenges and prospects of the interface research in the improvement of the performance and durability of a SOC device are discussed.     

H2S气体浓度及流率对复合质子传导膜燃料电池性能的影响

采用溶胶—凝胶法制备了纳米级Li2SO4+Li2WO4+Al2O3复合质子传导膜,研究了不同H2S气体浓度、流率和操作温度对结构为H2S、（复合MoS2阳极催化剂）/ 复合质子传导膜/（复合NiO阴极催化剂）、空气的燃料电池电化学性能影响。燃料电池的性能与通入阳极侧的H2S浓度和流率有关,H2S浓度和流率增加,提高了阳极侧气体扩散速率和电化学活性组分,使燃料电池的开路电压、输出电流与功率密度提高,电化学性能变好。即使气体中的H2S浓度低达5%时,该气体也可作为电池的燃料并用来发电。操作温度增加,质子传导膜的电传导率和电化学反应速率增加,电池的输出电流与功率密度提高。比较了MoS2与复合MoS2催化剂的性能,复合MoS2催化剂比MoS2催化剂具有更好的性能和化学稳定性。当采用纯H2S作为燃料,通入阳极和阴极侧的H2S和空气的流率分别为35mlmin-1和100mlmin-1,操作温度为650、700和750oC时,燃料电池产生的最大功率密度为12.4、52.9和130 mWcm-2、最大电流密度为45、281和350 mAcm-2。     

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.     

A thermally self-sustained micro solid-oxide fuel-cell stack with high power density

High energy efficiency and energy density, together with rapid refuelling capability, render fuel cells highly attractive for portable power generation. Accordingly, polymer-electrolyte direct-methanol fuel cells are of increasing interest as possible alternatives to Li ion batteries. However, such fuel cells face several design challenges and cannot operate with hydrocarbon fuels of higher energy density. Solid-oxide fuel cells (SOFCs) enable direct use of higher hydrocarbons, but have not been seriously considered for portable applications because of thermal management difficulties at small scales, slow start-up and poor thermal cyclability. Here we demonstrate a thermally self-sustaining micro-SOFC stack with high power output and rapid start-up by using single chamber operation on propane fuel. The catalytic oxidation reactions supply sufficient thermal energy to maintain the fuel cells at 500-600 degrees C. A power output of approximately 350 mW (at 1.0 V) was obtained from a device with a total cathode area of only 1.42 cm2.     

Osmotic Pressure of Water in Nafion~

Mechanical failure modes leading to cracks or breeches in proton exchange membrane fuel cells are driven by mechanical forces associated with swelling from water uptake and shrinkage from dehumidifi-cation. To determine the magnitude of compressive mechanical stress imposed by water swelling in a proton exchange fuel-cell membrane, the osmotic pressure of water in a perfluorosulfonic acid ionomer (Nafion? N 117) membrane was measured using a hydrostatic piston-cylinder device with an in-situ hydrophilic frit. Experiments indicate that hydrostatic stresses greater than 103.5 MPa are created in a membrane when swollen with water at 23℃ suggesting that pressure from water swelling can distort Nafion N 117-based structures as the osmotic pressure is of the same order of magnitude as the flow stress of Nafion N 117.     

Pt含量对燃料电池膜电极组件结构及性能的影响

本文基于Catalyst Coated Membrane（CCM）技术,采用70%Pt/C催化剂制备质子交换膜燃料电池（PEMFC）的核心部件膜电极组件（Membrane electrolyte assembly,MEA）。考察了电池的放电性能,并利用循环伏安（CV）、电化学阻抗谱（EIS）、扫描电镜（SEM）等技术对电池的电化学性能进行了表征。研究表明采用质量分数为70%的Pt/C催化剂与Nafion的最佳质量比例为6：1,MEAΩ在600mA/cm~2电流密度下,电压能达到0.69V,催化层的厚度显著降低,性能也明显优于40%Pt/C催化剂制备的MEA。     

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.     

Electrolyte membranes for intermediate temperature proton exchange membrane fuel cell

An overview of intermediate temperature (100–300 °C) proton conducting membrane electrolyte materials for fuel cells is presented in this review. The fuel cells operated in intermediate temperature range could enhance the electrochemical kinetics, simplify water management, and improve impurities resistance. Polyfluorosulfonic acid polymer membrane represented by Nafion, and non-fluorinated arylene polymer membranes represented by polybenzimidazole are the two most widely polymer electrolyte membranes for intermediate temperature membrane. The structure regulation and fillers addition are two effective ways to maintain the conductivity and mechanical properties of membranes at intermediate temperature. Moreover, heteropolyacids, metal pyrophosphates and inorganic membranes also have attracted widespread attention when they operate at intermediate temperature.     

固体氧化物燃料电池用导电陶瓷材料的研究进展

综述了导电陶瓷材料在固体氧化物燃料电池中的应用现状,分别从燃料电池的关键组件（电解质材料、阴极材料、阳极材料和连接材料等方面）对导电陶瓷的要求及其研究现状进行了讨论,提出目前研究广泛的导电陶瓷在固体氧化物燃料电池中存在问题。     

Development and Experimental Research of kW—scale Molten Carbonate Fuel Cells

A kW-scale moten carbonate fuel cells stack was developed and 800-hours‘ operating test and performance experimental research had been done.Utilizing domestic materials completely,we developed NiO cathode and Ni-Al aonde with the active area of 336cm^2 and γ-LiAlO2 electrolyte tile and bipolar plate with the area of 900cm^2,The stack was composed of thirth cells,with 62% Li2CO3 38% K2CO3 as its electrolyte,During the 800hours continuous operating,the performance of the stack was stable.With 99.7%(mole fraction)H2 as fuel and O2 from air as oxidant,the average operating voltage of a cell was about 0.72V.The maximal current density attained to 165mA/cm^2.and the maximal output power attained to 1080Watt.The whole perfomance of the stack approached to the international level in the early 90‘s ,This paper gives the main works and experimants results.     

基于正交试验的低压燃料电池性能

通过对低压质子交换膜燃料电池的正交试验研究,得到如下结论:氢气的湿度与氢气的当量比对于燃料电池性能的影响较小,相对于空气的湿度、当量比以及燃料电池的工作温度而言,可以不予考虑;空气当量比对燃料电池性能的影响在5个运行参数中是最复杂的.它不是有固定的影响效果,而是随着工况点的变化,随着燃料电池电流大小的变化,而发生较大的变化.随着电流的增大,空气当量比对燃料电池性能的影响也增大,当电流达到较高水平时(本试验中电流达到120A之后),这种影响会下降.     

Ionic Transfer in Hybrid Inorganic/Organic Membranes

1 Results In last years increasing interest has been devoted to the development and research of transport properties of hybrid organic/inorganic membranes. Traditionally, these membranes are used as electrolyte in fuel cells. However a number of their properties allow considering them as perspective materials for water treatment and substance purification. In this work transport properties of some ion exchange membranes modified by inorganic nanoparticles (hydrated oxides or solid acids) are discussed. ...     

Micro PEM Fuel Cells and Stacks

1 Results The effects of different operating parameters on micro proton exchange membrane (PEM) fuel cell performance were experimentally studied for three different flow field configurations (interdigitated,mesh,and serpentine).Experiments with different cell operating temperatures and different backpressures on the H2 flow channels,as well as various combinations of these parameters,have been conducted for three different flow geometries.The micro PEM fuel cells were designed and fabricated in-house t...