Este trabalho teve como objetivo a combinação de ânodos e eletrólitos otimizados, para a formação de células a combustível de etanol direto (DEFC), operantes em elevadas temperaturas (130 ºC). Como materiais de ânodo, foram produzidos eletrocatalisadores baseados em PtSn/C, com diversas razões atômicas Pt:Sn, preparados pelo método do poliol modificado, essa metodologia possibilita a produção de eletrocatalisadores auto-organizados com estreita distribuição de tamanhos de partículas e elevado grau de liga. Os eletrocatalisadores foram caracterizados por DRX e stripping de CO. Os resultados mostraram que esses materiais apresentaram elevado grau de liga e Eonset de oxidação de CO em potenciais menores do que os materiais comerciais. Como eletrólito, foram sintetizados híbridos Nafion-SiO2 com a incorporação do óxido diretamente nos agregados iônicos de diversos tipos de membranas Nafion. Os parâmetros de síntese, tais como o solvente em meio solgel, a espessura da membrana, e a concentração do precursor de sílica foram avaliados em termos do percentual de sílica incorporada e da estabilidade mecânica do híbrido. Por fim, ânodos e eletrólitos otimizados foram avaliados em DEFCs nas temperaturas de 80 e 130 ºC. Os resultados mostraram um significativo incremento no desempenho de polarização (122 mW cm-2), resultado da aceleração na taxa de oxidação de etanol devido ao material de ânodo otimizado e do aumento de temperatura de operação, uma vez que o uso de eletrólitos híbridos possibilita o aumento da temperatura sem perdas de condutividade. Nesse sentido, a combinação de eletrodos e eletrólitos otimizados é uma alternativa promissora para o desenvolvimento de tais dispositivos. / This work has as objective to evaluate anodes and electrolytes in direct ethanol fuel cells (DEFC) operating at high temperature (130 ºC). As anode materials, electrocatalysts based on PtSn/C were prepared by Modified Polyol Method with various Pt:Sn atomic ratios. Such methodology promotes selforganized electrocatalysts production with narrow particle size distribution and high alloying degree. The eletrocatalysts were characterized by XRD, and CO stripping. The results showed that these materials presented high alloying degree and Eonset CO oxidation at lower potential as commercial materials. As electrolyte, Nafion-SiO2 hybrids were synthesized by sol-gel reaction, by the incorporation of oxide directly into the ionic aggregates of various kinds of Nafion membranes. The synthesis parameter, such sol-gel solvent, membrane thickness and silicon precursor concentration were studied in terms of silica incorporation degree and hybrid mechanical stability. Finally, the optimized anodes and electrolytes were evaluated in DEFC operating at 80 130 ºC temperature range. The results showed a significant improvement of the DEFC performance (122 mW cm-2), resulted from the acceleration of ethanol oxidation reaction rate due to anode material optimization and high temperature operation once the use of hybrids possibilities the increase of temperature without a significant conductivity loses. In this sense, the combination of optimized electrodes and electrolytes are a promising alternative for the development of these devices.

A fabricação e a caracterização de eletrólitos compósitos Nafion - TiO2, e seu uso em células PEM (Proton Exchange Membrane) operando em temperaturas elevadas (~ 130 ºC) foram estudados. A operação em altas temperaturas da célula PEM traz benefícios, como o aumento da cinética das reações eletródicas, o aumento da cinética de transporte difusional nos eletrodos e o aumento da tolerância da célula ao contaminante monóxido de carbono. O Nafion ®, eletrólito polimérico comumente empregado em células PEM, possui condutividade elétrica dependente da quantidade de água contida em sua estrutura. Desta forma, o aumento da temperatura de operação da célula acima de 100 ºC causa a desidratação do polímero diminuindo acentuadamente sua condutividade elétrica. Para aumentar o desempenho dos eletrólitos operando em altas temperaturas, eletrólitos compósitos (Nafion-TiO2) foram preparados pelo método de conformação por evaporação em molde. A adição de partículas higroscópicas de titânia (TiO2) na matriz polimérica visa melhorar as condições de umidificação do eletrólito em temperaturas elevadas. Três tipos de partículas de titânia com diferentes áreas de superfície específica e formas distintas foram investigados. Compósitos à base de Nafion com adição de 2,5 a 15% em massa de partículas de titânia com forma aproximadamente esférica e com área de superfície específica de até ~115 m2g-1 apresentaram maiores valores da temperatura de transição vítrea do que o polímero. Este aumento melhora a estabilidade do eletrólito durante a operação de células a combustível PEM em 130 ºC. Os compósitos formados a partir da adição de nanotubos derivados de titânia apresentaram pronunciado ganho de desempenho e maior estabilidade térmica em operação de células acima de 100 ºC. Neste caso, a elevada área superficial e a forma dos nanotubos de titânia contribuíram significativamente para o aumento da absorção e da retenção de água do compósito. Por outro lado, as curvas de polarização mostraram um aumento na polarização por queda ôhmica com o aumento da concentração das partículas cerâmicas adicionadas. A morfologia do polímero não foi alterada com a adição de partículas inorgânicas, portanto, o desempenho dos compósitos reflete uma competição entre a adição de uma fase isolante, que diminui a condutividade elétrica, e o aumento da estabilidade térmica ou da retenção de água do compósito. Os eletrólitos compósitos testados provaram serem promissores na aplicação em células PEM em temperaturas acima de 100 ºC. / The fabrication and characterization of Nafion - TiO2 composites, and the use of such electrolytes in PEM (Proton Exchange Membrane) fuel cell operating at high temperature (130 °C) were studied. The operation of a PEM fuel cell at such high temperature is considered as an effective way to promote fast electrode reaction kinetics, high diffusional transport, and high tolerance to the carbon monoxide fuel contaminant. The polymer Nafion® is the most used electrolyte in PEM fuel cells due to its high proton conductivity. However, the proton transport in Nafion is dependent on the water content in the polymeric membrane. The need of absorbed water in the polymer structure limits the operation of the fuel cell to temperatures close to 100 °C, above which Nafion exhibits a fast decrease of the ionic conductivity. In order to increase the performance of the electrolyte operating at high temperatures, Nafion-TiO2 composites have been prepared by casting. The addition of titania hygroscopic particles to the polymeric matrix aims at the enhancement of the humidification of the electrolyte at temperatures above 100 °C. Three types of titania particles with different specific surface area and morphology have been investigated. Nafion-based composites with the addition of titania nanoparticles, in the 2.5-15 wt.% range, with nearly spherical shape and specific surface area up to ~115 m2g-1 were found to have higher glass transition temperature than the polymer. Such an increase improves the stability of the electrolyte during the fuel cell operation at high temperatures. The addition of titania-derived nanotubes results in a pronounced increase of the performance of PEM fuel cell operating at 130 °C. In this composite, the high specific surface area and the tubular shape of the inorganic phase are responsible for the measured increase of both the absorption and retention of water of the composite electrolyte. Nonetheless, the polarization curves of fuel cell using the composite electrolytes exhibited an increase of the ohmic polarization associated with the addition of the insulating titania particles. As the chemical structure of Nafion was observed to be insensitive to the addition of the inorganic particles, the high performance of the composite electrolytes is a result of competing effects: the decrease of the electrical conductivity and a higher thermal stability or water absorption/retention capacity. The experimental results suggest that the Nafion-TiO2 composites are promising electrolytes for PEM fuel cells operating at temperatures above ~100 °C.

Electro-organic reactions are often complicated by the need to add supporting electrolytes and co-solvents. In many cases these additives take part in side reactions causing low yields and hinder the purification stages. The solid polymer electrolyte (SPE) reactor uses an ion exchange membrane to transfer charged species between the electrodes and so eliminates the need for any additives. In this way improvements in electrochemical processing can be achieved. The SPE reactor has only been studied for model organic and aqueous based electrochemical reactions. The aims of this project were to develop the reactor for use as a suitable means of synthesising alcohols and acids based on substituted toluenes. This involved selection of suitable electrode material, polymer electrolyte pre-treatment and reactor modelling. According to published reports the direct electro-oxidation of toluene takes place with maximum yields of 19% with an acetic acid co-solvent and a nitric acid supporting electrolyte. Higher yields are possible with inorganic mediators such as Mn³⁺ and Cr⁶⁺. 30% yields of methoxylated products are possible from electrolysis in methanol although many non volatile by-products are formed. Initial research was spent investigating the oxidation of toluene in sulphuric acid at a lead dioxide rotating disk electrode. It was found that the reaction is mass transfer limited in the potential region below gas evolution. The order of reaction with respect to toluene was 0.5. Electrolysis of toluene on platinum mesh in nitric acid with and without acetic acid was found to produce benzyl alcohol and benzaldehyde with low current efficiencies. Without co-solvent the maximum current efficiency was 10% at 2S0Alm². An SPE reactor fabricated from glass with an active electrode area of Scm2 was used to perform electrode tests. Highest yields of benzaldehyde were obtained using nickel foam, graphite felt and palladium coated mesh electrodes. The current efficiencies were 52.4%, 20.3% and 10.7% respectively. This work highlighted the need for a good membrane-electrode contact. The oxidation of benzyl alcohol in the same reactor using nickel foam Abstract was accomplished with a current efficiency of 85.4% showing that the difficult step in the oxidation of toluene was the first one to benzyl alcohol. Pre-treatment of the membrane by swelling in solvents was considered to be an important factor in the performance of the SPE reactor. Several ion exchange membranes were pre-treated in a variety of aqueous and organic solvents including methanol, toluene, DMF, water and sulphuric acid. Nafion® 117 was found to increase in size more than the other tested membranes in all solvents except water and sulphuric acid. Many of the pre-treated membranes were tested in an SPE reactor made from steel with an active electrode area of 2lcm2 for the oxidation of toluene in methanol. The anode-membrane potential was measured as a function of time and current density with Nafion® 117 having the lowest values of potential. Selection of the pre-treatment method for future use was determined by assessing the performance in the reactor, contamination of products and chemical hazards. Swelling in aqueous solvents was the chosen procedure. The steel SPE reactor was operated in continuous mode with recycle for the oxidation of toluene in methanol. Galvanostatic electrolysis took place at several current densities, temperatures and feed concentrations. Two products were identified as ⍺-methoxytoluene and ⍺,⍺-dimethoxytoluene and these were formed at low current efficiencies between 1.4% and 9%. The main product was thought to be an oligomer of toluene. The gas generated was found to be mainly hydrogen with a small amount of oxygen thought to come from residual water in the pre-treated membrane. A computer simulation of the SPE reactor for toluene oxidation in methanol was based on two series and one parallel reaction. These were first order in reactant species and followed Tafel type kinetics. Mass transfer of dilute reactants was based on Fickian diffusion. Parameters not available in the literature such as membrane potential and electro-osmotic flow were correlated to applied variables using experimental data and multiple linear regression. The importance of electro-osmotic flow in the SPE reactor was demonstrated by considering its effect on product distribution. The model showed that the oligomerisation of toluene was the dominant reaction making the SPE reactor unsuitable for the oxidation of toluene.

The dynamical characteristics and the structure of lithium in Nafion were investigated by solid state magic angel spinning nuclear magnetic resonance(MAS NMR). Variable temperature, longitudinal NMR relaxation time(T1), self-diffusion coefficients and rotational activation energy of various concentrations were determined. The distribution of the 7Li MAS NMR spectra of Nafion/Li represent the pore size, and T1 of Nafion/Li is slower than the bulk lithium solution, it implied the lithium were crowed in the pore(exchanged with the proton). Rotational activation energy illustrated the block level of lithium in different pores of Nafion. In the longitudinal NMR relaxation rate of various concentrations, instead, the type of bonding between lithium and water were different. The variable temperature experiments of 7Li MAS NMR spectra also illustrated the temperature about 60~66¢J result in the change of microstructure of Nafion.

Perfluororated proton exchange membrane Nafion is the mostly used type of ion exchange membrane in fuel cells. Over the past decades, various studies have been carried out on their structures at different scales, proton conduction mechanism, electrochemical performance, thermal and mechanical properties etc, but many problems are still open, such as the precise picture of proton conduction, degradation and aging of the membrane, even the distribution of pores and channels etc. Because membrane degradation is crucial for practical operation of fuel cells and its understanding offers insights for developing new generation membranes, more and more attention is paid to this issue. Methanol is used in direct methanol fuel cells (DMFC) and alcohols are sensitive to the structure and dynamics of Nafion. In addition, aqueous solutions of alcohols are known to have special mesoscopic structures. Therefore, this thesis employs the aqueous solution of methanol as a probe and investigate the physicochemical mechanism of the degradation of Nafion 117 by means of solid state NMR spectra, relaxation, exchange, diffusion and micro-imaging. A series of methanol-water binary solution samples covering the entire range of concentration (0% ~ 99%(w/w)) were prepared and the 1H,17O NMR spectra,T1¡BT2, exchange rate, diffusion coefficient of these samples in bulk and in Nafion were measured. In bulk samples, the OH peak of water and that of methanol could be resolved with concentration at or above 40% (w/w). The microscopic and mesoscopic structure and dynamics of methanol solutions (in bulk) were subsequently investigated with variable temperature and diffusion experiments. By measuring the variable temperature 1H and 17O spectra, T1, T2, diffusion and micro-images of the methanol solutions in Nafion 117, the structure and dynamics of methanol solutions in bulk and in Nafion 117 were then compared. Based on these data, the structure an dynamics of Nafion 117 and the correlations between methanol and proton conduction and membrane degradation are discussed. The results of this work provides valuable reference for further understanding the structure, dynamics and degradation of Nafion and their relationship with proton conduction.

Techn. Hochsch., Diss., 2002--Aachen.

No description available.

Perfluorosulfonate ionomer (PFSI) membranes were annealed at elevated temperature for various periods of time in order to investigate the morphological effects of thermal treatments. For Nafion® 117, the DSC thermograms of Na+-, Cs+- and tetramethylammonium(TMA+)-form membranes show an endothermic peak develops upon annealing at 200ºC, indicating the development of crystallinity in the membrane. For these three samples annealed under same conditions, the heat of fusion (ΠH) values of the endothermic event increases with increasing counterion size. Larger tetraalkylammonium ions, tetraethylammonium(TEA+) and tetrapropylammonium(TPA+), result in no significant peak upon annealing at 200ºC. DSC thermograms of annealed Na+-form 3M Ionomer show no peak upon annealing and DSC thermograms of annealed TMA+-form 3M Ionomer show a very small peak that develops with annealing time at high equivalent weights. Annealed TMA+-form Dow Ionomer, which has a side chain shorter than both Nafion® and 3M Ionomer and a smaller mole% of side chains at the same equivalent weight, shows a relatively high ΠH value, which might also be related to its blocky nature. These results show that the isothermal crystallization kinetics of PFSI is affected by the counterion attached to the sulfonate group, the length of side chain, the mole% of side chains and the nature of the membrane. Water uptake analysis has been performed on annealed membranes, and the result shows that water uptake decreases with increasing degree of crystallinity. / Master of Science

No description available.

Traditionally, water has been used as the diluent for ionomeric polymer transducers. The water mobilizes the counterions within the polymer and allows electromechanical transduction to occur. However, these water-swollen devices have limited stability when operated in a non-aqueous environment. In this work, ionic liquids are demonstrated as viable diluents for ionomeric polymer transducers based on Nafion membranes. Ionic liquids are molten salts that are highly thermally stable and have an immeasureably low vapor pressure. Therefore, the ionic liquid-swollen transducers exhibit enhanced stability in their performance when operated for long periods of time in air. Methods for swelling Nafion membranes with ionic liquids are presented. Also, techniques for plating the ionic liquid-swollen transducers with metal electrodes are discussed. The performance of the ionic liquid-swollen transducers is compared to that of water-swollen transducers and differences are observed. Apart from the superior stability of the ionic liquid-swollen devices, they are observed to not exhibit the characteristic back-relaxation that is often associated with water-swollen transducers and limits their low frequency response. In order to investigate the physics of transduction in the ionic liquid-swollen membranes, structured experiments are performed using two different ionic liquids: 1-ethyl-3-methylimidazolium trofluoromethanesulfonate (EMI-Tf), which is water miscible, and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-Im), which is hydrophobic. The other experimental parameters are the counterion of the Nafion membrane and the swelling level of ionic liquid. Small-angle X-ray scattering (SAXS) is used to characterize the morphology of the ionic liquid-swollen Nafion membranes. The SAXS testing reveals that the clustered morphology of the Nafion membrane is preserved by the EMI-Tf ionic liquid, which is compatible with the hydrophilic cluster phase. By contrast, the hydrophobic EMI-Im ionic liquid is found to disrupt the clustered morphology and lead to partial homogenization of the polymer. This has the effect of inhibiting the ionic conductivity. The SAXS testing also reveals that the mean intercluster spacing increases as the content of ionic liquid and size of the counterions increases. Based on assumptions regarding the swelling mechanism, this is thought to arise from an increase in the mean size of the clusters. Spectroscopic investigations were also performed using Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). These studies show that the ionic liquid interacts with the Nafion polymer by displacing the counterions away from the sulfonate exchange sites. The cations of the ionic liquid then associate with the sulfonate sites and the counterions associate with the anions of the ionic liquid. Above a certain critical uptake of ionic liquid, this displacement is complete and additional ionic liquid does not associate with the ions of the polymer. The critical uptake is found to decrease with increasing size of the counterions. / Ph. D.