Spelling suggestions: "subject:"anode."" "subject:"inode.""
101 |
Concept and design of a hall-effect thruster with integrated thrust vector controlStark, Willy, Gondol, Norman, Tajmar, Martin 01 March 2024 (has links)
Hall-effect thrusters (HETs) are among the most commonly used propulsion systems for attitude and orbit control of satellites. As an arrangement in a cluster or individually, equipped with a mechanical suspension, thrust in all three spatial directions can be generated, but requires additional mechanisms and components. Therefore, the Technische Universität Dresden (TU Dresden) is currently working on a concept for developing a Hall-effect thruster with integrated thrust vector control, which would allow steering in all three spatial directions with just a single thruster. This new concept is intended to work solely by influencing the ion beam and should not have any additional mechanical components. The HET will come with a segmented anode to set different electrical potentials at the anode and cause an inhomogeneous distribution of the electric field within the discharge channel, which results in an inhomogeneous force vector distribution at the exit plane. It is assumed that this will generate turning moments around the center of gravity. Deliberately causing those turning moments can therefore be used for steering with just one thruster. This work presents the concept of the propulsion system, gives an outlook on the advantages of its technology and shows capabilities for space applications.
|
102 |
Synthèse et caractérisation électrochimique de liquides ioniques à base de phosphonium pour les applications aux batteries au lithiumKwamou Kouayep, Bertrand Mirador January 2014 (has links)
Les besoins énergétiques de la population mondiale ne cessent de croître, cette croissance est beaucoup plus attribuée à la venue de nouveaux consommateurs des pays émergents. Les réserves de gisement de pétrole fossile, principale source d’énergie de notre civilisation ne suivant pas la demande, la recherche de nouvelles sources d’énergie ou compléments énergétiques de ceux classiques demeure un challenge important pour l’avenir de notre société. Les batteries au lithium demeurent une réponse dite énergie renouvelable pour la lutte que se livrent les pays du globe pour limiter l’échéance de la fin des énergies nécessaires à la survie de notre système économique. Cette batterie offre des performances énergétiques plus grandes que celle alcaline par exemple. Ce travail s’inscrit dans la lignée de l’amélioration continue de la technologie des batteries lithium- ion. Cette amélioration passe par l’optimisation des différentes composantes des piles au lithium comme les électrodes (anode et cathode) et les électrolytes (solvants et ion principal à base de lithium). Ainsi, ce travail comporte trois parties. Dans un premier temps, nous avons investigué de nouveaux solvants dits liquides ioniques à base de phosphonium, ces solvants étant tous des précurseurs respectifs de tri-n-buthylphosphine et tri-n-éthylphosphine (TBPhexTFSI, TBPmetTFSI, TBPhoxTFSI, TBPmetOetTFSI, TEPhexTFSI et TEPhoxTFSI, voir la liste des abréviations). Le choix de ces liquides ioniques à base de phosphonium a été fait dans l’optique de la recherche de ceux ayant les meilleures propriétés chimico-physiques et électrochimiques. De ce fait, les mesures de ces propriétés physico-chimiques comme leur conductivité, viscosité, stabilité thermique ont été effectuées. La supériorité des liquides à base de phosphonium ayant des cations à chaîne oxygénée sur ceux non oxygénées a été démontrée. La conductivité du TBPhoxTFSI respectivement supérieure à celle du TBPhexTFSI et la viscosité de TBPhoxTFSI est inférieure à celle du TBPhexTFSI). Cette étude a aussi démontré l’importance d’avoir des liquides ioniques de phosphonium à cation asymétrique de petite dimension pour bénéficier des meilleures propriétés chimico-physiques, notamment les conductivités des TEPhexTFSI et TEPhoxTFSI étant meilleures que celle du TBPhexTFSI et TBPhoxTFSI.
Les études électrochimiques, notamment la voltampérométrie cyclique à balayage, ont permis d’étudier les fenêtres de potentiel électrochimique de certains de ces liquides ioniques. Il a été démontré que les liquides ioniques ayant un cation à chaîne carbonylée asymétrique courte et non oxygénée ont des fenêtres de potentiel électrochimique plus large (respectivement 5 et 5,5V pour le TBPmetTFSI et TEPhexTFSI). Notre étude s’est basée seulement sur deux liquides ioniques ayant pour précurseur la tri-n-buthylphosphine : le TBPmetTFSI et le TBPhoxTFSI. Le choix de ces deux liquides ioniques de phosphonium découle aussi des études effectuées sur leurs propriétés chimico-physiques intéressantes.
Dans l’amélioration des composantes des batteries lithium-ion, la recherche des meilleures électrodes demeure aussi un enjeu stratégique important dans cette technologie. Les cathodes à plus grande capacité énergétique sont dans cette logique. Les cathodes des piles rechargeables au lithium sont composées de matériaux du type oxydes mixtes des métaux de transition. Un des facteurs importants du choix de ces matériaux est la diffusion rapide du lithium dans leur structure interne c’est-à-dire la vitesse des réactions d’intercalations et de désintercalations des ions de lithium pendant le fonctionnement de ces types de piles. Les matériaux dits à structure cristalline olivine type LiFePO[indice inférieur 4] ont eu une grande percée il y a environ 10 ans. De nos jours ils sont encore présents, mais de façon améliorée par l’ajout des additifs de carbone généralement dans un pourcentage de 7 à 10% en poids et prennent le nom de LiFePO[indice inférieur 4]/C. Nous avons ainsi réussi à synthétiser par approche sol-gel le LiFePO[indice inférieur 4]/C ; ce matériau a ensuite été caractérisé par diffraction à rayon-X, par microscope électronique à balayage (MEB) et comparé à ce matériau de LiFePO[indice inférieur 4] commercial de la compagnie MTI Corporation. Deux conditions expérimentales ont été utilisées pour les caractérisations électrochimiques de ces cathodes de LiFePO[indice inférieur 4] commercial et LiFePO[indice inférieur 4]/C, soit dans les électrolytes classiques 1M LiPF[indice inférieur 6]–EC-DMC (3/7 vol) et dans les électrolytes mixtes 1M LiPF[indice inférieur 6]–EC-DMC (3/7 vol.) + x TBPmetTFSI ou TBPhoxTFSI. Les voltampérogrammes cycliques obtenus dans ces conditions classiques et mixtes ont démontré que les liquides ioniques TBPmetTFSI et TBPhoxTFSI pouvaient être utilisés comme additifs aux solvants classiques jusqu’à des concentrations de 50% en volume de ceux classiques comme EC-DMC (3/7 vol.) tout en favorisant les processus d’intercalation et dedésintercalation du lithium durant le cycle de fonctionnement des batteries lithium-ion. La quasi-réversibilité des pics redox dans ces proportions des liquides ioniques est un indice de bon fonctionnement des batteries lithium-ion avec des électrolytes mixtes composés de solvants classiques et de liquides ioniques à base de phosphonium.
|
103 |
In situ characterization of electrochemical processes of solid oxide fuel cellsLi, Xiaxi 07 January 2016 (has links)
Solid oxide fuel cells (SOFCs) represent a next generation energy source with high energy conversion efficiency, low pollutant emission, good flexibility with a wide variety of fuels, and excellent modularity suitable for distributed power generation. As an electrochemical energy conversion device, SOFC’s performance and reliability depend sensitively on the catalytic activity and stability of the electrode materials. To date, however, the development of electrode materials and microstructures is still based largely on trial-and-error methods because of inadequate understanding of the mechanisms of the electrode processes. Identifying key descriptors/properties of electrode materials or functional heterogeneous interfaces, especially under in situ conditions, may provide guidance to the design of electrode materials and microstructures. This thesis aims to gain insight into the electrochemical and catalytic processes occurring on the electrode surfaces using unique characterization tools with superior sensitivity, high spatial resolution, and excellent surface specificity applicable under in situ/operando conditions.
Carbon deposition on nickel-based anodes is investigated with in situ Raman spectroscopy and SERS. Analysis shows a rapid nucleation of carbon deposition upon exposure to small amount of propane. Such nucleation process is sensitive to the presence of surface coating (e.g., GDC) and the concentration of steam. In particular, operando analysis of the Ni-YSZ boundary indicates special function of the interface for coking initiation and reformation.
The coking-resistant catalysts (BaO, BZY, and BZCYYb) are systematically studied using in situ Raman spectroscopy, SERS, and EFM. In particular, time-resolved Raman analysis of the surface functional groups (-OH, -CO3, and adsorbed carbon) upon exposure to different gas atmospheres provides insight into the mechanisms related to carbon removal. The morphology and distribution of early stage carbon deposition are investigated with EFM, and the impact of BaO surface modification is evaluated.
The surface species formed as a result of sulfur poisoning on nickel-based anode are examined with SERS. To identify the key factors responsible for sulfur tolerance, model cells with welldefined electrode-electrolyte interfaces are systematically studied. The Ni-BZCYYb interface exhibits superior sulfur tolerance.
The oxygen reduction kinetics on LSCF, a typical cathode material of SOFC, is studied using model cells with patterned electrodes. The polarization behaviors of these micro- electrodes, as probed using a micro-probe impedance spectroscopy system, were correlated with the systematically varied geometries of the electrodes to identify the dominant paths for oxygen reduction under different electrode configurations. Effects of different catalyst modifications are also evaluated to gain insight into the mechanisms that enhance oxygen reduction activity.
The causes of performance degradation of LSCF cathodes over long term operation are investigated using SERS. Spectral features are correlated with the formation of surface contamination upon the exposure to air containing Cr vapor, H2O, and CO2. Degradation in cathode performance occurs under normal operating conditions due to the poisoning effect of Cr from the interconnect between cells and the high operating temperature. The surface-modified LSCF cathode resists surface reactions with Cr vapor that impairs electrode performance, suggesting promising ways to mitigate performance degradation.
|
104 |
Chemical modification of nanocolumnar semiconductor electrodes for enhanced performance as lithium and sodium-ion battery anode materialsAbel, Paul Robert 24 October 2014 (has links)
Chemical Engineering / The successful commercialization of lithium-ion batteries is responsible for the ubiquity of personal electronics. The continued development of battery technology, as well as its application to new emerging markets such as electric vehicles, is dependent on developing safer, higher energy density, and cheaper electrode materials and battery chemistries. The focus of this dissertation is on identifying, characterizing and optimizing new materials for lithium- and sodium-ion batteries. Batteries are incredibly complex engineered systems with each electrode composed of conductive additive and polymeric binder in addition to the active material. All of these components must work together for the electrode system to function properly. In this work, glancing angle deposition (GLAD) and reactive ballistic deposition (RBD) are employed to grow thin films of novel materials with reproducible morphology for use as battery electrodes. The use of these thin film electrodes eliminated the need for conductive additives and polymer binders allowing for the active materials themselves to be studied rather than the whole electrode system. Two techniques are employed to modify the chemical properties of the electrode materials grown by RBD and GLAD: Alloying (Si-Ge alloys for Li-ion batteries and Sn-Ge alloys for Na-ion batteries) and partial chalcogenation (partial oxidation of silicon, and partial sulfidation and selenidation of germanium for Li-ion batteries). Both of these techniques are successfully employed to enhance the electrochemical properties of the materials presented in this dissertation. / text
|
105 |
A Density Functional Theory of a Nickel-based Anode Catalyst for Application in a Direct Propane Fuel CellVafaeyan, Shadi 25 September 2012 (has links)
The maximum theoretical energy efficiency of fuel cells is much larger than those of the steam-power-turbine cycles that are currently used for generating electrical power. Similarly, direct hydrocarbon fuel cells, DHFCs, can theoretically be much more efficient than hydrogen fuel cells. Unfortunately the current densities (overall reaction rates) of DHFCs are substantially smaller than those of hydrogen fuel cells. The problem is that the exchange current density (catalytic reaction rate) is orders of magnitude smaller for DHFCs. Other work at the University of Ottawa has been directed toward the development of polymer electrolytes for DHFCs that operate above the boiling point of water, making corrosion rates much slower so that precious metal catalysts are not required. Propane (liquefied petroleum gas, LPG) was the hydrocarbon chosen for this research partly because infrastructure for its transportation and storage in rural areas already exists. In this work nickel based catalysts, an inexpensive replacement for the platinum based catalysts used in conventional fuel cells, were examined using density functional theory, DFT. The heats of propane adsorption for 3d metals, when plotted as a function of the number of 3d electrons in the metal atom, had the shape of a volcano plot, with the value for nickel being the peak value of the volcano plot. Also the C-H bond of the central carbon atom was longer for propane adsorbed on nickel than when adsorbed on any of the other metals, suggesting that the species adsorbed on nickel was less likely to desorb than those on other metals. The selectivity of the propyl radical reaction was examined. It was found that propyl radicals
|
106 |
Studies of anode supported solid oxide fuel cells (SOFCs) based on La- and Ca-Doped SrTiO₃Lu, Lanying January 2015 (has links)
Solid oxide fuel cells (SOFCs) have attracted much interest as the most efficient electrochemical device to directly convert chemical energy to usable electrical energy. The porous Ni-YSZ anode known as the state-of-the-art cermet anode material is found to show serious degradation when using hydrocarbon as fuel due to carbon deposition, sulphur poisoning, and nickel sintering. In order to overcome these problems, doped strontium titanate has been investigated as a potential anode material due to its high electronic conductivity and stability in reducing atmosphere. In this work, A-site deficient strontium titanate co-doped with lanthanum and calcium, La₀.₂Sr₀.₂₅Ca₀.₄₅TiO₃ (LSCT[sub](A-)), was examined. Flat multilayer ceramics have been produced using the aqueous tape casting technique by controlling the sintering behaviour of LSCT[sub](A-), resulting in a 450µm thick porous LSCT[sub](A-) scaffold with a well adhered 40µm dense YSZ electrolyte. Impregnation of CeO₂ and Ni results in a maximum power density of 0.96Wcm⁻² at 800°C, higher than those of without impregnation (0.124Wcm⁻²) and with impregnation of Ni alone (0.37Wcm⁻²). The addition of catalysts into LSCT[sub](A-) anode significantly reduces the polarization resistance of the cells, suggesting an insufficient electrocatalytic activity of the LSCT[sub](A-) backbone for hydrogen oxidation, but LSCT[sub](A-) can provide the electronic conductivity required for anode. Later, the cells with the configuration of LSCT[sub](A-)/YSZ/LSCF-YSZ were prepared by the organic tape casting and impregnation techniques with only 300-m thick anode as support. The effects of metallic catalysts in the anode supports on the initial performance and stability in humidified hydrogen were discussed. The nickel and iron impregnated LSCT[sub](A-) cell exhibits a maximum powder density of 272mW/cm² at 700°C, much larger than 43mW/cm² for the cell without impregnation and 112mW/cm² for the cell with nickel impregnation. Simultaneously, the bimetal Ni-Fe impregnates have significantly reduced the degradation rates in humidified hydrogen (3% H₂O) at 700°C. The enhancement from impregnation of the bi-metal can possibly be the result of the presence of ionic conducting Wustite Fe₁₋ₓO that resides underneath the Ni-Fe metallic particles and better microstructure. Third, in order to improve the ionic conductivity of the anode support and increase the effective TPBs, ionic conducting ceria was impregnated into the LSCT[sub](A-) anode, along with the metallic catalysts. The CeO₂-LSCT[sub](A-) cell shows a poor performance upon operation in hydrogen atmosphere containing 3% H₂O; and with addition of metallic catalysts, the cell performance increases drastically by almost three-fold. However, the infiltrated Ni particles on the top of ceria layer cause the deposition of carbon filament leading to cell cracking when exposure to humidified methane (3% H₂O). No such behaviour was observed on the CeO₂-NiFe impregnated anode. The microstructure images of the impregnated anodes at different times during stability testing demonstrate that the grain growth of catalysts, the interaction between the anode backbone and infiltrates, and the spalling of the agglomerated catalysts are the main reasons for the performance degradation. Fourth, the YSZ-LSCT[sub](A-) composites including the YSZ contents of 5-80wt.% were investigated to determine the percolation threshold concentration of YSZ to achieve electronic and ionic conducting pathways when using the composite as SOFC anode backbone. The microstructure and dilatometric curves show that when the YSZ content is below 30%, the milled sample has a lower shrinkage than the unmilled one due to the blocking effect from the well distributed YSZ grains within LSCT[sub](A-) bulk. However, at the YSZ above 30% where two phases start to form the individual and interconnected bulk, the composites without ball milling process show a lower densification. The impact of YSZ concentration and ball milling process on the electrical properties of the composites reveals that the percolation threshold concentration is not only dependant on the actual concentration, but also related to the local arrangement of two phases. In Napier University, the electroless nickel-ceramic co-depositon process was investigated as a manufacturing technique for the anodes of planar SOFCs, which entails reduced costs and reduced high-temperature induced defects, compared with conventional fabrication techniques. The Ni-YSZ anodes prepared by the electroless co-deposition technique without the addition of surfactant adhere well to the YSZ electrolyte before and after testing at 800°C in humidified hydrogen. Ni-YSZ anodes co-deposited with pore-forming starch showed twice the maximum power density compared with those without the starch. It has therefore been demonstrated that a porous Ni-YSZ cermet structure was successfully manufactured by means of an electroless plating technique incorporating pore formers followed by firing at 450°C in air. Although the use of surfactant (CTAB) increases the plating thickness, it induces the formation of a Ni-rich layer on the electrolyte/anode interface, leading to the delamination of anode most likely due to the mismatched TECs with the adjacent YSZ electrolyte.
|
107 |
[en] THE EFFECT OF DIFFERENT METALLIC ELECTRODES ON THE ELECTROCOAGULATION OF OILY WASTEWATER / [pt] O EFEITO DE DIFERENTES ELETRODOS METÁLICOS NA ELETROCOAGULAÇÃO DE EFLUENTES OLEOSOSLORGIO GILBERTO VALDIVIEZO GONZALES 12 February 2009 (has links)
[pt] No presente trabalho, foi avaliado num modo sistemático o
processo de
eletrocoagulação (EC) usando eletrodos de alumínio e ferro
como material
de anodo e aço inoxidável como material de catodo, operando
com diferentes
parâmetros tais como: concentração inicial do óleo,
distanciamento entre os
eletrodos, relação área-volume (SA/V) e densidade de
corrente. A redução
da demanda química de oxigênio (DQO) e turbidez foram às
principais
variáveis respostas analisadas. Os ensaios foram feitos em
batelada com um
efluente sintético (5,1 litros) e com agitação magnética
(150 rpm). A densidade
de corrente e a relação SA/V foram os parâmetros com maior
influência
no processo. O aumento deles reduz notoriamente o tempo de
tratamento.
Os resultados mostraram que a eletrocoagulação, para os dois
tipos de
materiais (Fe/Al), conseguem uma excelente redução da DQO e
da turbidez
nas seguintes condições experimentais: densidade de
corrente, 9,4 mA/cm(2),
distanciamento entre os eletrodos, 10 mm, relação
área-volume(SA/V), 30,35
m(2)/m(3) e 30 minutos de operação.
Eficiências de redução de 99% e 98,3% foram alcançadas para
a DQO e a
turbidez com anodos de alumínio. Do mesmo modo 94,8% da DQO
e 98,5%
da turbidez para o caso do ferro foi reduzido do efluente
sintético. O processo
de eletrocoagulação, operando nessas condições envolve um
custo total de 7,1
R$/m(3) e 5 R$/m(3) por metro cúbico para alumínio e ferro,
respectivamente.
Estes custos só incluem custo de energia e consumo dos
eletrodos. A borra
produzida foi de 2,23 kg/m(3) para alumínio e 2,76 kg/m(3)
para o ferro.
Finalmente, o consumo de energia foi de 4,15 kWh/m(3) e 3,72
kWh/m(3) para
alumínio e ferro, respectivamente. Um tratamento de
eletrocoagulação para
um efluente oleoso sintético foi satisfatoriamente
implementado do ponto de
vista da redução destes parâmetros. / [en] In the present work, electrocoagulation process (EC) with
aluminum
and iron as materials for anode and stainless steel as
cathode, under different
operational parameters, such as: initial concentration of
oil, distance between
electrodes, area-volume relation (SA/V) and current density,
were examined in
a systematic manner. Chemical oxygen demand (COD) and
turbidity removals
were selected as a performance criteria. Tests were carried
out batch-wise in an
electrochemical cell (5.1 liter) with synthetic wastewater
and with magnetic
stirring (150 rpm); the current density and SA/V relation
were found to be
the most significant parameters, an increase of theses
notably reduces the
electrocoagulation required time for the treatment. The
results have shown
that electrocoagulation, using both kind of materials
(Fe/Al), successfully
removes the COD and turbidity in experimental conditions
such as: the current
density, 9.4 mA/cm(2), distance between electrodes, 10 mm;
SA/V relation,
30.35 m(2)/m(3) and 30 minutes of operation .
Removal efficiencies over 99% and 98.3% were measured for
COD and turbidity,
using anodes of aluminum. Likewise 94.8% of COD and 98.5% of
turbidity
were removed from synthetic wastewater, using anode of iron.
Electrocoagulation
process operated under theses conditions involves a total
cost of
7.1 R$/m(3) for aluminum and 5 R$/m(3) for iron per meter
cubic of treated
wastewater. These costs only include energy cost and
electrode consumptions.
The sludge produced after electrocoagulation treatment was
2.23 kg/m(3) for
aluminum and 2.76 kg/m(3) for iron, and the power
requirements were 4.15
kWh/m(3) and 3.72 kWh/m(3) for aluminum and iron. An
electrocoagulation
treatment of a synthetic wastewater was successfully
implemented from removal
efficiency point of view.
|
108 |
[en] INFLUENCE OF ANODE PAD INSTALLATION OVER THE BUCKLING OF PIPES SUBJECTED TO REELING / [pt] INFLUÊNCIA DA INSTALAÇÃO DE SAPATAS DE ANODO SOBRE A FLAMBAGEM DE DUTOS SUJEITOS AO ENROLAMENTOCARLOS ROBERTO CHARNAUX 03 September 2008 (has links)
[pt] Um dos principais métodos de instalação offshore de dutos
rígidos é o de enrolamento (reeling), o qual submete os
dutos a esforços de flexão que ocasionam deformações
plásticas. O processo de proteção catódica destas
tubulações exige a instalação de uma determinada quantidade
de anodos para a proteção contra corrosão. O contato dos
anodos com os dutos é estabelecido através das sapatas de
anodo. Estas geram imperfeições geométricas na espessura do
duto, resultando em regiões concentradoras de deformações
durante o processo de enrolamento nas embarcações de
instalação. Esta dissertação propõe entender e quantificar
o efeito da instalação das sapatas de anodo no que se refere
à introdução das concentrações de deformações e sua
influência na resistência à flambagem dos dutos durante o
processo de enrolamento. O estudo das falhas estruturais
por flambagem durante este processo requer a avaliação das
deformações longitudinais para comparação com os critérios
definidos pelas normas. Esta avaliação propõe a utilização
de métodos de cálculos analíticos e numéricos. A partir do
estudo desenvolvido foi possível propor um fluxograma
para avaliação de dutos com sapatas de anodo. Desta forma
foi possível definir um novo valor limite de deformação,
caso uma análise simplificada de enrolamento não atenda os
critérios propostos pelas normas. Considerando que o
estudo de sapatas de anodo é apenas um exemplo para
representar o problema de elementos concentradores de
deformação durante o processo de enrolamento, a
metodologia apresentada pode ser empregada com outros tipos
de elementos anexados às tubulações, para a avaliação de
falhas por flambagem. / [en] One of the main steel pipelines offshore installation
methods is the reeling, which subject the pipes to bending
loads that produces plastic strains. The cathodic
protection process of these rigid pipelines demands the
installation of a determined quantity of anodes for the
corrosion protection. The anodes contact with the pipes is
established through anode pads. These pads create
geometrical imperfections at pipe wall thickness, resulting
in strain concentration areas during the reeling process at
installation vessels. This dissertation proposes
to understand and quantify the pads installation effects
with reference to the introduction of strain concentrations
and its influence on the pipe buckling strength during the
reeling process. The pipe buckling failure study during the
reeling process requires the evaluation of longitudinal
strains for the comparison with the standards defined
criteria. This evaluation proposes the use of analytical
and numerical calculation methods. From the developed
study, it was possible to propose a flow chart for the
evaluation of pipes with anode pads. From this, it was
possible to define a newer strain limit value, in the event
of a simplified reeling analysis is not in agreement with
the standards proposed criteria. Considering that
anode pads study is only one example to represent the
strain concentration elements during reeling process, the
herein presented methodology can be applied to other types
of parts attached to the pipelines, for the evaluation of
buckling failures.
|
109 |
Síntese e caracterização de manganita-cromita de lantânio dopada com rutênio para anodos de células a combustível de óxidos sólidos / Synthesis and characterization of manganite-cromite lanthanum doped with ruthenium anodes for solid oxide fuel cellsMonteiro, Natalia Kondo 30 August 2011 (has links)
Diversos anodos para célula a combustível de óxido sólido (SOFC) têm sido estudados devido aos problemas de deterioração dos anodos tradicionalmente usados, os compósitos à base de zircônia estabilizada/Ni (YSZ/Ni). Estudos prévios evidenciaram que a perovskita La0,75Sr0,25Cr0,50Mn0,50O3 (LSCM) possui desempenho similar em SOFCs usando hidrogênio e metano como combustível, tornando essa cerâmica um possível substituto dos compósitos à base de níquel. No presente estudo, foram sintetizados compostos La0,75Sr0,25Cr0,50-xMn0,50- yRux,yO3 (LSCM-Ru) pelo método dos precursores poliméricos. Análises termogravimétrica e térmica diferencial (TG/ATD) simultâneas e difração de raios X (DRX) foram utilizadas para monitorar a evolução térmica das resinas precursoras e a formação de fase dos compostos. As propriedades elétricas de amostras sinterizadas foram estudadas pela técnica de 4 pontas de prova dc na faixa de temperatura entre 25 °C e 800 °C. Os resultados experimentais indicaram a formação de fase única dos compostos LSCM-Ru calcinados a ~1200 °C. Os parâmetros de rede, calculados a partir dos dados de DRX, revelaram que a substituição parcial dos íons Cr ou Mn pelo Ru não altera significativamente a estrutura cristalina do LSCM até x,y ~ 0,10; uma característica consistente com os raios iônicos similares dos cátions Cr, Mn e Ru com número de coordenação seis. Medidas de resistividade elétrica ao ar mostraram que o mecanismo de transporte não é alterado e que o efeito da substituição de Ru nas propriedades elétricas do composto depende do íon substituído (Cr ou Mn) de maneira consistente com suas substituições parciais. Os testes de SOFCs unitárias revelaram que células com os anodos constituídos por uma camada coletora de corrente do anodo cerâmico LSCM-Ru e uma camada funcional de YSZ/Ni têm desempenho superior a células contendo apenas o anodo cerâmico. As células contendo os anodos cerâmicos LSCM-Ru foram testadas em hidrogênio e etanol, entre 800 °C e 950 °C, e mostraram desempenho em etanol superior ao em hidrogênio; uma característica que foi associada às propriedades de transporte eletrônico dos compostos LSCM-Ru em atmosfera redutora. Os resultados sugerem que os compostos LSCM com substituição parcial de Ru são anodos promissores para SOFC operando com etanol. / Several anodes for solid oxide fuel cell (SOFC) have been studied because of serious degradation exhibited by the traditionally used yttria-stabilized zirconia/Ni cermets (YSZ/Ni). Previous studies showed that the perovskite La0.75Sr0.25Cr0.50Mn0.50O3 (LSCM) has similar performance in SOFCs running on hydrogen and methane fuels, making such a ceramic a potential alternative to YSZ/Ni cermets. In the present study, compounds La0.75Sr0.25Cr0.50- xMn0.50-yRux,yO3 (LSCM-Ru) were synthesized by the polymeric precursor method. Simultaneous thermogravimetric and differential thermal analysis (TG/DTA) and X-ray diffraction (XRD) were used to monitor the thermal evolution of the precursor resins and the formation of crystalline phases. The electrical properties of sintered samples were studied by the 4-probe dc technique in the temperature range between 25 °C and 800 °C with controlled atmosphere. The experimental results showed the formation of single phase LSCM-Ru compounds after heat treatment at ~ 1200 °C. Lattice parameters, calculated from the XRD data, revealed that the partial substitution of Cr or Mn by Ru has no significant effect on the crystal structure of LSCM up to Ru x,y ~ 0.10; in agreement with the similar ionic radius of Cr, Mn and Ru with coordination number six. Electrical resistivity measurements showed that the transport mechanism is unchanged and that the effect of Ru addition on the electrical properties of the compound depends on the substituted ion (Cr or Mn). Electrochemical tests of SOFCs demonstrated that single cells comprised of a current collector layer of LSCM-Ru ceramic anode and a functional layer for YSZ/Ni have superior performance when compared to single cells with only one layer of the ceramic anode. Single cells with the LSCM-Ru ceramic anode layer were tested under both hydrogen and ethanol fuels, in the 800 °C - 950 °C temperature range. The main results showed that the single fuel cells exhibited higher performance under ethanol than under hydrogen; a feature that was related to the enhanced electronic transport properties of LSCM-Ru in reducing atmosphere. The experimental results suggest that the LSCM-Ru compounds are promising anodes for ethanol fueled SOFCs.
|
110 |
Fabricação de um sistema para decomposição de naftaleno e tolueno como compostos modeladores de alcatrão por meio da aplicação individual e combinada de plasma e micro-ondas / Fabrication of a system for the decomposition of naphthalene and toluene as tar model compounds by the individual and combined application of plasma and microwave.Moreira, Lucia Hiromi Higa 08 February 2019 (has links)
Neste trabalho foi apresentado um sistema para decomposição de aerossóis partindo de soluções contendo naftaleno (C10H8) e tolueno (C7H8) diluídos em nitrogênio por meio da aplicação individual e combinada de plasma e micro-ondas. O naftaleno e o tolueno são chamados nesta tese como \"compostos modeladores de alcatrão\" como sugere a literatura. A disposição e geometria das câmaras de plasma e micro-ondas foram estabelecidas por meio do auxílio de simulações fluidodinâmicas empregando o FloEFD V.16 (Mentor Graphics) associado aos modelos sólidos desenhados no Solid Edge ST10 (SIEMENS). Os processos de coleta de resíduos dos compostos modeladores de alcatrão, seja das cinzas, sejam da fração não decomposta foram obtidos de acordo com um protocolo bem estabelecido baseado em estudos descritos na literatura. As concentrações de tolueno e naftaleno foram obtidas utilizando espectrometria de mobilidade iônica com ionização por electrospray (ESI-IMS). Não foram empregados materiais catalisadores. As densidades de energia empregadas ao longo deste trabalho foram 0,73, 1,22 e 1,98 kWh·m-3, sob uma vazão constante de 10 L·min-1 de N2 para concentrações de 3,0 e 5,0 g·m-3 de naftaleno e tolueno. As temperaturas empregadas na decomposição térmica assistida por micro-ondas foram de 845, 960 e 1.016 °C. Para cada uma das densidades de energia, considerando a concentração de 3,0 g·m-3 de naftaleno, as eficiências obtidas por meio do plasma foram de 48,3, 59,6 e 72,2%, enquanto que aplicando micro-ondas foram de 46,2, 57,9 e 68,2%. Por outro lado, considerando a concentração de 5,0 g·m-3, as eficiências foram 31,5, 45,9 e 64,8% para plasma e 26,6, 44,3 e 56,8% empregando a decomposição térmica assistida por micro-ondas, respectivamente. Analogamente, considerando a concentração de 3,0 g·m-3 de tolueno, as eficiências foram de 52,2, 69,9 e 84,5 % por meio de plasma e 49,3, 66,8 e 79,9% por meio de micro-ondas. Finalmente, considerando a concentração de 5,0 g·m-3, as eficiências foram 33,8, 60,7 e 80,7 % empregando plasma e 30,1, 54,1 e 72,9% empregando a decomposição térmica assistida por micro-ondas, respectivamente. Por meio do teste pareado de Wilcoxon, pôde ser afirmado com evidência estatística suficiente a 95% de certeza de que decomposição por plasma foi mais eficiente do que a decomposição térmica assistida por micro-ondas e SiC. / In this work a system for the aerosols decomposition from aerosols containing naphthalene (C10H8) and toluene (C7H8) diluted in nitrogen by means of the individual and combined application of plasma and microwaves was presented. Naphthalene and toluene are referred to in this thesis as \"modeling compounds of tar\" as suggested by the literature. The arrangement and geometry of the plasma and microwave chambers were established with the aid of fluid dynamics simulations using FloEFD V.16 (Mentor Graphics) associated to solid models drawn in Solid Edge ST10 (SIEMENS). The residues collection processes of the tar model compounds, whether from the ashes or from the non-decomposed fraction of the tar model compounds were constructed according to a protocol based on well-established studies presented in the literature. The toluene and naphthalene concentrations were obtained using ion mobility spectrometry with ionization by electrospray (ESI-IMS). No catalyst materials were used. The energy densities employed during this work were 0.73, 1.22 and 1.98 kWh·m-3, under a constant flow rate of 10 L·min-1 of N2 at concentrations of 3.0 and 5.0 g·m-3 of naphthalene and toluene. The temperatures obtained in microwave assisted thermal decomposition were 845, 960 and 1016 °C. For each of the energy densities, considering the concentration of 3.0 g·m-3 of naphthalene, the efficiencies obtained by means of plasma were 48.3, 59.6 and 72.2%, while applying microwave were 46.2, 57.9 and 68.2%. On the other hand, considering the concentration of 5.0 g·m-3, the efficiencies were 31.5, 45.9 and 64.8% for plasma and 26.6, 44.3 and 56.8% using decomposition microwave assisted thermal power, respectively. Similarly, considering the 3.0 g·m-3 concentration of toluene, the efficiencies were 52.2, 69.9 and 84.5% by means of plasma and 49.3, 66.8 and 79.9% by means of microwaves. Finally, considering the concentration of 5.0 g·m-3, efficiencies were 33.8, 60.7 and 80.7% using plasma and 30.1, 54.1 and 72.9% employing assisted thermal decomposition by microwave, respectively. The Wilcoxon paired test was applied and it was stated sufficient statistical evidence with a 95% level of certainty that plasma decomposition was more efficient than microwave and SiC assisted thermal decomposition.
|
Page generated in 0.0447 seconds