Atmospheric plasma spraying is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (600 to 750°C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. Processes were developed to manufacture metal-supported SOFC cathodes by axial-injection plasma spraying. Cathodes consisted of LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) or SSC (Sm0.5Sr0.5CoO3) as the primary material. Initially, the plasma spray process parameters were varied, and x-ray diffraction analyses were performed on the cathode coatings to detect material decomposition and the formation of undesired phases. These results determined the envelope of plasma spray parameters in which coatings of LSCF and SSC can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured. Subsequently, composite cathodes were fabricated by mixing up to 40 wt. % of the ionic conducting SDC (Ce0.8Sm0.2O1.9) material into the feedstock. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency. Electrochemical impedance spectroscopy was performed in symmetrical cells: at 750°C, LSCF-SDC cathodes had polarization resistances as low as 0.101 Ωcm², and SSC cathodes had polarization resistances as low as 0.0056 Ωcm². Finer mixing of the ceramic phases was achieved by using a nano-structured feedstock that contained both LSCF and SDC phases agglomerated together in larger particles. Fuel cells containing a yttria-stabilized zirconia (YSZ) electrolyte and a nickel-YSZ anode were fabricated, and the effect of the cathode microstructure on cell impedance was studied using the analysis of differential impedance spectra. The degradation of composite LSCF-SDC cathodes on porous 430 stainless steel supports was also investigated. To reduce degradation, La2O3 and Y2O3 reactive element oxide coatings were deposited on the internal pore surfaces of the metal supports. As a result, polarization resistance degradation rates as low as 0.00256 Ω·cm2 /1000 h were observed over 100 hours on coated substrates, compared to 0.1 Ω·cm2 /1000 h on uncoated substrates.

Solid oxide fuel cells (SOFCs) are electrochemical devices based on solid oxide electrolytes that convert chemical energy in fuels directly into electricity via electrode reactions. SOFCs have the advantages of high energy efficiency and low emissions and hold the potential to be the power of the future, especially for small power generation systems (1-10 kW). Another unique advantage of SOFCs is the potential to directly utilize hydrocarbon fuels such as natural gas through internal reforming. However, all hydrocarbon fuels contain some sulfur compounds, which transform to hydrogen sulfide (H2S) in the reforming process and dramatically degrade the performance of the existing SOFCs. In this study, the interactions between sulfur contaminant (in the form of H2S) and the anodes for SOFCs were systematically investigated in order to gain a fundamental understanding of the mechanism of sulfur poisoning and ultimately to achieve rational design of sulfur-tolerant anodes. The sulfur poisoning behavior of the state-of-the-art Ni-YSZ cermet anodes was characterized using electrochemical measurements performed on button cells (of different structures) under various operating conditions, including H2S concentration, temperature, cell current density/terminal voltage, and cell structure. Also, the mechanisms of interactions between sulfur and the Ni-YSZ cermet anode were investigated using both ex situ and in situ characterization techniques such as Raman spectroscopy. Results suggest that the sulfur poisoning of Ni-YSZ cermet anodes at high temperatures in fuels with ppm-level H2S is due not to the formation of multi-layer conventional nickel sulfides but to the adsorption of sulfur on the nickel surface. In addition, new sulfur-tolerant anode materials were explored in this study. Thermodynamic principles were applied to predict the stability of candidate sulfur-tolerant anode materials and explain complex phenomena concerning the reactivity of candidate materials with hydrogen sulfide. The enhanced sulfur tolerance for some candidate anode materials such as (Gd2Ti1.4Mo0.6O7) is attributed to the transition of the surface from metal oxides to sulfides (i.e., MoS2), which enhances the catalytic activity and increases the number of reaction sites.

Made available in DSpace on 2014-10-09T12:27:27Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:46Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:27:27Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:46Z (GMT). No. of bitstreams: 0 / Células a combustível de óxido sólido são sistemas capazes de gerar energia elétrica por meio da oxidação de moléculas hidrogenadas. Normalmente os sistemas planares e tubulares, são compostos por quatro constituintes bem definidos: cátodo, ânodo, eletrólito e selante. Este último componente é o foco do presente estudo, sendo que suas principais características são estabilidade química na temperatura de operação da célula, isolamento elétrico e coeficiente de expansão térmica compatível com os outros constituintes, além da viscosidade elevada e resistência química em atmosferas oxidantes e redutoras. Devido à geometria planar e de multicamadas da célula se optou por usar como selante vidros niobofosfatos. A selagem foi realizada a partir de dispersão de pó de vidro em álcool etílico, gerando uma solução viscosa que foi aplicada sobre o substrato. Posteriormente realizou se um tratamento térmico para a consolidação do selamento. Os vidros estudados foram denominados de Nb30, Nb37, Nb40 e Nb44, de acordo com o teor nominal de óxido de nióbio utilizado na composição. O objetivo desse trabalho foi caracterizar, a partir de precursores os selantes a base de vidros niobofosfatos para aplicar em células a combustível de óxido sólido do tipo planar. Foram feitos caracterizações dos pós dos vidros e de pastilhas cristalizadas para determinar os coeficientes de expansão térmica (CET), resistividade elétrica, difração de raio X e microscopia eletrônica de varredura (MEV), além de, caracterizar visualmente sua adesividade, molhabilidade, resistência mecânica em substratos de alumina e em conjunto com os componentes das SOFC, sendo também testados os selantes em operação nas unidades previamente formadas de SOFC (ciclos térmicos). / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22773号 / 工博第4772号 / 新制||工||1746(附属図書館) / 京都大学大学院工学研究科航空宇宙工学専攻 / (主査)教授 岩井 裕, 教授 吉田 英生, 教授 江口 浩一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

This work represents the integration of a hybrid system based on Micro Gas Turbine system available at the division of Heat and Power Technology at KTH and Solid Oxide Fuel Cell.  The MGT available is an externally fired recuperated and the SOFC is of planar type. Before the integration, these two different candidates of environmentally friendly power generation systems are discussed separately. The advantages and performances of the two separate systems are presented. The operation conditions as pressure and temperature are fixed at different stations based on the previous experiments. Keeping the parameters constant a reduction of fuel to the combustor could be achieved. Finally, layout of the hybrid system diagram is suggested and orientation of a computer designed layout is also presented. An efficiency of 65% from SOFC has been achieved and reductions of the fuel by more than 50% to the MGT are noteworthy.

This thesis focuses on developing an appropriate cathode material throughnanotechnology as a key component for a promising alternative of renewable energygenerating systems, Intermediate Temperature Solid Oxide Fuel Cells (IT-SOFC).Aiming at a working cathode material for IT-SOFC, a recently reported capable oxideperovskite material has been synthesized through two different chemical methods.BaxSr1-xCoyFe1-yO3−δ (BSCF) with y =0.8 and x =0.2 was fabricated in nanocrystallineform by a novel chemical alloying approach, co-precipitation- as well as conventionalsol-gel method to produce oxide perovskites. The thermal properties, phase constituents,microstructure and elemental analysis of the samples were characterized by TG-DSC,XRD, SEM and EDS techniques respectively. Thermodynamic modeling has beenperformed using a KTH-developed software (Medusa) and Spark Plasma Sintering (SPS)has been used to obtain pellets of BSCF, preserving the nanostructure and generatingquite dense pellets for electrical conductivity measurements.The results show that the powders synthesized by solution co-precipitation have cubicperovskite-type structure with a high homogeneity and uniform distribution and meanparticle size of 50-90 nm range, while sol-gel powders are not easy to form a pure phaseand mostly the process ends up with large particle containing two or three phases.Finer resultant powder compared to sol-gel technique and earlier research works onBSCF has been achieved in this project using oxalate co-precipitation method. Topreserve nanoscaled features of BSCF powder which possess a significant increase ofelectrical conductivity due to decrease the electrical resistivity of grain boundaries, forthe sample synthesized through co-precipitation, ~92% dense pellet sintered by SPS atV1080 °C and under 50 MPa pressure and its electrical conductivity has been measuredfrom room temperature to 900 °C.Specific conductivity values were precisely measured and the maximum of 63 S.cm-1 at430 °C in air and 25 S.cm-1 at 375°C in N2 correspondingly are two times higher thanconventional BSCF implying a high pledge for nano-BSCF as a strong candidate ascathode material in IT-SOFC.

Polygeneration systems attract attention recently because of their high efficiency and low emission compare to the conventional power generation technology. Three different polygeneration systems based on low temperature solid oxide fuel cell, atmospheric solid oxide fuel cell/ micro gas turbine, and pressurized solid oxide fuel cell/ micro gas turbine are mathematically modeled in this study using MATLAB (version 7.12.0.635). These systems are designed to provide space heating, cooling and hot domestic water simultaneously. This report provides the design aspects of such systems. Furthermore, the effects of some important operating properties on the polygeneration systems performance are investigated.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21424号 / 工博第4534号 / 京都大学大学院工学研究科航空宇宙工学専攻 / (主査)教授 吉田 英生, 教授 黒瀬 良一, 准教授 岩井 裕, 教授 江口 浩一 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Solid oxide fuel cells (SOFCs) are devices that convert chemical energy into electrical energy and have the potential to become a reliable renewable energy source that can be used on a large scale. SOFCs have 3 main components; the electrolyte, the anode, and the cathode. Typically, SOFCs work by reducing oxygen at the cathode into O2- ions which are then transported via the electrolyte to the anode to combine with a fuel such as hydrogen to produce electricity. Research into better materials and manufacturing methods is necessary to reduce costs and improve efficiency to make the technology commercially viable. The goal of the research is to optimize and simplify the production of single SOFCs using high performance ceramics. This includes the use of 8mol% Y2O3-ZrO2 (YSZ) and 10mol% Sc2O3-1mol%CeO2-ZrO2 (SCSZ) layered electrolytes which purport higher conductivity than traditional pure YSZ electrolytes. Prior to printing the electrodes onto the electrolyte, the cathode side of the electrolyte was coated with 20mol% Gd2O3-CeO2 (GDC). The GDC coating prevents the formation of a nonconductive La2Zr2O7 pyrochlore layer, which forms due to the interdiffusion of the YSZ electrolyte ceramic and the (La0.6Sr0.4)0.995Fe0.8Co0.2O3 (LSCF) cathode ceramic during sintering. The GDC layer was deposited by spin coating a suspension of 10wt% GDC in ethanol onto the electrolyte. Variation of parameters such as time, speed, and ramp rate were tested. Deposition of the electrodes onto the electrolyte surface was done by screen printing. Ink was produced using a three roll mill from a mixture of ceramic electrode powder, terpineol, and a pore former. The pore former was selected based on its ability to form a uniform well-connected pore matrix within the anode samples that were pressed and sintered. Ink iii development involved the production of different ratios of powder-to-terpineol inks to vary the viscosity. The different inks were used to print electrodes onto the electrolytes to gauge print quality and consistency. Cells were produced with varying numbers of layers of prints to achieve a desirable thickness. Finally, the densification behaviors of the major materials used to produce the single cells were studied to determine the temperatures at which each component needs to be sintered to achieve the desired density and to determine the order of electrode application, so as to avoid over-densification of the electrodes. Complete cells were tested at the National Energy Technology Laboratory in Morgantown, WV. Cells were tested in a custom-built test stand under constant voltage at 800°C with 3% humidified hydrogen as the fuel. Both voltage-current response and impedance spectroscopy tests were conducted after initial startup and after 20 hours of operation. Impedance tests were performed at open circuit voltage and under varying loads in order to analyze the sources of resistance within the cell. A general increase in impedance was found after the 20h operation. Scanning electron micrographs of the cell microstructures found delamination and other defects which reduce performance. Suggestions for eradicating these issues and improving performance have been made.