Métodos de preparação de nanopartículas metálicas suportadas em carbono de alta área superficial, como eletrocatalisadores em células a combustível com membrana trocadora de prótons

Fuel cells are attracting much interest as efficient and clean energy conversion devices. The main components of low temperature fuel cells are the electrocatalysts used to promote the anodic and cathodic reactions, which are based on platinum and platinum alloys. These electrocatalysts are normally prepared in the form of metal nanoparticles supported on a conductive material, usually high surface area carbon, to improve catalyst utilization and reduce cost. This work presents and comments some methods used presently to produce these electrocatalysts. The performances of the produced electrocatalysts are compared to that of state-of-the-art commercial E-TEK electrocatalysts.

Pilhas a combustível de óxido sólido: materiais, componentes e configurações

In this paper the current status of fuel cells is described with particular emphasis on high (T > 800 ºC) and intermediate (T < 800 ºC) temperature solid oxide fuel cells. Also the importance of the fuel cell technology is shown. Reviewed are the fundamental features, the basic principles, types of fuel cell, fabrication methods, cell configurations and the development of components (cathodes, anodes, electrolytes, interconnect) and materials.

Montagem e caracterização elétrica de pilhas a combustível de óxido sólido (PaCOS)

This paper is focused on a review of the design features and the electrochemistry characterization of anode-supported planar SOFC. Studies and results of metallic alloy interconnectors and recovery for protection against corrosion and for contact layer are showed. Moreover a discussion of examples of measurements of impedance spectrometry, according to the literature and our experimental results are made. For the anode supported fuel cells the power density varies from 0.1 to 0.5 Wcm², according to results in the literature (showed in this paper). For electrolyte supported fuel cell the power density can be 10 Wcm-2 for high temperatures. An English-Portuguese glossary of most used terms in SOFC stack is given for greater clarity and to introduce new terms to the reader.

Pilhas de combustíveis microbianas utilizadas na produção de eletricidade a partir de rejeitos orgânicos: uma perspectiva de futuro

In this review is presented an innovative technology for use of animal and vegetable waste with high pollution levels in microbial fuel cell (MFC) as an alternative to waste remediation and simultaneously producing electricity and fertilizer for agriculture. A brief history of MFC, the studies about the electron transfer mechanisms, discussion of the biological nanowires in bacteria and the use of chemical mediators or carriers of electrons are explained. The factors influencing the performance of MFCs, the application in waste and sewage treatment and power generation are also discussed.

Effect of temperature on the electro-oxidation of ethanol on platinum

We present in this work an experimental investigation of the effect of temperature (from 25 to 180 ºC) in the electro-oxidation of ethanol on platinum in two different phosphoric acid concentrations. We observed that the onset potential for ethanol electro-oxidation shifts to lower values and the reaction rates increase as temperature is increased for both electrolytes. The results were rationalized in terms of the effect of temperature on the adsorption of reaction intermediates, poisons, and anions. The formation of oxygenated species at high potentials, mainly in the more diluted electrolyte, also contributes to increase the electro-oxidation reaction rate.

Interação de átomos leves com clusters de metais de transição

Density Functional Theory (DFT) calculations on the interactions of small atoms (H, C, O, and S) on first-row transition metal clusters were performed. The results show that the adsorption site may vary between the metal surface and the edge of the cluster. The adsorption energies, adatom-nearest neighbor and adatom-metal plane distances were also determined. Finally, the authors present a discussion about the performance of these metals as anodes on solid oxide fuel cells. The results obtained agree with empirical data, indicating that the theoretical model used is adequate

A utilização de etanol em célula a combustível de óxido sólido

This work reports a review on the status and technical feasibility of the application of ethanol as fuel for Solid Oxide Fuel Cells (SOFC), presenting both external reform and cell with direct utilization of ethanol. Based on this survey, both experimental results and mathematical modeling indicated the technical feasibility of power generation by ethanol SOFC, with cell units producing 450 mW/cm², sufficient for scale up to large stationary plants. The quantitative assessments in the literature show this field to be promising for researchers and private sector investment as well being a strategic technology for government policy in the short and long term.

Tasajännitetason nosto polttokennosovelluksessa

Polttokennojen, erityisesti SOFC-kennojen, tutkimuksessa on viime vuosina saavutettu merkittäviä edistysaskelia ja mahdollisuudet kennojen laajamittaiseen hyödyntämiseen paranevat koko ajan. Polttokennojen yleistyessä tarvitaan tehoelektroniikkaa muokkaamaan kennojen tasajännite verkkoon sopivaksi vaihtojännitteeksi. Verkkovaihtosuuntaaja vaatii korkeamman jännitetason, kuin polttokennosta on saatavissa, joten tasajännitetasoa on ensin nostettava. Tässä diplomityössä esitellään kolme eri hakkuritopologiaa ja perehdytään kokosiltahakkurin optimointiin. Hakkurin pääasialliset häviölähteet olivat toision diodisilta ja transistorit. Diodien vaihtaminen piidiodeista piikarbididiodeihin ei parantanut hyötysuhdetta, koska toision jännite tarkastellussa sovelluksessa oli matala. Muuntajan käämiminen litz-johtimella paransi hyötysuhdetta merkittävästi.

Vertailu kahden erityyppisen virtasyötetyn hakkurin soveltuvuudesta polttokennokäyttöihin

Concerns about condition of the environment and rising fossil fuel prices have accelerated the research of finding new cheap and environmental friendly energy source. Fuel cells are one of the most promising green technologies, especially in the field of distributed energy generation, backup power systems, transportation and mobile power generation. In this bachelor’s thesis use of fuel cells is studied, especially from the DC-DC converter point of view. This bachelor’s thesis concentrates on study of two different DC-DC converters. The aim of this thesis is to study design and steering methods for proposed converters. The ultimate aim of this thesis is to determine which one of proposed converters is most suitable for fuel cell applications.

Diskreettiaikainen liukuvan moodin säätö kiinteäoksidipolttokennon DC-tasonnostossa

Huoli ympäristön tilasta ja fossiilisten polttoaineiden hinnan nousu ovat vauhdittaneet tutkimusta uusien energialähteiden löytämiseksi. Polttokennot ovat yksi lupaavimmista tekniikoista etenkin hajautetun energiantuotannon, varavoimalaitosten sekä liikennevälineiden alueella. Polttokenno on tehonlähteenä kuitenkin hyvin epäideaalinen, ja se asettaa tehoelektroniikalle lukuisia erityisvaatimuksia. Polttokennon kytkeminen sähköverkkoon on tavallisesti toteutettu käyttämällä galvaanisesti erottavaa DC/DC hakkuria sekä vaihtosuuntaajaa sarjassa. Polttokennon kulumisen estämiseksi tehoelektroniikalta vaaditaan tarkkaa polttokennon lähtövirran hallintaa. Perinteisesti virran hallinta on toteutettu säätämällä hakkurin tulovirtaa PI (Proportional and Integral) tai PID (Proportional, Integral and Derivative) -säätimellä. Hakkurin epälineaarisuudesta johtuen tällainen ratkaisu ei välttämättä toimi kaukana linearisointipisteestä. Lisäksi perinteiset säätimet ovat herkkiä mallinnusvirheille. Tässä diplomityössä on esitetty polttokennon jännitettä nostavan hakkurin tilayhtälökeskiarvoistusmenetelmään perustuva malli, sekä malliin perustuva diskreettiaikainen integroiva liukuvan moodin säätö. Esitetty säätö on luonteeltaan epälineaarinen ja se soveltuu epälineaaristen ja heikosti tunnettujen järjestelmien säätämiseen.

Performance and scalability of isolated DC-DC converter topologies in low voltage, high current applications

Fuel cells are a promising alternative for clean and efficient energy production. A fuel cell is probably the most demanding of all distributed generation power sources. It resembles a solar cell in many ways, but sets strict limits to current ripple, common mode voltages and load variations. The typically low output voltage from the fuel cell stack needs to be boosted to a higher voltage level for grid interfacing. Due to the high electrical efficiency of the fuel cell, there is a need for high efficiency power converters, and in the case of low voltage, high current and galvanic isolation, the implementation of such converters is not a trivial task. This thesis presents galvanically isolated DC-DC converter topologies that have favorable characteristics for fuel cell usage and reviews the topologies from the viewpoint of electrical efficiency and cost efficiency. The focus is on evaluating the design issues when considering a single converter module having large current stresses. The dominating loss mechanism in low voltage, high current applications is conduction losses. In the case of MOSFETs, the conduction losses can be efficiently reduced by paralleling, but in the case of diodes, the effectiveness of paralleling depends strongly on the semiconductor material, diode parameters and output configuration. The transformer winding losses can be a major source of losses if the windings are not optimized according to the topology and the operating conditions. Transformer prototyping can be expensive and time consuming, and thus it is preferable to utilize various calculation methods during the design process in order to evaluate the performance of the transformer. This thesis reviews calculation methods for solid wire, litz wire and copper foil winding losses, and in order to evaluate the applicability of the methods, the calculations are compared against measurements and FEM simulations. By selecting a proper calculation method for each winding type, the winding losses can be predicted quite accurately before actually constructing the transformer. The transformer leakage inductance, the amount of which can also be calculated with reasonable accuracy, has a significant impact on the semiconductor switching losses. Therefore, the leakage inductance effects should also be taken into account when considering the overall efficiency of the converter. It is demonstrated in this thesis that although there are some distinctive differences in the loss distributions between the converter topologies, the differences in the overall efficiency can remain within a range of a few percentage points. However, the optimization effort required in order to achieve the high efficiencies is quite different in each topology. In the presence of practical constraints such as manufacturing complexity or cost, the question of topology selection can become crucial.

Kaksisuuntaisen DC/DC-hakkurin virtasäätö polttokennosovelluksessa

Ilmastonmuutos ja fossiilisten polttoaineiden ehtyminen ovat edesauttaneet uusiutuvien energialähteiden tutkimusta huomattavasti. Lisäksi alati kasvava sähköenergian tarve lisää hajautetun sähköntuotannon ja vaihtoehtoisten energialähteiden kiinnostavuutta. Yleisimpiä hajautetun sähköntuotannon energialähteitä ovat tuulivoima, aurinkovoima ja uutena tulokkaana polttokennot. Polttokennon kytkeminen sähköverkkoon vaatii tehoelektroniikkaa, ja yleensä yksinkertaisessa polttokennosovelluksessa polttokenno kytketään galvaanisesti erottavan yksisuuntaisen DC/DC-hakkurin ja vaihtosuuntaajan kanssa sarjaan. Polttokennon rinnalla voidaan käyttää akkua tasaamaan polttokennon syöttämää jännitettä, jolloin akun ja polttokennon väliin tarvitaan kaksisuuntainen DC/DC-hakkuri, joka pystyy siirtämään energiaa molempiin suuntiin. Tässä diplomityössä on esitetty kaksisuuntaisen DC/DC-hakkurin tilayhtälökeskiarvoistusmenetelmään perustuva malli sekä mallin perusteella toteutettu virtasäätö. Tutkittava hakkuritopologia on kokosilta-tyyppinen boost-hakkuri, ja säätömenetelmä keskiarvovirtasäätö. Työn tuloksena syntyi tilayhtälömalli kaksisuuntaiselle FB boost -hakkurille sekä sen tulokelan virran säätämiseen soveltuva säädin. Säädin toimii normaalitilanteissa hyvin, mutta erikoistilanteissa, kuten hakkurin tulojännitteen äkillisessä muutostilanteessa, vaadittaisiin tehokkaampi säädin, jolla saavutettaisiin nopeampi nousuaika ilman ylitystä ja oskillointia.

Hydrogen Sensor Application of Anodic Titanium Oxide Nanostructures

Hydrogen (H2) fuel cells have been considered a promising renewable energy source. The recent growth of H2 economy has required highly sensitive, micro-sized and cost-effective H2 sensor for monitoring concentrations and alerting to leakages due to the flammability and explosiveness of H2 Titanium dioxide (TiO2) made by electrochemical anodic oxidation has shown great potential as a H2 sensing material. The aim of this thesis is to develop highly sensitive H2 sensor using anodized TiO2. The sensor enables mass production and integration with microelectronics by preparing the oxide layer on suitable substrate. Morphology, elemental composition, crystal phase, electrical properties and H2 sensing properties of TiO2 nanostructures prepared on Ti foil, Si and SiO2/Si substrates were characterized. Initially, vertically oriented TiO2 nanotubes as the sensing material were obtained by anodizing Ti foil. The morphological properties of tubes could be tailored by varying the applied voltages of the anodization. The transparent oxide layer creates an interference color phenomena with white light illumination on the oxide surface. This coloration effect can be used to predict the morphological properties of the TiO2 nanostructures. The crystal phase transition from amorphous to anatase or rutile, or the mixture of anatase and rutile was observed with varying heat treatment temperatures. However, the H2 sensing properties of TiO2 nanotubes at room temperature were insufficient. H2 sensors using TiO2 nanostructures formed on Si and SiO2/Si substrates were demonstrated. In both cases, a Ti layer deposited on the substrates by a DC magnetron sputtering method was successfully anodized. A mesoporous TiO2 layer obtained on Si by anodization in an aqueous electrolyte at 5°C showed diode behavior, which was influenced by the work function difference of Pt metal electrodes and the oxide layer. The sensor enabled the detection of H2 (20-1000 ppm) at low operating temperatures (50–140°C) in ambient air. A Pd decorated tubular TiO2 layer was prepared on metal electrodes patterned SiO2/Si wafer by anodization in an organic electrolyte at 5°C. The sensor showed significantly enhanced H2 sensing properties, and detected hydrogen in the range of a few ppm with fast response/recovery time. The metal electrodes placed under the oxide layer also enhanced the mechanical tolerance of the sensor. The concept of TiO2 nanostructures on alternative substrates could be a prospect for microelectronic applications and mass production of gas sensors. The gas sensor properties can be further improved by modifying material morphologies and decorating it with catalytic materials.

Caracterització electroquímica de catalitzadors de Pt/C per a PEMFC

Màster en Química Avançada: Química Física de Materials, Curs: 2007-2008

On discrimination algorithms for ill-posed problems with an application to magnetic tomography

In this paper we explore classification techniques for ill-posed problems. Two classes are linearly separable in some Hilbert space X if they can be separated by a hyperplane. We investigate stable separability, i.e. the case where we have a positive distance between two separating hyperplanes. When the data in the space Y is generated by a compact operator A applied to the system states ∈ X, we will show that in general we do not obtain stable separability in Y even if the problem in X is stably separable. In particular, we show this for the case where a nonlinear classification is generated from a non-convergent family of linear classes in X. We apply our results to the problem of quality control of fuel cells where we classify fuel cells according to their efficiency. We can potentially classify a fuel cell using either some external measured magnetic field or some internal current. However we cannot measure the current directly since we cannot access the fuel cell in operation. The first possibility is to apply discrimination techniques directly to the measured magnetic fields. The second approach first reconstructs currents and then carries out the classification on the current distributions. We show that both approaches need regularization and that the regularized classifications are not equivalent in general. Finally, we investigate a widely used linear classification algorithm Fisher's linear discriminant with respect to its ill-posedness when applied to data generated via a compact integral operator. We show that the method cannot stay stable when the number of measurement points becomes large.