Polymer electrolyte membrane fuel cells (PEMFCs) have been looked as potential alternative energy conversion devices to conventional energy conversion systems such as combustion engines. Proton conducting membranes (PEMs) are one critical component of PEMFCs. The development of novel electrolyte membranes with dense structure, good mechanical flexibility, and high proton conductivity, but with little or no dependence on humidity at temperatures above 100¡ãC remains an important challenge to the realization of practical PEM fuel cells. In this thesis, to solve the technical difficulties existing in current high temperature PEM systems based on phosphoric acid and imidazole, a new type of proton conducting species 1H-1,2,3-triazole has been explored, and proved to have high proton conductivity and also enough electrochemical stability for fuel cell applications. In further experiments, effective methods have been developed to synthesize triazole derivatives and polymers. The properties of the synthesized polymers have studied and reported in this thesis. Preliminary computational simulations have also been performed to study the proton conducting mechanism to provide intrinsic information of the proton conducting process in 1H-1,2,3-triazole. In the final part, research works on other proton conducting species including H3PO4 and other heterocycles have been reported.

An important challenge for PEMFC is stability and durability of the membrane separator. In this dissertation, we applied both experimental and modeling methods to investigate the chemical durability of PFSA membranes for fuel-cell applications. Degradation data were collected after Fenton's tests and the membrane samples were analyzed by XPS after Fenton's test; FTIR was also invoked to validate the XPS results. The effects of Fe2+ concentration and temperature on membrane degradation were discussed. The experimental results provide evidence of chemical attack of the CF2 backbone. Since the level of H2O2 was found to be key to membrane degradation, we designed a novel spectrophotometric method to quantitatively determine H2O2 concentration in a fuel cell by using a multilayer MEA. In addition, a model for H2O2 formation, transport, and reaction in PEMFCs is established for the first time to validate experimental data and study formation mechanism. The humidity effect on membrane degradation was studied by collecting vent water during the tests. The membrane conductivities and mechanical properties were measured by ex-situ high-throughput instruments. FTIR was applied to study both the formation of new groups and the relative abundance of existing groups in the degraded membrane. The thermal stability of degraded membranes was determined by TGA. The cross section of a degraded MEA sample was imaged with SEM to investigate the mechanical structure change. The effect of temperature on membrane degradation was also investigated. XPS spectra were collected from both anode and cathode sides of fuel-cell membrane to compare the effect of temperature on each side. Atomic analysis was performed to study the impact of temperature on both backbone decomposition and side group degradation. A multilayer MEA was used to study the effects of location and thickness on membrane degradation. An improved kinetic model of membrane degradation was built to simulate the experimental data. Finally, an attempt to mitigate membrane degradation by using peroxide decomposition reagent was performed. OCV curves were recorded during two fuel-cell durability tests with and without the addition of this additive. Both FER and TER were compared. Recommendations for the improvement of peroxide decomposition additive were suggested.

Durability of carbon-supported platinum nanoparticle is one of the limiting factors for PEM fuel cell commercial applications. In our research work, we applied both experimental and mathematical simulative tools to study the mechanisms of Pt/C catalyst degradation. An accelerated catalyst degradation protocol by cycling the cathode potential in a square-wave profile was applied to study the losses of cell performances, catalyst ORR activity, and Pt active surface areas. Post-mortem analyses of cathode Pt particle size by X-ray diffraction and platinum distributions in CCMs by SEM/EDS were also conducted. Increased cell temperature and relative humidity was found to accelerate the cathode catalyst degradation. High membrane water contents or abundant water/ionic channels within the polymer electrolyte were believed to accelerate Pt ion transport and cathode degradation. After degradation tests, significant amount of Pt loss into the membrane forming a Pt "band" was observed through cathode platinum dissolution and chemical reduction of soluble Pt ions by permeated hydrogen from the anode. Platinum deposition was confirmed at a location where the permeated hydrogen and oxygen had the complete catalytic combustion over the deposited Pt clusters/particles as the catalyst. A cathode degradation model was built including the processes of platinum oxidation, dissolution/replating, diffusion of Pt ions and Pt band formation in electrolyte. A simplified bi-modal particle size distribution was applied with equal numbers of small and large type particles uniformly distributed in the cathode initially. Processes of Pt mass exchange between two types of particles were demonstrated to cause the overall particle growth. This was due to the particle size effect that platinum dissolution from the small type particles and replating of Pt ions onto the large particles was favored. Parametric study found the increased upper cycling potential was the dominated factor to accelerate the catalyst degradation. Also high frequency of potential cycle and low surface oxide coverage accelerated the degradation rate. Pt dissolution and oxidation processes in perchloric acid were preliminary investigated, and both chemical and electrochemical processes of oxidation and dissolution were believed to be involved under closed-circuit fuel cell conditions with oxygen presence at cathode.

Thesis (Ph. D.)--Ohio State University, 2008.

Made available in DSpace on 2014-10-09T12:28:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:29Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:53:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:58:46Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

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Made available in DSpace on 2014-10-09T12:42:16Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:20Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:28:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:29Z (GMT). No. of bitstreams: 0 / Este trabalho teve como objetivo sintetizar eletrólitos híbridos de Nafion-TiO2 e eletrocatalisadores de PtSn/C para a aplicação em células a combustível de oxidação direta de etanol (DEFC) em alta temperatura (130oC). Para tanto, partículas de TiO2 foram incorporadas in-situ em membranas comerciais de Nafion via processo sol-gel. Os materiais resultantes foram caracterizados por análise gravimétrica, absorção de água, DSC, DRX e EDX. Eletrocatalisadores baseados em platina-estanho dispersos em carbono (PtSn/C), de diferentes composições, foram produzidos pelo método de redução por álcool e utilizados como eletrodos anódicos. Os eletrocatalisadores foram caracterizados por DRX, EDX, XPS e MET. A avaliação eletroquímica dos eletrocatalisadores foi realizada por voltametria cíclica, varredura linear anódica de monóxido de carbono (stripping de CO) e cronoamperometria. Ânodos de PtSn/C e cátodos de Pt/C comercial foram dispostos juntamente com os híbridos Nafion-TiO2 para a formação do conjuntos membrana-eletrodos. A avaliação final dos materiais foi realizada por meios de curvas de polarização em células unitárias alimentadas com misturas padrão H2/CO ou etanol no ânodo e com oxigênio no cátodo no intervalo de temperatura de 80 a 130oC. As análises demonstraram que o uso de membranas híbridas diminuiu o crossover de combustível, melhorando o desempenho da célula e que o eletrocatalisador PtSn/C 70:30, produzido pelo método de redução por álcool, foi o que demonstrou melhor desempenho para oxidação de etanol. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP