Electrochemical impedance spectra of solid-oxide fuel cells and polymer membrane fuel cells

Electrochemical impedance spectroscopy (EIS) is a very useful method for the characterization of fuel cells. The anode and cathode transfer functions have been determined independently without a reference electrode using symmetric gas supply of hydrogen or oxygen on both electrodes of the fuel cell at open circuit potential (OCP). EIS are given for both polymer electrolyte fuel cells (PEFC) and solid oxide fuel cells (SOFC) at current densities up to 0.76 A cm⁻² (PEFC) and 0.22 A cm⁻² (SOFC). With increasing current density the PEFC-impedance decreases significantly in the low frequency range reaching a minimum at 0.4 A cm⁻². At even higher current densities an increasing contribution of water diffusion is observed: the cell impedance increases again. From EIS of SOFC a finite diffusion behavior is observed even at OCP, depending on water partial pressure of the anodic gas supply. This additional element reflects the influence of water partial pressure on the cell potential. The simulation of the measured EIS with an equivalent circuit enables the calculation of the individual voltage losses in the fuel cell.     

燃料电池的发展趋势

介绍了燃料电池的工作原理、优缺点;同时以燃料电池应用为背景,综述不同类型的燃料电池如车用质子交换膜燃料电池、航天飞行器用再生燃料电池、小型便携式产品用直接甲醇燃料电池、中小型电站用固体氧化物燃料电池(SOFC)、微生物燃料电池(MFC)的技术发展现状与研究热点,并指出了未来燃料电池的发展趋势.     

Integrated methane decomposition and solid oxide fuel cell for efficient electrical power generation and carbon capture

This work proposes the application of methane decomposition (MD) as a fuel processor to replace methane steam reforming (MSR) for hydrogen production for a methane-fuelled solid oxide fuel cell (SOFC) system. In this work, comparison between the MD–SOFC and the MSR–SOFC was performed in terms of SOFC performances and economic analysis to demonstrate a benefit of using MD as a fuel processor. Energy analysis of SOFC system was evaluated based on thermally self-sufficient condition where no external energy is required for the system. Although the MD–SOFC system offers lower electrical efficiency than that of the MSR–SOFC as solid carbon is generated without being further combusted to generate energy; however, the MD–SOFC stack can be operated at higher power density due to high purity of hydrogen supplied to the fuel cell, resulting in smaller size of the system when compared to the MSR–SOFC. Moreover, the MD–SOFC system is less complicated than that of the MSR–SOFC as the CCS facility is not necessary to be included to reduce CO₂ emission. Economic analysis demonstrated that the SOFC system with MD is more competitive than the conventional system with MSR when considering the valuable by-products of solid carbon even with the low-valued carbon black. It is suggested that the success of this proposed SOFC system with MD relies on the technology development on cogeneration of hydrogen and valuable carbon products.     

Solid oxide fuel cells in combination with biomass gasification for electric power generation

Biomass, a source of renewable energy, represents an effective substitute to fossil fuels. Gasification is a process that organics are thermochemically converted into valuable gaseous products(e.g. biogas). In this work, the catalytic test demonstrated that the biogas produced from biomass gasification mainly consists of H_2,CH_4, CO,and CO_2, which were then be used as the fuel for solid oxide fuel cell(SOFC). Planar SOFCs were fabricated and adopted. The steam reforming of biogas was carried out at the anode of a SOFC to obtain a hydrogen-rich fuel.The performance of the SOFCs operating on generated biogas was investigated by I–V polarization and electrochemical impedance spectra characterizations. An excellent cell performance was obtained, for example,the peak power density of the SOFC reached 1391 mW·cm~(-2) at 750℃ when the generated biogas was used as the fuel. Furthermore, the SOFC fuelled by simulated biogas delivered a very stable operation.     

固体氧化物燃料电池系统及其应用

对固体氧化物燃料电池系统和单体电池及其工作原理、材料组成等作了简要介绍,并介绍了固体氧化物燃料电池在电厂混合发电方面与燃气轮机组成的联合系统技术以及以天然气为燃料家庭热电联产方面的应用。并指出固体氧化物燃料电池由于其高效、环保清洁将是未来能源利用的主要方式。     

铋离子掺杂固体氧化物燃料电池阴极材料的研究进展

固体氧化物燃料电池(SOFC)是一种可以将燃料中的化学能直接转化为电能的发电装置,具有燃料选择灵活、效率高、环境友好等优点。基于SOFC运行成本和长期稳定性的要求,降低工作温度已成为当前研究的热点。传统阴极较低的催化活性制约了SOFC的技术发展,因此开发具有良好催化性能的阴极材料至关重要。大量的研究表明,铋离子的掺杂能够有效提高材料的电导率和氧催化活性。从铋离子掺杂的角度出发,综述了铋离子掺杂对阴极材料的制备、结构、电导率和电化学性能的影响,并对掺铋SOFC阴极材料未来的发展趋势进行了展望。     

硫化氢固体氧化物燃料电池研究进展

综述了H2 S固体氧化物燃料电池 (SOFC)的发展历史和研制现状 ,包括固体电解质薄膜如质子传导膜和氧离子传导膜的开发、电极催化材料尤其是阳极催化材料的研制、以及整个电池系统的性能研究。指出H2 SSOFC在工业化过程中所面临和必须解决的关键技术问题是 :电解质薄膜材料的研制及其制备 ,尤其是薄膜化的制备技术 ;电极材料的开发及制备 ,特别是阳极催化材料的选择与制备技术 ;膜 -电极三合一制备技术。并对H2 SSOFC的开发及工业应用前景作了展望     

质子传导陶瓷电解质燃料电池特性分析

An electrolyte model for the solid oxide fuel cell (SOFC) with proton conducting perovskite electrolyte is developed in this study, in which four types of charge carriers including proton, oxygen vacancy (oxide ion), free electron and electron hole are taken into consideration. The electrochemical process within the SOFC with hydrogen as the fuel is theoretically analyzed. With the present model, the effects of some parameters, such as the thickness of electrolyte, operating temperature and gas composition, on the ionic transport (or gas permeation) through the electrolyte and the electrical performance, i.e., the electromotive force (EMF) and internal resistance of the cell, are investigated in detail. The theoretical results are tested partly by comparing with the experimental data obtained from SrCe0.05M0.05O3-α(M=Yb, Y) cells.     

Alternative concept for SOFC with direct internal reforming operation: Benefits from inserting catalyst rod

Mathematical models of direct internal reforming solid oxide fuel cell (DIR‐SOFC) fueled by methane are developed using COMSOL® software. The benefits of inserting Ni‐catalyst rod in the middle of tubular‐SOFC are simulated and compared to conventional DIR‐SOFC. It reveals that DIR‐SOFC with inserted catalyst provides smoother temperature gradient along the system and gains higher power density and electrochemical efficiency with less carbon deposition. Sensitivity analyses are performed. By increasing inlet fuel flow rate, the temperature gradient and power density improve, but less electrical efficiency with higher carbon deposition is predicted. The feed with low inlet steam/carbon ratio enhances good system performances but also results in high potential for carbon formation; this gains great benefit of DIR‐SOFC with inserted catalyst because the rate of carbon deposition is remarkably low. Compared between counter‐ and co‐flow patterns, the latter provides smoother temperature distribution with higher efficiency; thus, it is the better option for practical applications. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

基于天然气自热重整的SOFC系统性能分析

建立一个天然气自热重整的固体氧化物燃料电池(SOFC)系统模型,利用Aspen Plus化工流程模拟软件链接基于Fortran语言编写的电堆模型,在质量守恒和能量守恒的基础上,分析不同参数对系统性能的影响。模拟结果表明:随着水碳比的增加,甲烷和一氧化碳的转化率增大,导致氢气和二氧化碳含量增加;氧碳比和系统效率在水碳比为1.5时达到最大。随着燃料利用率的增加,电流密度增大,导致空气过量系数增大,空气利用率降低;系统的总效率和净效率均随之增大。尾气温度随着水碳比和燃料利用率的增加均呈现下降趋势。系统的最大总效率和净效率分别为44.5%和39.2%。研究结果为进一步优化自热重整系统指明了方向。     

Trends for fuel cell membrane development

Fuel cells are considered a promising energy conversion technology of the future owing to inherent advantages of electrochemical conversion over thermal combustion processes. In the polymer electrolyte fuel cell (PEFC) a proton-conducting polymer membrane is utilized as solid electrolyte, having to allow the transport of protons from anode to cathode yet block the passage of reactants (e.g. H₂, O₂) and electrons. Although PEFC technology has matured substantially over the past two decades, technological barriers, such as insufficient durability and high cost, still delay commercialization in many applications. In this contribution, we review current fuel cell membrane technology and outline approaches that are taken to improve the functionality as well as the chemical and mechanical stability of proton conducting polymers in fuel cells.     

应用于大尺寸平板型固体燃料电池电堆的Al2O3-SiO2-CaO基密封材料软化特性及其验证

设计研制了Al₂O₃-SiO₂-CaO基密封材料,对其高温晶化与软化、热性能、界面黏结特性开展了原位观察,并进行了电堆实际应用验证。结果表明:在不高于1 100℃时该密封材料均为非晶态,850℃开始软化,900~1 000℃出现球化。热重分析表明密封材料在0~960℃的质量损失较小,约为0.06%;密封材料与连接板、电池界面黏结紧密,利于固体氧化物燃料电池(SOFC)电堆密封应用。采用研制的密封材料组装了2个5单元SOFC短堆,分别进行了热循环与稳定性研究。结果表明:2个5单元电堆的开路电压达到6.0 V,平均开路电压1.2 V,电堆1热循环前后在35 A(0.56 A/cm²)条件下输出功率为运行无衰减,电堆2在27 A(电流密度0.43 A/cm²)进行恒流放电,运行300 h较为稳定。     

Operation viability and performance of solid oxide fuel cell fuelled by different feeds

The performances of solid oxide fuel cells (SOFCs) fed by different types of feed, i.e. biogas, biogas-reformed feed, methane-reformed feed and pure hydrogen, are simulated in this work. Maximum temperature gradient and maximum cell temperature are regarded as indicators for operation viability investigation whereas power density and electrical efficiency are considered as performance indicators. The change in operating parameters, i.e. excess air, fuel feed rate and operating voltage, affects both the performance and operation viability of SOFC, and therefore, these operating parameters should be carefully selected to obtain best possible power density and reasonable temperature and temperature gradient. Pure hydrogen feed offers the highest SOFC performance among the other feeds. Extremely high excess air is required for SOFC fed by biogas to become operation viable and, in addition, its power density is much lower than those of SOFCs fed by the other feeds. Methane-reformed feed offers higher power density than biogas-reformed feed since H₂ concentration of the former one is higher.     

固体氧化物燃料电池阳极材料的研究进展

固体氧化物燃料电池（solid oxide fuel cells,SOFC）有着能量转换效率高,燃料适应性强和环境友好等优点,因此受到了人们的普遍关注,但是固体氧化物燃料电池的商业化应用还取决于其关键材料的进一步发展。介绍了SOFC对阳极材料的基本要求,重点评述了各种阳极材料的优缺点及其研究进展（包括金属、金属陶瓷、混合导体氧化物等）,并对改进阳极材料性能的各种措施进行了归纳总结。     

实心多孔支撑体全膜化微型固体氧化物燃料电池的制备及性能

提出一种实心多孔支撑体全膜化微型固体氧化物燃料电池(micro solid oxide fuel cell,μSOFC)设计模型.电池用氧化钇部分稳定的氧化锆[(ZrO2)0.97(Y2O3)0.03,partially stabilized zirconia,PSZ]多孔陶瓷作为支撑体,在其上制备NiO-YSZ阳极层,分别采用离心和浸渍两种成膜工艺制备YSZ电解质膜,以La0.8Sr0.2MnO3-YSZ复合材料为阴极,对组装好的单电池进行了电化学性能测试.在850℃和800℃时,离心沉积工艺制备的单电池最大输出功率密度分别为286 mW/cm2和254 mW/cm2,而浸渍涂布法制备单电池的最大输出功率密度则分别达到572 mW/cm2和388 mW/cm2.电化学阻抗谱显示;电极极化是影响电池性能的主要因素.     

Analysis of a solid oxide fuel cell system for combined heat and power applications under non-nominal conditions

In this paper, a model for a solid oxide fuel cell (SOFC) system for decentralized electricity production is developed and studied. The proposed system, operated on natural gas, consists of a planar anode supported fuel cell section and a balance of plant (BoP) which includes gases supply, a fuel processor, a heat management system, an after-burner and a power conditioning system. A reference case is defined and evaluated taking into account the state of the art of the technology and the related technical constrains. Electrical and thermal efficiency of the system, for non-reference conditions are evaluated. In particular, the effect of the deviation from the reference conditions of fuel utilization, gas temperature spring in fuel cell stack, anode off-gas recirculation rate, air inlet temperature and external pre-reforming reaction extent is analyzed. The present study revealed to be a powerful tool for evaluating the SOFC system performance under a wide range of operation and paves the way for defining control strategies in order to maintain high system efficiency under part-load operations.     

阳极孔隙率对固体氧化物燃料电池性能影响的数值分析

基于商用计算流体动力学软件及开发的燃料电池多孔介质内多组分流动和扩散、传热传质、电化学反应、电流场等复杂的物理过程的计算程序,对采用不同孔隙率阳极的平板式阳极支撑固体氧化物燃料电池(planar-electrode-support solid oxide fuel cell,PES-SOFC)的性能进行数值计算,得到不同阳极孔隙率下单电池内部各气体组分浓度、温度、电势、电流、电流密度等参数的分布。由计算结果可知,在阳极孔隙率为0.3～0.4之间时,以氢气为燃料的该类型SOFC单电池表现出较好的气体扩散和电流传导特性,相应输出电压也较高。     

Implications for Using Biogas as a Fuel Source for Solid Oxide Fuel Cells: Internal Dry Reforming in a Small Tubular Solid Oxide Fuel Cell

The feasibility of operating a solid oxide fuel cell (SOFC) on biogas has been studied over a wide compositional range of biogas, using a small tubular solid oxide fuel cell system operating at 850 °C. It is possible to run the SOFC on biogas, even at remarkably low levels of methane, at which conventional heat engines would not work. The power output varies with methane content, with maximum power production occurring at 45% methane, corresponding to maximal production of H₂ and CO through internal dry reforming. Direct electrocatalytic oxidation of methane does not contribute to the power output of the cell. At higher methane contents methane decomposition becomes significant, leading to increased H₂ production, and hence transiently higher power production, and deleterious carbon deposition and thus eventual cell deactivation.     

三种燃料电池发电技术

燃料电池是一种新型的能量转换装置，本文详细介绍了磷酸型、熔融碳酸盐型以及固体氧化物电解质型三种主要类型的燃料电池的单电池结构、材料、设计及研究方向等几个方面的问题。     

Application of oxygen ion-conductive membranes for simultaneous electricity and hydrogen generation

The high temperature of the air in power generation gas-turbine cycles involving natural gas (mainly methane) oxidation accounts for the utilization of ion-conductive membranes within solid oxide fuel cells (SOFCs) and membrane reactors (MRs). In SOFCs, the electricity is directly derived from the chemical exergy of methane (SOFCs with internal methane reforming are considered here). Within a membrane reactor (MR), which is considered a substitute for combustion chambers in traditional gas-turbine units, the ion-conductive membranes separate oxygen from air and allow the flow of the hot combustion products (carbon dioxide and steam) to be separated from air. It permits the use of combustion products which are not diluted in nitrogen in the process of methane conversion into hydrogen. A modified gas-turbine cycle that includes a SOFC stack, an MR (instead of a traditional combustion chamber), and a catalytic reactor to convert methane to hydrogen is proposed. An exergy analysis of the proposed system is conducted to evaluate its exergy efficiency and the exergy losses for the processes occurring within the system. It is shown that, in comparison to the traditional gas-turbine cycle, there is a significant reduction (more than three times) in the exergy losses for the most irreversible process occurring in the system, natural gas combustion. It is also found that the proposed cogeneration scheme, including both power generation and the industrial catalytic conversion of methane to hydrogen, permits improved efficiencies for both technologies. The efficiency of this cogeneration, as well as the reduction in exergy losses, is demonstrated by the following observation: if the value of energy (exergy) efficiency of hydrogen production is considered equal to that for a traditional process, the corresponding thermal (energy) efficiency for electricity generation would reach values of 80–96% depending on the efficiency of a SOFC stack. The combined SOFC and MR application also eliminates the possibility of toxic nitrogen oxides formation and, at the same time, makes carbon dioxide removal from flue gases feasible (due to its high concentration). The development of the proposed technology is especially important, within the context of the hydrogen economy, if the produced hydrogen is used as a fuel for fuel cell vehicles.