RODRIGO PIRES DA SILVA
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Artigo IPEN-doc 29609 Numerical validation of direct ethanol fuel cell operating at high temperature2023 - PANESI, A.R.Q.; SILVA, R.P.; SANTIAGO, E.I.In the present work, a three-dimensional steady-state model was developed to analyze the performance of high-temperature direct ethanol fuel cell (HT-DEFC) based on polybenzimidazole (PBI) electrolytes. A non-isothermal model of a HT-DEFC setup using a PBI/H3PO4 membrane was employed using computational fluid dynamics (CFD). This work is aiming at a validation of experimental data of HT-DEFC prototypes based on the simulation of polarization curves. The model predicts the mole concentration of H3PO4, heat and current density distributions, as well as mass fraction ethanol during operation at 180 °C. The heat transfer model was coupled to the electrochemical and mass transport, allowing that a particular heating configuration was investigated considering the temperature distribution on the PBI membrane. We have found that temperature and relative humidity (RH) are mostly related to PBI properties resulting from H3PO4 lixiviation and conductivity decreasing as well as ethanol crossover strongly interferes on the oxygen reduction reaction (ORR) rate, leading to poor HT-DEFC performance.Artigo IPEN-doc 28365 Three-dimensional CFD modeling of H2/O2 HT-PEMFC based on H3PO4-doped PBI membranes2021 - PANESI, A.R.Q.; SILVA, R.P.; CUNHA, E.F.; KORKISCHKO, I.; SANTIAGO, E.I.A complete non-isothermal model of a HT-PEMFC setup using a PBI/ H3PO4 membrane was developed, modeled, and solved using COMSOL Multiphysics. Polarization curves were simulated and compared to the corresponding experimental data. In this work, a serpentine flow field and an active area of 5 cm2 have been implemented in a computational fluid dynamics (CFD) application. The model predicts water vapor transport, mass concentration of H3PO4, temperature, and membrane current density distribution. In this model, the anode feed is pure hydrogen, and oxygen is introduced at the cathode side. The heat transfer model was coupled with the electrochemical and mass transport; a particular heating configuration is investigated for temperature distribution, emphasizing the membrane. The models showed consistency and were used to investigate the behavior of H3PO4 concentration and all transport characteristics. The concentration of phosphoric acid decreases with increasing temperature and relative humidity and the diffusive flux of water vapor increases with the decrease of the operating voltage. Two different configurations of inlet and outlet flow channels were analyzed and the results were compared.Dissertação IPEN-doc 28019 Desenvolvimento de membranas não fluoradas a base de PBI para aplicação em células a combustível de etanol direto de alta temperatura2021 - SILVA, RODRIGO P. daA maioria das células a combustível de membrana de troca protônica (PEMFC) utiliza o Nafion® como eletrólito. Como possui um mecanismo de condução de prótons dependente de moléculas de água, estas células têm uma temperatura de operação limitada até 80°C. O aumento da temperatura de operação de uma célula PEMFC é desejado devido à contribuição da temperatura na aceleração das reações eletroquímicas, que são processos termoativados. Neste contexto, as membranas PBI (polibenzimidazol) dopadas com ácido fosfórico têm sido consideradas um polímero base bastante promissor para eletrólitos sólidos operantes em alta temperatura, devido à combinação de condução de prótons satisfatória em condições de baixa umidade relativa e excelente estabilidade térmica. No entanto, membranas baseadas em PBI apresentam algumas desvantagens, tais como lixiviação do ácido (veículo condutor), diminuição de sua resistência mecânica, permeabilidade aos combustíveis utilizados em PEMFC operante em alta temperatura (HT-PEMFC), permitindo que uma parte migre do ânodo para o cátodo da célula (crossover) e diminuindo assim a eficiência e o desempenho global do dispositivo. Neste contexto, o objetivo do trabalho foi o desenvolvimento e otimização de membranas compósitas a base de PBI e óxido de silício (SiO2), que além de atuar como reforço mecânico, pode contribuir na mitigação do crossover e, dessa forma, se apresentar como uma alternativa ao Nafion como eletrólito sólido em células a combustível de etanol direto de alta temperatura (HT-DEFC). Nesse sentido, membranas puras de PBI e compósitos PBI-SiO2 com diferentes frações de SiO2 (2,5%, 5%, e 10%) foram sintetizadas e caracterizadas por Raman, termogravimetria, microscopia eletrônica de varredura e espectroscopia de impedância eletroquímica. Por fim, as membranas foram avaliadas em protótipos de HT-DEFC a 180°C após parametrização e otimização dos componentes dos conjuntos eletrodos-membranas (MEA). Ainda, eletrocatalisadores anódicos baseados em Pt/C, PtSn/C e PtRu/C foram estudados com o objetivo de avaliar o efeito da natureza do catalisador no desempenho de HT-DEFCs.Artigo IPEN-doc 27193 SAXS signature of the lamellar ordering of ionic domains of perfluorinated sulfonic-acid ionomers by electric and magnetic field-assisted casting2020 - SILVA, JAQUELINE S. da; CARVALHO, SABRINA G.M.; SILVA, RODRIGO P. da; TAVARES, ANA C.; SCHADE, ULRICH; PUSKAR, LJILJANA; FONSECA, FABIO C.; MATOS, BRUNO R.At present, small angle X-ray scattering (SAXS) studies of perfluorinated sulfonic-acid ionomers (PFSAs) are unable to fully determine the true shape of their building blocks, as recent SAXS modelling predicts disk- and rod-like nanoionic domains as being equally possible. This scenario requires evidence-based findings to unravel the real shape of PFSA building blocks. Herein, a SAXS pattern signature for a lamellar nanophase separation of the ionic domains of Nafion is presented, backed by mid and far infrared spectroscopy (MIR and FIR) and wide angle X-ray scattering (WAXS) data of Nafion in different ionic forms, a broad range of ionic phase contents (EW ~ 859–42 252 g eq-1) and temperatures. The study indicates that the lamellar arrangement of the ionic domains is the most representative morphology that accounts for the physical properties of this ionomer. The lamellar SAXS reflections of Nafion are enhanced in electric and magnetic field-aligned membranes, as confirmed by atomic force microscopy (AFM). Electric and magnetic field-assisted casting of Nafion allowed producing nanostructured and anisotropic films with the lamellas stacked perpendicularly to the field vector, which is the direction of interest for several applications. Such nanostructured Nafion membranes are bestowed with advanced optical and proton transport properties, making them promising materials for solar and fuel cells.Resumo IPEN-doc 26798 Development of non-fluorinated membranes based on PBI for application in high temperature fuel cells (HT-PEM)2019 - SILVA, R.P.; SOUZA, R.F.B. de; SANTOS, C.M.G.; SILVA, A.J.; SANTIAGO, E.I.Most of Proton Exchange Membrane Fuel Cells (PEMFCs) use the Nafion as electrolyte, which has a limitation in the operating temperature. Usually, these cells operate up to 80°C since the proton conduction is dependent on water molecules carriers. The increase in the operating temperature of a PEMFC cell is desired due to the contribution of the temperature in the acceleration of the electrochemical reactions, which are thermoactivated processes. In the context of searching alternative polymeric electrolytes, PBI (polybenzimidazole) membranes have been considered a promising membrane for high temperature operating PEMFC (HT-PEMFC) due to the combination of satisfactory proton conduction in conditions of low relative humidity (RH) and excellent thermal stability. Pure PBI membranes were prepared by casting a solution of PBI / N, N'-dimethylacetamide (DMAc) and doped with phosphoric acid at different times (1, 3, 5, 7 10 and 15 days). Each membrane was evaluated in Fuel Cell tests, doping level and online Raman tests in order to determine effects of doping level, chemical degradation and fuel cell performance. The electrodes were optimized by studying different catalytic layer composition and the cell tested at different operational conditions.