Master Thesis, Department of Mechanical Engineering / A comprehensive analytical model of an indirect internal reforming type tubular Solid Oxide Fuel Cell (IIR-T-SOFC) has been developed. Two-dimensional axisymmetric multicomponent gas flow fields and quasi-three-dimensional electric potential/current fields in the tubular cell are simultaneously treated in the model with consideration of the involved phenomena such as internal reforming, electrochemical reactions and radiative heat transfer. By using this model, the characteristics of the operating state of an IIR-T-SOFC were numerically examined. As a result, it was shown how the thermal field and power generation characteristics of the cell were affected by the gas inlet temperature, air flow rate, steam-methane ratio, reforming catalyst distribution and thickness of the electrodes. In particular, the optimized catalyst distribution greatly reduced both the maximum temperature and temperature gradients of the cell with little negative impact on the power generation performance of the cell. / 京都大学 / 0048 / 修士 / 修士(工学) / Kyoto University / TFtmp

Solid oxide fuel cells (SOFCs) are electrochemical energy conversion devices that directly transform the chemical energy of fuel into electrical energy. They generate electricity far more efficiently and with fewer emissions per megawatt-hour compared to any combustion-based power generation system. More remarkably, SOFCs can directly use hydrocarbon fuels without requiring external fuel reforming, employing low-cost Ni catalyst instead of noble-metal catalysts used for low-temperature fuel cells. However, the conventional SOFCs using Ni-based anodes fed with carbon-containing fuels have one pitfall; the carbon produced by hydrocarbon cracking is deposited on the Ni surface, thereby precluding the surface of the Ni-based anodes from being available for further fuel oxidation and consequently impeding SOFC operation. This dissertation focuses on overcoming this critical drawback to allow for the simultaneous use of Ni-based anodes and hydrocarbon fuels. Further work focuses on improving SOFC performance to provide the highest efficiencies possible. To boost the power densities of SOFCs, a novel, facile approach to modify the surface structure of anode powders and thereby enlarge the three-phase boundary (TPB) regions of anodes is presented. One such powder preparation method based on the electric charge variation of oxides depending upon the pH of the solution results in significantly extended TPB regions and thus a remarkable increase in power densities of SOFCs. Another method involves the formation of Ce₁₋[subscript x]Gd₁₋[subscript y]Ni[subscript x+y]VO₄₋[subscript delta] at the phase boundaries between NiO and Ce₀.₈Gd₀.₂O₁.₉ (GDC) by V⁵⁺-incorporation onto NiO surface; this method improves the microstructure of Ni-GDC-based anodes and considerably lowers GDC electrolyte sintering temperature, thereby enhancing the SOFC performance. With these high performance anodes, natural gas-fueled SOFCs are studied through two strategies to alleviate coking: incorporation of catalytic materials onto the Ni surface and the introduction of catalytic functional layers (CFLs) to the outer surface of an anode-supported single cell. Hydrogen tungsten bronze and hydroxylated Sn formed on the Ni surface provide hydroxyls for the deposited solid carbon, removing it from the anodes as CO₂. Moreover, the use of hydrophilic Sn or Sb-incorporated Ni-GDC CFLs prevents the anode from being exposed directly to hydrocarbon fuels and controls the solid carbon accumulation similarly to the former strategy. / text

La mise au point d'une cellule de SOFC haute performance de configuration anode support pour un fonctionnement sous méthane pur nécessite l'élaboration d'un film mince d'électrolyte et le développement d'une architecture innovante permettant le reformage d'hydrocarbures. La première partie du travail a consisté en l'élaboration de films minces d'électrolyte de zircone stabilisée à l'oxyde d'yttrium par atomisation électrostatique sur un substrat composite poreux NiO-8YSZ. Cette technique originale a permis l'obtention de films minces, denses et étanches à partir d'une suspension, présentant des propriétés électriques comparables à celles d'un échantillon massif de même composition. La seconde partie du travail a porté sur la mise au point d'une cellule de SOFC optimisée dont l'architecture innovante intégrant une membrane anodique catalytique est basée sur le concept associant le reformage interne progressif et le découplage électro-catalytique. Une séquence d'élaboration établie spécifiquement conditionne l'assemblage des éléments optimisés de la cellule. L'adaptation de la cellule dans un banc de mesures a permis la réalisation de tests électrochimiques sous hydrogène et méthane à haute température. Le fonctionnement stable du dispositif pendant plus de 1000 h sous méthane pur avec un taux d'utilisation optimisé, sans apport extérieur d'eau et sans dépôt de carbone a validé le concept étudié. / The design of a high performance anode supported SOFC operating under pure methane requires the elaboration of a thin film of electrolyte and the development of an original architecture adapted to the reforming of hydrocarbons. The first part of this work was dedicated to the elaboration of yttria stabilized zirconia thin films of electrolyte by ESD onto a NiO-8YSZ porous substrate. This original technique has allowed the fabrication of thin, dense and gas-tight films starting from a suspension, with good electrical properties comparable to that of a bulk sample of the same nature. The second part of this work concerned the design of an optimized SOFC cell with an original architecture integrating an anodic catalytic membrane based on a concept gathering the gradual internal reforming and the electro-catalytic dissociation. The assembly of the optimized components is conditioned by an elaboration sequence specifically established. The adjustment of the cell in a test bench led to the achievement of electrochemical tests in hydrogen and methane at 800°C. The stable operating of the cell fueled by pure and dry methane with optimized faradaic efficiency for more than 1000 h without carbon deposition proved the viability of the studied concept.

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

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17560号 / 工博第3719号 / 新制||工||1566(附属図書館) / 30326 / 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 中部 主敬, 准教授 松本 充弘 / 学位規則第4条第1項該当

Células a combustível de óxido sólido suportadas no eletrólito de zircônia estabilizada com ítria (YSZ) foram fabricadas usando a técnica do recobrimento por rotação (spin-coating) para deposição de catodos de manganita de lantânio dopada com estrôncio (LSM) e anodos compósitos de níquel e YSZ (Ni-YSZ). Parâmetros microestruturais dos eletrodos, tais como espessura, tamanho médio de partículas e temperatura de sinterização foram otimizados, visando reduzir a resistência de polarização da célula e melhorar o seu desempenho. Estes estudos serviram de base para a fabricação de células com camada catalítica para uso com etanol direto. Sobre o anodo Ni-YSZ da célula foi depositada uma camada catalítica de céria dopada com gadolínia (CGO) com 0,1% em peso de irídio (Ir-CGO). A camada catalítica visa reformar o etanol antes do seu contato com o anodo Ni-YSZ, evitando o depósito de carbono na superfície do Ni que inviabiliza o uso de combustíveis primários contendo carbono nestas células a combustível. Inicialmente, a célula a combustível foi testada com etanol e as melhores condições de operação foram determinadas. Em seguida, as células unitárias foram testadas com etanol sem adição de água por períodos de tempo de até 390 horas. As células a combustível a etanol direto com camada catalítica operam no modo de reforma interna gradual, apresentando boa estabilidade e densidades de corrente similares às obtidas na operação com hidrogênio. Após a operação das células a combustível a etanol direto, análises de microscopia eletrônica de varredura mostraram que não houve formação significativa de depósitos de carbono na superfície do Ni, indicando que a camada catalítica de Ir-CGO foi efetiva para operação com o etanol. Testes de células a combustível a etanol direto sem a camada catalítica revelaram uma rápida degradação nas horas iniciais de operação com formação de grandes quantidades de depósitos de carbono identificados visualmente. Considerando-se a operação estável com etanol a seco por tempos relativamente longos de operação, os resultados alcançados representam um avanço significativo e apontam para o desenvolvimento de células a combustível a etanol direto usando-se os componentes tradicionais com a adição de uma camada catalítica. / Yttria-stabilized zirconia (YSZ) electrolyte supported solid oxide fuel cells were fabricated with spin-coated strontium-doped lanthanum manganite (LSM) cathodes and Ni-YSZ cermet anodes. The microstructural parameters of the electrodes such as thickness, average particle size, and sintering temperature were optimized to decrease the polarization resistance of the single cells and to improve their electrochemical performance. These preliminar studies provided the basis for the fabrication of single fuel cells with a catalytic layer of gadolinia-doped ceria (CGO) and 0.1 wt% iridium (Ir-CGO) deposited onto the anode. The catalytic layer aims at the stable operation with dry (direct) ethanol; it avoids the contact of the alcohol with the anode, preventing the anode degradation by carbon deposition. Initially, the single cells were tested with ethanol and optimized operating parameters were determined. Then, the single cells were operated with anhydrous ethanol for periods of time up to 390 hours. The single cells with catalytic layer operate by the gradual internal reforming of ethanol, with good stability and delivering similar electric current densities as the ones measured using hydrogen as fuel. After single cell operation on direct ethanol, scanning electron microscopy analyses identified no significant carbon deposition on the surface of Ni, indicating that the Ir-CGO catalytic layer was effective for the reforming of ethanol. Such results were compared to the ones of standard single cells operating on dry ethanol, which showed a fast degradation and the formation of large amounts of carbon deposits. Considering the rather stable performance of single cells running on dry ethanol for relatively long times, such results represent a significant advance towards the development of direct ethanol solid oxide fuel cells using the standard components and a catalytic layer.

A CO2 emission analysis and system investigation of a direct fuel cell waste energy recovery and power generation system (DFC-ERG) for pressure letdown stations was undertaken. The hybrid system developed by FuelCell Energy Inc. is an integrated turboexpander and a direct internal reforming molten carbonate fuel cell system in a combined circle. At pressure letdown stations, popularly called city gates, the pressure of natural gas transported on long pipelines is reduced by traditional pressure regulating systems. Energy is lost as a result of pressure reduction. Pressure reduction also results in severe cooling of the gas due to the Joule Thompson effect, thus, requiring preheating of the natural gas using traditional gas fired-burners. The thermal energy generated results in the emission of green house gases. The DFC-ERG system is a novel waste energy recovery and green house gas mitigation system that can replace traditional pressure regulating systems on city gates. A DFC-ERG system has been simulated using UniSim Design process simulation software. A case study using data from Utilities Kingston’s city gate at Glenburnie was analysed. The waste energy recovery system was modelled using the design specifications of the FuelCell Energy Inc’s DFC 300 system and turboexpander design characteristics of Cryostar TG120. The Fuel Cell system sizing was based on the required thermal output, electrical power output, available configuration and cost. The predicted performance of the fuel cell system was simulated at a current density of 140mA/cm2, steam to carbon ratio of 3, fuel utilization of 75% and oxygen utilization of 30%. The power output of the turboexpander was found to strongly depend on the high pressure natural gas flowrate, temperature and pressure. The simulated DFC-ERG system was found to reduce CO2 emissions when the electrical power generated by the DFC-ERG system replaced electrical power generated by a coal fired plant. / Thesis (Master, Chemical Engineering) -- Queen's University, 2010-08-31 02:02:11.392

Células a combustível de óxido sólido suportadas no eletrólito de zircônia estabilizada com ítria (YSZ) foram fabricadas usando a técnica do recobrimento por rotação (spin-coating) para deposição de catodos de manganita de lantânio dopada com estrôncio (LSM) e anodos compósitos de níquel e YSZ (Ni-YSZ). Parâmetros microestruturais dos eletrodos, tais como espessura, tamanho médio de partículas e temperatura de sinterização foram otimizados, visando reduzir a resistência de polarização da célula e melhorar o seu desempenho. Estes estudos serviram de base para a fabricação de células com camada catalítica para uso com etanol direto. Sobre o anodo Ni-YSZ da célula foi depositada uma camada catalítica de céria dopada com gadolínia (CGO) com 0,1% em peso de irídio (Ir-CGO). A camada catalítica visa reformar o etanol antes do seu contato com o anodo Ni-YSZ, evitando o depósito de carbono na superfície do Ni que inviabiliza o uso de combustíveis primários contendo carbono nestas células a combustível. Inicialmente, a célula a combustível foi testada com etanol e as melhores condições de operação foram determinadas. Em seguida, as células unitárias foram testadas com etanol sem adição de água por períodos de tempo de até 390 horas. As células a combustível a etanol direto com camada catalítica operam no modo de reforma interna gradual, apresentando boa estabilidade e densidades de corrente similares às obtidas na operação com hidrogênio. Após a operação das células a combustível a etanol direto, análises de microscopia eletrônica de varredura mostraram que não houve formação significativa de depósitos de carbono na superfície do Ni, indicando que a camada catalítica de Ir-CGO foi efetiva para operação com o etanol. Testes de células a combustível a etanol direto sem a camada catalítica revelaram uma rápida degradação nas horas iniciais de operação com formação de grandes quantidades de depósitos de carbono identificados visualmente. Considerando-se a operação estável com etanol a seco por tempos relativamente longos de operação, os resultados alcançados representam um avanço significativo e apontam para o desenvolvimento de células a combustível a etanol direto usando-se os componentes tradicionais com a adição de uma camada catalítica. / Yttria-stabilized zirconia (YSZ) electrolyte supported solid oxide fuel cells were fabricated with spin-coated strontium-doped lanthanum manganite (LSM) cathodes and Ni-YSZ cermet anodes. The microstructural parameters of the electrodes such as thickness, average particle size, and sintering temperature were optimized to decrease the polarization resistance of the single cells and to improve their electrochemical performance. These preliminar studies provided the basis for the fabrication of single fuel cells with a catalytic layer of gadolinia-doped ceria (CGO) and 0.1 wt% iridium (Ir-CGO) deposited onto the anode. The catalytic layer aims at the stable operation with dry (direct) ethanol; it avoids the contact of the alcohol with the anode, preventing the anode degradation by carbon deposition. Initially, the single cells were tested with ethanol and optimized operating parameters were determined. Then, the single cells were operated with anhydrous ethanol for periods of time up to 390 hours. The single cells with catalytic layer operate by the gradual internal reforming of ethanol, with good stability and delivering similar electric current densities as the ones measured using hydrogen as fuel. After single cell operation on direct ethanol, scanning electron microscopy analyses identified no significant carbon deposition on the surface of Ni, indicating that the Ir-CGO catalytic layer was effective for the reforming of ethanol. Such results were compared to the ones of standard single cells operating on dry ethanol, which showed a fast degradation and the formation of large amounts of carbon deposits. Considering the rather stable performance of single cells running on dry ethanol for relatively long times, such results represent a significant advance towards the development of direct ethanol solid oxide fuel cells using the standard components and a catalytic layer.