固体氧化物燃料电池阴极材料第一性原理研究进展

固体氧化物燃料电池(SOFC)具有能量转换效率高和燃料适应性广等突出优势,被认为是未来最有前景的清洁能源技术之一。目前SOFC研究热点是降低工作温度到500～800℃中低温区,以降低运行成本、增加可靠性,进而加速SOFC的商业化进程。阴极作为SOFC的重要组元,合理的设计和优化中低温下对氧还原反应具有较高催化活性的阴极材料至关重要。具有钙钛矿结构或由钙钛矿结构衍生出的层状结构的电子-离子混合导电型（MIECs）氧化物是目前研究最多的SOFC阴极材料。第一性原理可以弥补实验方面信息的缺失,能够提供电子结构、几何参数、吸附能及过渡态等相关信息,可以为合理设计和开发高性能的新型SOFC阴极材料提供科学依据和理论指导。本文通过对钙钛矿阴极氧空位的形成及迁移,氧分子在阴极（包括贵金属引入）表面上的吸附、解离、扩散过程及其规律进行了综述并总结了我们前期的研究成果,最后针对当前研究存在的问题及今后钙钛矿阴极的计算模拟研究方向进行了总结与展望。     

Dip coating technique in fabrication of cone-shaped anode-supported solid oxide fuel cells

A simple and cost-effective dip coating technique was successfully developed to fabricate NiO-YSZ anode substrates for cone-shaped anode-supported solid oxide fuel cells. A single cell, NiO-YSZ/YSZ/LSM-YSZ, was assembled and tested to demonstrate the feasibility of the technique applied. Using humidified hydrogen (75 ml/min) as fuel and ambient air as oxidant, the maximum power density of the cell was 0.78 and 1.0 W/cm² at 800 and 850 °C, respectively. The observed open-circuit voltages (OCV) was closed to the theoretical value and the scanning electron microscope (SEM) results revealed that the microstructures of the anode substrate and the cathode layer are porous and the electrolyte film is dense.     

Evaluation of commercial alloys as cathode current collector for metal-supported tubular solid oxide fuel cells

Ferritic stainless steels have become promising candidate materials for interconnects in tubular metal-supported solid oxide fuel cell stacks. A number of ferritic alloys containing between 18 and 26 mass% Cr and discrete changes in minor alloying elements and reactive elements were isothermally oxidized at 800 °C in air and their electrical resistance was measured with the objective of obtaining an overview of the properties relevant for applications for cathode side interconnect. The alloys containing Mn showed a (Mn,Cr)₃O₄ spinel layer on top of a Cr₂O₃ oxide. The electrical conductivity of the steels forming this kind of oxide layer was higher than the measured for only Cr₂O₃ former or oxide dispersion strengthened alloys and increased when the alloy contained Ti or Nb. Oxide scale spallation was observed for F18TNb and E-Brite, both containing Si. The influence of different cyclic oxidations was studied for the Crofer22APU steel, showing an irregular oxide growth as well as an increase in conductivity of the oxide scale formed when 12-h cycles were applied.     

Intermediate temperature solid oxide fuel cell based on fully integrated plasma-sprayed components

This work addresses the fabrication of membrane-type solid oxide fuel cells (SOFCs) operating at medium temperatures, where all components are fabricated by plasma spray technology, and the evaluation of the performance of the SOFC single unit in a temperature range of 500 to 800 °C. Single cells composed of LaSrMgO₃ cathodes, LaSrGaMgO₃ (LSGM) electrolytes, and Ni/yttria-stabilized zirconia anodes were fabricated in successive atmospheric plasma-spraying processes. Plasma-spraying processes have been optimized and tailored to each layer to achieve highly porous cathode and anode layers as well as high-density electrolyte layers. A major effort has been devoted to the production of the LSGM electrolyte that has a high density and is free of cracks. Electrochemical impedance spectroscopy was used to investigate the conductivity of the electrode layers, and particularly the resistance of the electrolyte layer. It revealed that the heat treatment had a great influence on the specific conductivity of the sprayed electrolyte layers and that the specific conductivity of the heat-treated layers was dramatically increased to the same magnitude as is typical for sintered LSGM pellets. The experimental results have demonstrated that the plasma-spraying process has a great potential for the integrated fabrication of medium-temperature SOFC units. The original version of this article was published as part of the ASM Proceedings, Thermal Spray 2003: Advancing the Science and Applying the Technology, International Thermal Spray Conference (Orlando, FL), May 5–8, 2003, Basil R. Marple and Christian Moreau, Ed., ASM International, 2003.     

Selection and surface treatment of alloys in solid oxide fuel cell systems

Cost and performance considerations determine the selection of various component materials in a solid oxide fuel cell power system. While the use of commercial alloys provides an opportunity for cost reduction, the requirements of different components vary widely. The interconnect materials must provide low electrical resistance while isolating the oxidizing and reducing gases. The air preheat and heat-exchanger components face high-temperature oxidizing conditions, while the fuel feed and reformer sections encounter highly reducing atmospheres that may contain varying levels of sulfur and CO, and thus are prone to sulfidation and metal dusting. Thus, each of the components requires both a judicious selection of the alloy composition and appropriate surface treatments. Coating processes were developed for two classes of alloy materials for potential use as interconnects and fuel feed hardware or process piping. This paper was presented at the ASM Materials Solutions Conference & Show held October 18–21, 2004 in Columbus, OH.     

Improving plasma-sprayed yttria-stabilized zirconia coatings for solid oxide fuel cell electrolytes

Using a D-optimal design of experiments, the influences of feedstock powder and plasma gases on deposition efficiency, gas tightness, and the electrochemical behavior of vacuum plasma-sprayed yttria-stabilized zirconia for solid oxide fuel cell electrolytes were examined. In-flight particle temperature and velocity, measured by online particle diagnostics, were correlated with plasma and deposit properties. Electrochemical testing of cells was performed to determine the influence of gas tightness and microstructure of electrolyte deposit on cell behavior. This article was originally published inBuilding on 100 Years of Success: Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Manufacturing of high performance solid oxide fuel cells (SOFCs) with atmospheric plasma spraying (APS)

The potential of atmospheric plasma spraying (APS) technology has been investigated for the manufacture of anode, electrolyte and cathode of a solid oxide fuel cell. As the substrate a tape-casted FeCr alloy was used. It turned out that all layers can be applied by this technique, however, the APS cathode layer, although applied by suspension plasma spraying led to cells with rather low performance. Much better cell characteristics could be obtained by using screen-printed LSCF cathodes, which do not need any additional thermal treatment.Anode layers with high electrochemical activity were produced by separate injection of NiO and YSZ powders. The manufacturing of gastight electrolyte layers was a key-issue of the present development. As APS ceramic coatings typically contain microcracks and pores their leakage rate is not sufficiently low for SOFC applications.Based on the understanding of the formation of defects during spraying an optimized spraying process was developed which led to highly dense coatings with the appearance of a bulk, sintered ceramic. Open cell voltages above 1 V proofed the low leakage rates of the rather thin (< 50 μm) coatings. With these cells having a screen-printed cathode an output power of 500 mW/cm² could be achieved at 800 °C.It turned out that the long-term stability of the metal substrate based APS SOFCs was rather poor. The aging of the cells was probably due to interdiffusion of anode and substrate material. Hence, diffusion barrier was applied by APS between substrate and anode. These layers were very effective in reducing the degradation rate. For these cells the output power reached 800 mW/cm².     

Compatibility between glass sealants and electrode materials of solid oxide fuel cells

BaO-CaO-Al2O3-SiO2-La2O3-B2O3 system glass materials were investigated as sealants for a solid oxide fuel cell (SOFC).The transition temperature (Tg) and the crystal temperature (Td) values decrease greatly with the increase of BaCO3 content when the other components do not change.For the thermal expansion coefficient (TEC) values,the trend is inverse.The sealant has superior thermal expansion coefficient matching properties with La(Sr)MnO3 (LSM) cathode,La(Sr)FeO3 (LSF) cathode,Ni-LDC (La doped CeO2) anode,and Ni-YSZ (yttria stabilized zirconia) cermet anode.The sealant also has superior stability,compatibility,and good bonding characteristic with these electrode materials at 800-900℃.The results indicate that the aluminosilicate system glass sealant possesses superior compatibility with electrode materials of the solid oxide fuel cell.     

Plasma spraying of lanthanum silicate electrolytes for intermediate temperature solid oxide fuel cells (ITSOFCs)

A new challenge in the field of solid oxide fuel cells (SOFCs) concerns reducing their operating temperature to 973 K. Apatite ceramics are interesting candidates for SOFC electrolytes due to their high ionic conductivity at this temperature. The present work reports on the fabrication and characterization of La₉SrSi₆O_26.5 coatings obtained by atmospheric plasma spraying with two different plasma spray powers. The microstructure and the composition of the as-sprayed and heat-treated coatings were investigated by several techniques including X-Ray Diffraction, Inductively Coupled Plasma-Atomic Emission Spectroscopy and Scanning Electron Microscopy. The open porosity of the coatings was evaluated by the Archimedean method. It was found that the as-sprayed apatite coatings were composed of an amorphous phase as well as of a crystalline apatite phase, and that they contained chemical heterogeneities resulting from Si volatilization in the high-temperature plasma. Furthermore, a heat treatment rendered it possible to obtain denser, fully crystallized apatite coatings. Ionic conductivity measurements carried out with impedance spectroscopy demonstrated that the conductivity of the apatite coatings - depending on the spraying conditions - increased with sintering.     

Critical issues in catalytic diesel reforming for solid oxide fuel cells

Developing low-cost diesel-reforming catalysts and improving fuel mixing prior to catalytic reforming were addressed as two critical issues under the current study. Ruthenium-doped lanthanum chromite and aluminite were explored as catalysts for the autothermal reforming of diesel fuel. Dodecane was used as a surrogate fuel. Both catalysts yielded nearly 20 moles of hydrogen per mole of dodecane at oxygen-to-carbon ratios of 0.5 and steam-to-carbon ratios of 2 at space velocities near 100,000/h⁻¹. Both catalysts were shown to have good S tolerance when tested with a fuel mixture containing 50 parts per million S in the form of dibenzothiophene. Parallel to catalyst development, the impact of fuel mixing and vaporization through improved liquid injection also is under investigation. This paper was presented at the ASM Materials Solutions Conference & Show held October 18–21, 2004 in Columbus, OH.     

Rupture testing as a tool for developing planar solid oxide fuel cell seals

One of the critical issues in designing and fabricating high-performance planar solid oxide fuel cell (pSOFC) stacks is the ability to hermetically seal adjacent metal and ceramic components. In our pSOFC development program, we have designed a testing technique that allows us to screen through the numerous variables involved in developing glass seals. Using this test for example, we have found that the composition of the metal component plays an important role in the strength of the seal. Microstructural analysis of as-sealed specimens revealed that an interfacial reaction zone forms during joining, and it appears that the thickness and composition of this layer are the dominant parameters that control joint strength. In this paper the details of the seal test are reported. The results have proven particularly significant in the development of the next-generation stack design. Supporting microstructural and chemical analyses collected on the test specimens are also presented and used to interpret the seal test results in an effort to identify the necessary steps toward improving glass pSOFC seals. This paper was presented at the Fuel Cells: Materials, Processing, and Manufacturing Technologies Symposium sponsored by the Energy/Utilities Industrial Sector & Ground Transportation Industrial Sector and the Specialty Materials Critical Technologies Sector at the ASM International Materials Solutions Conference, October 13–15, 2003, in Pittsburgh, PA. The symposium was organized by P. Singh, Pacific Northwest National Laboratory, S.C. Deevi, Philip Morris USA, T. Armstrong, Oak Ridge National Laboratory, and T. Dubois, U.S. Army CECOM.     

High-temperature electrical testing of a solid oxide fuel cell cathode contact material

The development of high-temperature solid-state devices for energy generation and environmental control applications has advanced remarkably over the past decade. However, there remain a number of technical barriers that still impede widespread commercial application. One of these, for example, is the development of a robust method of conductively joining the mixed-conducting oxide electrodes that lie at the heart of the device to the heat resistant metal interconnect used to transmit power to or from the electrodes and electrochemically active membrane. This study investigated the high-temperature electrical and microstructural characteristics of a series of conductive glass composite paste junctions between two contact materials representative of those used in solid-state electrochemical devices, lanthanum calcium manganate, and 430 stainless steel. This paper was presented at the Fuel Cells: Materials, Processing, and Manufacturing Technologies Symposium sponsored by the Energy/Utilities Industrial Sector & Ground Transportation Industrial Sector and the Specialty Materials Critical Technologies Sector at the ASM International Materials Solutions Conference, October 13–15, 2003, in Pittsburgh, PA. The symposium was organized by P. Singh, Pacific Northwest National Laboratory, S.C. Deevi, Philip Morris USA, T. Armstrong, Oak Ridge National Laboratory, and T. Dubois, U.S. Army CECOM.     

Fabrication and study on Ni1−xFexO-YSZ anodes for intermediate temperature anode-supported solid oxide fuel cells

Bimetal oxides Ni_1−xFe_xO (x = 0.01, 0.04, 0.08, 0.1, 0.15, 0.2, 0.4, 0.5) were synthesized and studied as anodes for intermediate temperature solid oxide fuel cells (SOFCs) based on yttria-stabilized zirconia (YSZ) film electrolyte. A single cell consisted of Ni_1−xFe_xO-YSZ anode, YSZ electrolyte film, LSM–YSZ composite cathode was prepared and tested at the temperature from 600 °C to 850 °C with humidified hydrogen (75 ml min⁻¹) as fuel and ambient air as oxidant. It was found that the cell with Ni_0.9Fe_0.1O-YSZ anode showed the highest power density, 1.238 W cm⁻² at 850 °C, among the cells with different anode composition. The promising performance of Ni_1−xFe_xO as anode suggests that bimetal anodes are worth studied for SOFCs in future.     

A facile and environment-friendly method to fabricate thin electrolyte films for solid oxide fuel cells

A facile and environment-friendly method, the so-called vertical deposition (abbreviated as VD) method, is used to prepare thin yttria-stabilized zirconia (YSZ) films (≤5 μm) for solid oxide fuel cells (SOFCs). The YSZ films are self-assembled by VD process based on capillary force. The influence of experimental conditions (e.g. concentration of YSZ dispersion, deposition times, and sintering procedure) on the morphology of the films produced and thereby on the performance of SOFC devices is investigated. The single cell utilizing a 5 μm dense YSZ film as solid electrolyte achieves a high open circuit voltage of 1.05 V which remains stable at 700 °C for 4 h. The peak power density is 0.4 W cm⁻² at 800 °C for the phase inversion anode-supported fuel cell composed of an YSZ electrolyte film of 5 μm thick. The VD method developed herein is promising for preparing ultra-thin electrolyte films for SOFCs.     

Designing sealing glasses for solid oxide fuel cells

Thermal and chemical properties of “invert” glasses and glass-ceramics developed for hermetic seals for solid oxide fuel cells are described. The glasses crystallize to form thermally stable pyro- and orthosilicate phases with the requisite thermal expansion match to the Y-stabilized ZrO₂ (YSZ) electrolyte. In addition, the glasses bond to Cr-steel substrates at 800–850 °C without forming extensive interfacial reaction products. The thermal expansion characteristics of the glass-ceramics remain essentially unchanged after 28 days at 750 °C. Compositions with lower (≤2 mol%) B₂O₃ contents exhibit the lowest volatilization rates when exposed to wet forming gas at 750 °C. This paper was presented at the ASM Materials Solutions Conference & Show held October 18–21, 2004 in Columbus, OH.     

A radiation-based approach to planar solid oxide fuel cell modules

This article describes the initial analysis underlying the design of a core module consisting of a 1 to 3 kW solid oxide fuel cell (SOFC) stack and a radiant air preheater (RAP) module. The design and testing of three SOFC stack/RAP modules was part of a California Energy Commission-sponsored project with the Gas Technology Institute. The objective of the design was to improve the thermal management of an SOFC system through radiant heat transfer from the stack walls to adjacent air preheater panels. The testing of this and subsequent modules has suggested that use of the radiation-based approach significantly improved the management of stack-generated heat. This paper was presented at the ASM Materials Solutions Conference & Show held October 18–21, 2004 in Columbus, OH.     

Carbonate fuel cell materials

This article reviews the current status and discusses future opportunities for major direct fuel cell (DFC) materials. Major progress on DFC materials development (e.g., electrode, electrolyte, matrix, catalyst, cell hardware, and stack/power plant hardware) at fuel cell energy is discussed. Long-term (i.e., ∼18,000 h) field testing results are reported. These results confirm at least a five year operational life for selected key stack materials. Cost reduction is the current main focus. This paper was presented at the ASM Materials Solutions Conference & Show held October 18–21, 2004 in Columbus, OH.     

Development of porous anode layers for the solid oxide fuel cell by plasma spraying

This article focuses on the development of the anode layer for solid oxide fuel cells by plasma spraying. The composite (cermet) anode, developed by thermal spraying, consisted of nickel and yttria-stabilized zirconia (YSZ). The effect of different plasma-spraying technologies on the microstructure characteristics and the electrochemical behavior of the anode layer were investigated. Coatings were fabricated by spraying nickel-coated graphite or nickel oxide with YSZ using a Triplex II plasma torch under atmospheric conditions as well as a standard F4 torch under atmospheric or soft-vacuum conditions. The investigations were directed to have an open microporous structure, higher electrical conductivity, and catalytic activity of anode deposits. Porosity was investigated by measuring the gas permeability. Scanning electron microscopy and x-ray diffraction technologies were applied to examine the morphology, microstructure, and composition of the layers. Electrical conductivity measurements were carried out to determine the ohmic losses within the anode layer. The most promising layers were analyzed by measuring the electrochemical behavior to obtain information about catalytic activity and performance. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

SmBaCoCuO5+x as cathode material based on GDC electrolyte for intermediate-temperature solid oxide fuel cells

The performance of SmBaCoCuO_5+x (SBCCO) cathode has been investigated for their potential utilization in intermediate-temperature solid oxide fuel cells (IT-SOFCs). The powder X-ray diffraction (XRD), thermal expansion and electrochemical performance on Ce_0.9Gd_0.1O_1.95 (GDC) electrolyte are evaluated. XRD results show that there is no chemical reaction between SBCCO cathode and GDC electrolyte when the temperature is below 950 °C. The thermal expansion coefficient (TEC) value of SBCCO is 15.53 × 10⁻⁶ K⁻¹, which is ∼23% lower than the TEC of the SmBaCo₂O_5+x (SBCO) sample. The electrochemical impedance spectra reveals that SBCCO symmetrical half-cells by sintering at 950 °C has the best electrochemical performance and the area specific resistance (ASR) of SBCCO cathode is as low as 0.086 Ω cm² at 800 °C. An electrolyte-supported fuel cell generates good performance with the maximum power density of 517 mW cm⁻² at 800 °C in H₂. Preliminary results indicate that SBCCO is promising as a cathode for IT-SOFCs.