Este trabalho apresenta resultados de estudos e caracterizações de Conjuntos Eletrodo/Membrana (MEAs) de Células a Combustível a Membrana Polimérica (PEMFC). Algumas condições de operação de células e diferentes processos de produção de MEA foram investigados. A técnica de Espectroscopia de Impedância Eletroquímica (EIE) (em situ - 0 a 16 A) foi usada \"on-line\" como uma ferramenta de diagnóstico, relativa ao desempenho de célula. As medidas de EIE foram feitas através do Sistema de EIE para células a combustível FC350 (GAMRY), junto a um PC4 Potentiostato/Galvanostato e conectado à carga dinâmica (TDI) para experimentos de EIE \"on-line\" (100 mHz - 10 kHz, dU = 5 mV). MEAs com 25 cm2 de área ativa, usando eletrocatalisadores PtM/C 20 % (M = Ru, Sn ou Ni) fabricados usando o Método de Redução por Álcool (MRA). A tinta catalítica foi diretamente aplicada no Tecido de Carbono (GDL) e este prensado na membrana de Nafion® (105). MEAs usando eletrocatalisadores Pt/C e PtRu/C 20 % da E-TEK foram fabricados para comparação. Todos os cátodos foram confeccionados com Pt/C 20% da E-TEK. Foram fixadas as concentrações de metal nobre em 0,4 mg Pt.cm-2 no anodo e 0,6 mg Pt.cm-2 no catodo (E-TEK). Diagramas de Nyquist dos MEAs com Pt/C e PtRu/C da E-TEK ou PtM/C MRA apresentaram as mesmas resistências de ôhmicas para os MEAs. Este fato pode ser explicado por supressão de aglomerados durante o processo de preparação do MEA ou pela homogeneidade do eletrocatalisador ancorado ao carbono. Também pôde ser observado, a baixas densidades atuais que há uma diferença de desempenho significante entre o eletrocatalisadores da ETEK e os preparados pelo MRA. Os resultados das curvas de polarização confirmaram que PtM/C MRA apresentara um aumento de atividade para as células alimentadas com metanol e etanol. A técnica de EIE se mostrou eficiente para a avaliação do método de preparação dos MEAs e do desempenho da célula, os resultados de EIE mostraram uma coerência na escolha do modelo do circuito elétrico para os MEAs utilizando hidrogênio, metanol e etanol. Esta coerência indica que outras resistências não consideradas no modelo não são relevantes na resistência total dos MEAs. / This work reports results of studies and characterization on Membrane Electrode Assemblies (MEAs) for Proton Exchange Membrane Fuel Cell (PEMFC). Some cell operation conditions and different processes of MEA production were investigated. The Electrochemical Impedance Spectroscopy Technique (EIS) (in situ - 0 to 16 A) was used \"on-line\" as a tool for diagnosis, concerning the cell performance. The EIS measurements were carried out with a FC350 Fuel Cell EIS System (GAMRY), coupled to a PC4 Potentiostat/Galvanostat and connected to the electronic load (TDI) for \"on-line\" EIS experiments (100 mHz - 10 kHz, dU = 5 mV). MEAs with 25 cm2 surface area, using PtM/C 20% (M = Ru, Sn or Ni) electrocatalysts were manufactured using the Alcohol Reduction Process (ARP). The catalytic ink was applied directly into the Carbon Cloth (GDL) and pressed in the NafionR membrane (105). MEAs using Pt/C and PtRu/C 20% from E-TEK electrocatalysts were manufactured by comparison. All the cathodes were sprayed with Pt/C 20% from E-TEK. The noble metal concentrations used were set to 0.4 mg Pt.cm-2 at the anode and 0.6 mg Pt.cm-2 at the cathode (E-TEK). Nyquist diagrams of the MEAs with Pt/C and PtRu/C from E-TEK or PtM/C (M = Ru, Sn or Ni) ARP showed essentially the same ohmic resistances for the MEAs. This fact can be explained by suppression of agglomerates during the MEA preparation process or by the homogeneity of the anchored electrocatalysts at the carbon surface. It could also be observed, at low current densities, that there was a significant performance difference between the electrocatalysts from E-TEK and those prepared with the Alcohol Reduction Process. The polarization curves results confirmed that the PtM/C (M = Ru, Sn or Ni) ARP showed an activity increase for the methanol and ethanol fed cells. The technique of EIE was shown efficient for the evaluation of the method preparation of MEAs and the acting of the cell, the results of EIE showed coherence in the choice of the model the electric circuit for MEAs using hydrogen, methanol and ethanol. This coherence indicates that other resistances no considered in the model are not relevant in the total resistance of MEAs.

In many developing economies, a high percentage of domestic energy demand is for cooking based on fossil and biomass fuels. Their use has serious health consequences affecting almost 3 billion people. Cleaner cooking systems have been promoted in these countries such as solar cooking and smokeless stoves with varying degrees of success. In parallel, solar electrolytic hydrogen systems have been developed and increasingly used during the last 25 years for electricity, heat and automobile fueling applications. This study has developed and tested experimentally in the laboratory a solar hydrogen plant numerical model suitable for small communities, to generate and store cooking fuel. The numerical model was developed in TRNSYS and consists of PV panels supplying a PEM electrolyser of 63.6% measured stack efficiency and hydrogen storage in metal hydride cylinders for household distribution. The model includes novel components for the operation of the PEM electrolyser, its controls and the metal hydride storage, developed based on data of hydrogen generation, stack temperature and energy use from a purpose constructed small-scale experimental rig. The model was validated by a second set of experiments that confirmed the accurate prediction of hydrogen generation and storage rates under direct power supply from PV panels. Based on the validated model, large-scale case studies for communities of 20 houses were developed. The system was sized to generate enough hydrogen to provide for typical domestic cooking demand for three case-studies; Jamaica, Ghana and Indonesia. The daily cooking demands were calculated to be 2.5kWh/day for Ghana, 1.98kWh/day for Jamaica and 2kWh/day for Indonesia using data mining and a specific quantitative survey for Ghana. The suitability of weather data used in the model was evaluated through Finkelstein Schafer statistics based on composite and recent weather data and by comparing simulation results. A difference of 0.9% indicated that the composite data can be confidently used. Simulations results indicate that a direct connection system to the PV plant rather than using a battery is the optimal design option based on increased efficiency and associated costs. They also show that on average 10tonnes of CO2/year/household can be saved by replacing biomass fuel with hydrogen. The potential of total savings in the three case-study countries is shown in the form of novel solar hydrogen potential maps. The results of this study are a contribution towards better understanding the use of hydrogen systems and enhancing their role in renewable energy policy.

Magister Scientiae - MSc / The aim of my work is to model a segment of a unit cell of a fuel cell stack using numerical methods which is classified as computational fluid dynamics and implementing the work in a commercial computational fluid dynamics package, FLUENT. The focus of my work is to study the thermal distribution within this segment. The results of the work aid in a better understanding of the fuel cell operation in this temperature range. At the time of my investigation experimental results were unavailable for validation and therefore my results are compared to previously published results published. The outcome of the results corresponds to this, where the current flux density increases with the increasing of operating temperature and fixed operating voltage and the temperature variation across the fuel cell at varying operating voltages. It is in the anticipation of determining actual and or unique material input parameters that this work is done and at which point this studies results would contribute to the understanding high temperature PEM fuel cell thermal behaviour, significantly. / South Africa

The objective of the research is to synthesize the diazonium N-(perfluoroalkyl) benzenesulfonimide (PFSI)zwitterionicpolymers as electrolytes in polymerelectrolyte membrane (PEM) fuel cells. The proposed diazoniumPFSI zwitterionic polymer (I) is expected to enhance the thermal and chemical stability, increase the proton conductivity of electrolytes, and improve the catalyst efficiency for PEM fuel cells. Synthesis of the perfluorobenzoyl peroxide initiator, homopolymerization of perfluoro (3-oxapent-4-ene) sulfonyl fluoride,coupling reaction with4-sulfamonylacetanilide, couplingreaction with 4-nitrobenzene sulfonyl amide, n-deacetylation reaction, and diazotization reactionhave been carried outsuccessfully in the lab. The intermediate chemicals are characterized by GC-MS, IR, NMR, and GPC spectroscopies.

No description available.

Sjöfarten står för 3 % av världens totala växthusgaser och är idag högst beroende av fossila bränslen. Ett alternativ för att gå över till en fossilfri flotta är användning av bränsleceller och vätgas som drivmedel. Om vätgasen produceras från elektrolys med förnyelsebara energikällor så är driften utsläppsfri och koldioxidneutral. Bränsleceller kan användas i många olika sammanhang, men har ännu inte slagit igenom med full kraft. En anledning till detta är livslängden som är för kort. För att sjöfarten ska kunna implementera bränslecellsdrift behöver nedbrytningen av bränslecellen bli vidare utforskad och motverkad. Syftet med detta examensarbete var att hitta de mest signifikanta nedbrytningsmekanismerna för sjöfarten samt att bygga en modell för att förutspå livslängden utifrån lastprofiler från fartyg.  Rapportens avgränsningar var att enbart studera PEM-bränsleceller tack vare dess höga energitäthet och att teknologin är närmast marknaden för mobila applikationer. En litteraturstudie genomfördes för att fastställa de viktigaste nedbrytningsmekanismerna samt de faktorer som begränsar livslängden. Dessa bestämdes till start/stop cykler samt lastcykler vilka försämrar konduktiviteten i membranet samt minskar den elektrokemiska ytarean. En empirisk modell från experiment från litteraturen etablerades för att hitta relationen mellan parametrarna konduktivitet och elektrokemisk ytarea som funktion av start/stop cykler respektive lastcykler. En Comsol-modell användes för att utvärdera bränslecellens prestanda med dessa försämrade parametrar. Två lastprofiler analyserades och tolkades som antal start/stop cykler samt lastcykler för att utvärdera prestandan som funktion av antal år i drift. Båda fallen var i drift till dess att prestandan minskat med 20 % utvärderat vid strömtätheten 0.6 A/cm2. Båda lastprofilerna var utvärdera med olika körstrategier för att jämföra den modellerade livslängden beroende på ingångsvärden. Den första lastprofilen delades in i Case 1a och Case 1b där antalet start/stop cykler och lastcykler varierade. Resultatet visade att antalet timmar i drift mer än tredubblades i Case 1b där båda ingående indata hade minskats.   Case 2 delades upp i tre olika körstrategier där Case 2a var en referens som jämfördes mot Case 2b respektive Case 2c. Skillnaden mot Case 2b var att antalet start/stop cykler per dag multiplicerades med faktor 4. Resultatet från modellen var att livstiden minskade från 6 till 4 år. Vidare utvärderades Case 2c där istället antalet lastcykler dividerades med faktor 4, allt annat identiskt med Case 2a. Utfallet var en ökad livslängd från 6 år till 11 år, med totalt 32 032 timmar i drift. Denna livslängd kan jämföras med kommersialiserade marina produkter från Ballard och Powercell, där livslängden är 30 000 respektive 20 000 timmar i drift.  Sammanfattningsvis kan det konstateras att både start/stop cykler och lastcykler bryter ner bränslecellen och därmed minskar dess prestanda. Lastcykler var den faktor som var mest förödande gällande livslängden. Den modellerade livslängden på 32 032 timmar indikerar att den empirisk modellen tillsammans med Comsol-modellen genererade realistiska resultat. Slutligen kan sägas att ett område för framtida forskning inom ämnet innefattar lastcykler eftersom denna hade störst påverkan på modellen. Att särskilja olika typer av lastcykler och koppla till olika degradering skulle skapa än mer förståelse för livslängden. Då denna studie genomfördes på bränslecellsnivå skulle framtida studier kunna inkludera att analysera degradering på systemnivå för att få mer insikt i dessa processer. / The shipping industry emits 3 % of the global GHG-emissions and is highly dependent on fossil fuels. One alternative to decarbonise the sector is by utilising hydrogen in fuel cells. The propulsion is free from emissions if hydrogen is produced from renewables. The fuel cell technology can be applied in various applications but have not been fully commercialised. One of the biggest bottlenecks for fuel cell technology is the durability that needs to be improved. In order for marine vessels to implement hydrogen propulsion, the degradation need to be further understood and mitigated. The purpose of this thesis was to assess the most significant degradation mechanisms for marine applications and to build a model to evaluate the lifetime depending on load profiles. The scope of the thesis was to include PEMFCs since they have the highest power density and are closest to commercialisation for transport applications. A literature review was conducted to assess the most important degradation mechanisms and operating conditions that limits the lifetime, which concluded in start/stop cycling and load cycling. These conditions deteriorate the membrane conductivity and the electrochemical surface area. An empirical model based on experimental data from the literature was conducted to find relationships for conductivity and ECSA as function of start/stop cycling and load cycling, respectively. A Comsol model was established to evaluate performance reduction with degraded parameters. Two different load cycles were interpreted as number of start/stop cycles and load cycles in order to simulate the degradation. The output was polarization curves as function of operating years. Each case was operated until a performance reduction of 20 % was obtained at the current density of 0.6 A/cm2.  Both load profiles were analysed with different operation strategies to compare the resulting lifetime. The first load curve was divided into Case 1a and Case 1b where start/stop cycles and load cycles were altered. The results showed that the lifetime in operation hours was more than three-folded in Case 1b when the number of start/stop cycles and load cycles was reduced.  Case 2 was divided into three operating strategies. For comparison with Case 2a, the number of start/stop cycles per day in Case 2b was increased by a factor of 4. The result was that the lifetime declined from 6 to 4 years. Furthermore, Case 2c evaluated the lifetime if the number of load cycles per day decreased by a factor of 4, all else being equal to Case 2a. The outcome was an increment in lifetime from 6 to 11 years, with a total of 32 032 hours of operation. This lifetime can be compared to commercialised products from Ballard and Powercell with lifetimes of 30 000 and 20 000 operating hours, respectively. Conclusively, the simulations showed that both start/stop cycling and load cycling deteriorates the fuel cell performance. Load cycling is the operating condition that cause the most severe degradation. Moreover, the modelled lifetime of 32 032 hours indicates that the empirical model in combination with the Comsol model generate realistic lifetimes. Finally, since load cycling had the most vital impact on the lifetime, one of the topics for future research would be to distinguish different types of load cycles and connect to separate degradation outcomes. Since the model was on fuel cell level, future work could also include systems effects such as ripple current or distributions within fuel cell stacks.

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Sjöfarten är idag dominerad av förbränningsmotorer som är beroende av fossila drivmedel. Elektrifiering är en av huvudstrategierna för att möjliggöra fossilfri energiförsörjning inom internationell sjöfart. Polymerelektrolytbränslecellen (PEMFC) omvandlar vätgas till elektricitet med hög verkningsgrad och är för närvarande kommersiellt tillgängligt upp till MW-skala för ett fartyg. Vätgas är en utmärkt energibärare för att tillgodose hög energidensitet hos ett fraktfartyg. Rippelströmmar från elkraftskomponenter påstås accelerera åldring av materialen i PEMFC och kan därför skapa negativa effekter över tid som påverkar livslängden av systemet.  De tillgängliga studier som utvärderar rippelströmmars påverkan på åldring i PEMFC är begränsade. Resultaten i dessa studier är tvetydiga och saknar tydliga kopplingar mellan rippelströmmarnas inverkan på åldringsfenomen, som på sikt kan påverka den tekniska livslängden. Målet med examensarbetet var att identifiera effekten av rippelströmmar på åldring av bränslecellen vid typiska körförhållanden för ett fraktfartyg. Tester genomfördes på en PEMFC genom att applicera en sinusformad (70 Hz, 50 % amplitud) rippelström på en dynamisk last som simulerar ett fraktfartyg. En konstant lastcykling vid 0.4 A/cm2 utfördes som ett komplement för att verifiera den dynamiska lastens inverkan på bränslecellen.  Alla tester resulterade i prestandaförluster både under den konstanta och dynamiska lasten, med eller utan rippelström. Men resultaten indikerade att effekten av en sinusformad rippelström inte orsakade någon signifikant åldring varken vid konstant respektive dynamisk lastcykel. / The marine shipping industry is dominated by fossil fuel driven propulsion. Electrification of marine vessels is one of the main strategies to enable emission-free propulsion. Hydrogen is an excellent energy carrier to meet the power demand of a marine vessel. Proton exchange membrane fuel cells (PEMFC) is a commercially available alternative for converting hydrogen into electricity. However, durability issues of the PEMFC is a constraint with the technology which limits technical lifetime. Research around ripple currents impact on degradation of PEMFC is scarce and the reported results are ambiguous and lack clear correlation between the effects of the ripple current on the lifetime of a PEMFC. This master thesis evaluates the impact on degradation of a single cell PEMFC by imposing a sinusoidal (70 Hz, 50 % amplitude) AC ripple to a dynamic load cycle. The dynamic load cycle is designed to simulate typical operating conditions of a marine vessel. Constant load cycling at 0.4 A/cm2 with the same ripple characteristics was also conducted to verify the dynamic load cycling impact on the performance losses of the PEMFC. The in-situ characterization showed performance losses both during the dynamic and constant load cycling, for the ripple current and reference tests. To conclude, no significant effects on degradation by the sinusoidal ripple current of 70 Hz and 50% amplitude is found when applied to a single cell PEMFC despite of performance losses for all cases.

No description available.

No description available.