BRUNO RIBEIRO DE MATOS

BRUNO RIBEIRO DE MATOS

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Identification of the polymer and electrode polarizations of Nafion dielectric spectrum
2019 - MATOS, B.R.; SILVA, J.S. da; SCHADE, U.; PUSKAR, L.; FONSECA, F.C.
Nafion dielectric polarization effects on the fuel cell I-V curve
2019 - MATOS, B.R.; FONSECA, F.C.
Advancing direct ethanol fuel cell operation at intermediate temperature by combining Nafion-hybrid electrolyte and well-alloyed PtSn/C electrocatalyst
2021 - DRESCH, MAURO A.; MATOS, BRUNO R.; GODOI, DENIS R.M.; LINARDI, MARCELO; FONSECA, FABIO C.; VILLULLAS, HEBE de las M.; SANTIAGO, ELISABETE I.
The advancement of direct ethanol fuel cell (DEFC) represents a real challenge to electrochemical science because ethanol changes significantly the triple phase boundary properties such as the redox reactions and the proton transport. Ethanol molecules promote poor fuel cell performance due to their slow oxidation rate, reduction of the proton transport due to high affinity of ethanol by the membrane, and due to mixed potential when the ethanol molecules reach the cathode by crossover. DEFC performance has been improved by advances in the membranes, e.g., low ethanol crossover polymer composites, or electrode materials, e.g., binary/ternary catalysts. Herein, high temperature (130 °C) DEFC tests were systematically investigated by using optimized electrode and electrolyte materials: Nafion-SiO2 hybrid electrolyte and well-alloyed PtSn/C electrocatalyst. By optimizing both the electrode and the electrolyte in conjunction, DEFCs operating at 130 °C exhibited a threefold increase on performance as compared to standard commercially available materials.
Hybrids nanocomposites based on a polymer blend (linear low-density polyethylene/poly(ethylene-co-methyl acrylate) and carbonaceous fillers (graphene and carbon nanotube)
2021 - NUNES, MARIO A.B.S.; MATOS, BRUNO R. de; SILVA, GLAURA G.; ITO, EDSON N.; MELO, TOMAS J.A. de; FECHINE, GUILHERMINO J.M.
Interfacial or separate phase location of carbonaceous nanofillers (graphene and carbon nanotubes) in polymer blends with co-continuous phases can lead to double percolation behavior, significantly increasing rheological and electrical properties. The prediction of the morphology and the location of the nanofillers has been used as a tool to evaluate the proprieties of co-continuous polymer blends. This work aims to highlight the superior conductivity levels achieved using a low amount of carbon-based fillers, by the proper selection in a multiphase polymer matrix as a template for controlled dispersion and spatial distribution of the nanoparticles, offering a compromise between easy processability and enhanced performance. Here, two polymers (linear low-density polyethylene [LLDPE] and ethylene-co-methylacrylate [EMA]) and their cocontinuous blend (LLDPE/EMA) were loaded with nanofillers (few-layer graphene [FLG], few-walled carbon nanotube [FWCNT]) via continuous melt mixing in twin-screw extrusion, separate and simultaneously. It was observed that the addition of the nanofillers changed the co-continuity of the blend, with the probable migration of the nanofillers from the EMA (hydrophilic) phase to the LLDPE (hydrophobic) phase. Rheological percolation occurred preferentially in blends containing FWCNT and FLG/FWCNT. Electrical conductivity was observed in all compositions, with higher electrical conductivity being noticed in hybrids.
SAXS signature of the lamellar ordering of ionic domains of perfluorinated sulfonic-acid ionomers by electric and magnetic field-assisted casting
2020 - 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.
Properties and DEFC tests of Nafion
2020 - MATOS, B.R.; GOULART, C.A.; TOSCO, B.; SILVA, J.S. da; ISIDORO, R.A.; SANTIAGO, E.I.; LINARDI, M.; SCHADE, U.; PUSKAR, L.; FONSECA, F.C.; TAVARES, A.C.
Nafion based composites are promising materials to improve the performance of direct ethanol fuel cells. In this work, composite membranes of Nafion and titanate nanotubes functionalized with sulfonic acid groups were prepared by melt-extrusion and tested in a direct ethanol fuel cell. Far and mid infrared spectroscopies evidenced the formation of ionic bridges between the sulfonic acid groups of both functionalized nanoparticles and the ionomer. Small angle X-ray scattering measurements revealed that the melt-extrusion method leads to an uniform distribution of the inorganic phase in the ionomer matrix. Such structural analysis indicated that the improved the proton conduction properties of the composites, even with the addition of a high concentration of functionalized nanoparticles, are an outcome of the synergistic ionic network due to the hydrid organic/inorganic proton conducting phases. However, an improvement of the fuel cell performance is observed for 2.5 wt% of functionalized titanate nanotubes, which is a result of the lower ethanol crossover and the plasticizing effect of the aliphatic segments of the organic moieties grafted at the surface of the titanate nanoparticles.
The genuine ac-to-dc proton conductivity crossover of nafion and polymer dielectric relaxations as a fuel cell polarization loss
2020 - MATOS, B.R.
The non-ohmic behavior of Nafion electrical properties, i. e., the thickness and potential dependent conductivity, was studied in the impedance, dielectric and conductivity representations with the use of a special through-plane sampleholder in a 4-probe array. Such measurements allowed identifying the genuine ac-to-dc conductivity crossover frequency in Nafion, which occurs for f<10-1 Hz. In addition, the minimization of the interfacial electrode/ionomer polarizations with the 4-probe setup permitted the determination of the bulk dc conductivity and dielectric constant of Nafion, which are σ~0.03 Scm-1 and ε′~106 (T=40 °Cand RH=100%), respectively. The colossal dielectric constant is shown to increase the Debye length of the electric double layer to values comparable to the membrane thickness. Therefore, the exponential increase of the proton conductivity with increasing both membrane thickness and electric potential are a result of canceling out the non-linear effects of electric double layer caused by the high dielectric permittivity of Nafion. The ac-to-dc conductivity crossover in H2/O2 fuel cell impedance curves takes place for f<100 Hz and matches with the ex situ impedance spectroscopy study in excellent agreement, revealing a striking result: the potential dependent conductivity of Nafion requires extra fuel cell overpotential to overcome the electrode/ionomer interfacial polarization representing an additional polarization loss to polymer electrolyte fuel cells.
Synthesis and proton conductivity of Nafion with addition of CsHSO4
2016 - MATOS, BRUNO R.; MORAES, LETICIA P.R.; SANTIAGO, ELISABETE I.; FONSECA, FABIO C.
Advances on Nafion-based composites for high temperature proton exchange membrane fuel cells
2017 - SANTIAGO, ELISABETE I.; MATOS, BRUNO R.; DRESCH, MAURO A.; ISIDORO, ROBERTA A.; FONSECA, FABIO C.
PEMFC (Proton exchange membrane fuel cell) is considered a promising and efficient hydrogen fuelled electrical power source. However, PEMFC faces several technical problems, such as sluggish electrode reaction kinetics involving the limiting rate of the oxygen reduction and alcohol oxidation reactions, and high resistance to ion transport that could be surpassed with increasing of the operation temperature. The main impediment for such a temperature increase is the water dependent performance of the state-of-the-art Nafion electrolyte. Above 80 ºC water starts to evaporate considerably and Nafion microdomains begin to shrink, disrupting its percolative structure, leading from a conductor to insulator transition. In this work, the incorporation in-situ or ex-situ of an inorganic phase with hydrophilic properties, such as TiO2 and SiO2, into Nafion membranes has been evaluated as an interesting alternative to produce stable electrolytes able to operate at higher temperatures (130o C). The physical-chemistry and electrochemical characterisation has shown that the inorganic particles located in both the nonionic and ionic regions of the ionomer have important contributions to enhanced thermal stability and water uptake. Such features resulted in significant improvements of the PEMFCs using composite electrolytes tested at high operating temperature and low relative humidity. In addition, remarkable enhancement on the DEFC (Direct Ethanol Fuel Cell) performance (122 mW cm‑2) has been obtained as a result of an increase of ethanol oxidation reaction rate promoted by the combination of enhanced catalyst activity and high temperature of operation using stable composite Nafion-SiO2 electrolytes.
Efeito da relaxação do polímero na cristalinidade, fase iônica e formação de grupos sulfônicos anidridos no Nafion
2017 - MATOS, B.R.; SANTIAGO, E.I.; TOSCO, B.; REY, J.F.Q.; SILVA, J.S. da; SCHADE, U.; PUSKAR, L.; AZIZ, E.F.; FONSECA, F.C.
A relação entre as propriedades estruturais e elétricas de amostras de Nafion preparadas sob tratamento térmico em diferentes temperaturas (220 > T > 100 °C) foi investigada por espectroscopia no infravermelho (FTIR), espalhamento de raios-X em baixo ângulo (SAXS), calorimetria diferencial exploratória (DSC), análise dinâmico-mecânica (DMA) e espectroscopia de impedância (IS). Os resultados combinados de FTIR, SAXS, DSC, DMA revelaram que o tratamento térmico em baixas umidades relativas altera a morfologia do Nafion irreversivelmente devido a três características principais: i) o rearranjo das ligações de hidrogênio; ii) o reordenamento da fase cristalina; e iii) a formação de grupos sulfônicos anidridos. No entanto, a formação dos grupos anidridos é revertida pela reacidificação da membrana em soluções ácidas. O aspecto mais importante da dinâmica dos três processos descritos é que tais alterações são aceleradas acima de uma temperatura crítica: a temperatura de término da transição α do Nafion (Tendα ~ 160 °C). A transição α é atribuída ao enfraquecimento das interações eletrostáticas existentes entre os grupos sulfônicos do Nafion, que permitem a movimentação de longo alcance das cadeias poliméricas [1]. Este resultado indica que a maior dinâmica das cadeias do polímero em T > Tendα é o principal fator envolvido na modificação irreversível da morfologia do Nafion. As alterações da estrutura das ligações de hidrogênio afetaram negativamente as propriedades elétricas do Nafion. O aumento da temperatura de tratamento térmico reduz a condutividade protônica e aumenta a energia de ativação do transporte de cargas no Nafion. Tais resultados são relevantes para a preparação de conjuntos eletrodos-membrana (MEA) e para a operação de células a combustível de eletrólito polimérico (PEFC) em altas temperaturas [1].