Philosophiae Doctor - PhD / Catalysts play an essential role in nearly every chemical production process. Platinum supported on high surface area carbon substrates (Pt/C) is one of the promising candidates as an electrocatalyst in low temperature polymer electrolyte fuel cells. Developing the activity of the Pt/C catalyst with narrow Pt particle size distribution and good dispersion has been a main concern in current research. In this study, the main objective was the development and characterization of inexpensive and effective nanophase Pt/C electrocatalysts. A set of modified Pt/C electrocatalysts with high electrochemical activity and low loading of noble metal was prepared by the impregnation-reduction method in this research. The four home-made catalysts synthesized by different treatments conditions were characterized by several techniques such as EDS, TEM, XRD, AAS, TGA, BET and CV.Pt electrocatalysts supported on acid treatment Vulcan XC-72 electrocatalysts were produced successfully. The results showed that Pt particle sizes of Pt/C (PrOH)x catalysts between 2.45 and 2.81nm were obtained with homogeneous dispersion, which were more uniform than the commercial Pt/C (JM) catalyst. In the electrochemical activity tests, ORR was confirmed as a structure-sensitive reaction. The Pt/C (PrOH/pH2.5) showed promising results during chemically-active surface area investigation, which compared well with that of the commercial standard Johnson Matthey Pt/C catalyst. The active surface area of Pt/C (PrOH/pH2.5) at 17.98m2/g, was higher than that of the commercial catalyst (17.22 m2/g ) under the conditions applied. In a CV electrochemical activity test of Pt/C catalysts using a Fe2+/Fe3+ mediator system study, Pt/C (PrOH/pH2.5) (67mA/cm2) also showed promise as a catalyst as the current density is comparable to that of the commercial Pt/C (JM) (62mA/cm2).A remarkable achievement was attained in this study: the electrocatalyst Pt supported on CNTs was synthesized effectively. This method resulted in the smallest Pt particle size 2.15nm. In the electrochemically-active surface area study, the Pt/CNT exhibited a significantly greater active surface area (27.03 m2/g) and higher current density (100 mA/cm2) in the Fe2+/Fe3+ electrochemical mediator system than the other home-made Pt/C catalysts, as well as being significantly higher than the commercial Pt/C (JM) catalysts. Pt/CNT catalyst produced the best electrochemical activities in both H2SO4 and K4[Fe(CN)6] electrolytes. As a result of the characteristics of Pt/CNT, it can be deduced that the Pt/CNT is the best electrocatalyst prepared in this study and has great potential for use in fuel cell applications. / South Africa

Magister Scientiae - MSc / For a direct methanol fuel cell (DMFC), the proton exchange membrane must conduct protons and be a good methanol barrier. In addition to the high methanol permeability achieved by these membranes, they are very expensive and contribute greatly to theoverall cost of fuel cell set up. The high cost of the DMFC components is one of the main issues preventing its commercialization. The main objective of this study was thus to produce highly proton conductive membranes that are cheap to manufacture and have low methanol permeability. / South Africa

Concurrent engineering and virtual prototyping are two emerging techniques that are bringing considerable economical benefits to the manufacturing industry. This work proposes the use of virtual prototyping to produce quantitative measures of product lifecycle performances to facilitate the implementation of concurrent engineering. A multiobjective, virtual prototyping-based global optimization problem is formulated to close the open loop of present virtual prototyping methods and to allow concurrent engineering design to be carried out systematically and automatically. Virtual prototyping-based design optimization faces several technical challenges. First, virtual prototyping is usually computationally intensive; relations between design variables and product life-cycle performances are often implicit. Secondly, the optimization problem usually consists of multi-modal design (objective and constraint) functions. The complexity and multi-modal nature of the optimization problem preclude the direct use of conventional local and global optimization methods. In this work, a new and efficient search method for virtual prototyping-based global design optimization is introduced. The method, called Adaptive Response Surface Method (ARSM), carries out systematic “design experiments” through virtual prototyping to build second-order regression models to approximate the design functions. Through an iterative process, the regression models are improved and the global design optimum is obtained. The ARSM search scheme requires only a modest number of design function evaluations, making virtual prototyping-based global design optimization feasible. The proposed quantitative concurrent design method is then applied to the components, stack and system design of a transportation fuel cell. The approach led to an optimized multi-functional component, a reduction of the system cost, and an improvement of the system performance. The approach can be applied to the concurrent design and design optimization of other complex mechanical components, assemblies and systems. / Graduate

No description available.

Submitted in the fulfillment of the requirements for the Master of Engineering, Durban University of Technology, Durban, South Africa. 2016. / The effectiveness of using a low cost non - platinum (Pt) material for the catalyst layer of a polymer electrolyte fuel cell (PEMFC) was investigated. A test cell and station was developed. Two commercial Pt loaded membrane electrode assemblies (MEA) and one custom MEA were purchased from the Fuelcelletc store. Hydrogen and oxygen were applied to either side of the custom MEA which resulted in an additional sample tested. An aluminium flow field plate with a hole type design was manufactured for the reactants to reach the reaction sites. End plates made from perspex where used to enclose the MEA, flow field plates, and also to provide reactant inlet and outlet connection points. The developed test station consisted of hydrogen and oxygen sources, pressure regulators, mass flow controllers, heating plate, and humidification units. A number of experimental tests were carried out to determine the performance of the test cells. These tests monitored the performance of the test cell under no-load and loaded conditions. The tests were done at 25 °C and 35 °C at a pressure of 0.5 bar and varying hydrogen and oxygen volume flow rates. The no-load test showed that the MEA’s performed best at high reactant flow rates of 95 ml/min for hydrogen and 38 ml/min for oxygen. MEA 1, 2, 3, and 4 achieved an open circuit voltage (OVC) of 0.936, 0.855, 0.486 and 0.34 V respectively. The maximum current density achieved for the MEAs were 0.3816, 0.284, 15x10-6, and 50x10-6 A/cm2. Under loaded conditions the maximum power densities achieved at 25 °C for MEA’s 1, 2, 3, and 4 were 0.05, 0.038, 2.3x10-6, 1.99x10-6 W/cm2 respectively. Increasing the temperature by 10°C for MEA 1, 2, 3, 4 resulted in a 16.6, 22.1, 1.79, 10.47 % increase in the maximum power density. It was found that increasing platinum loading, flow rates, and temperature improved the fuel cell performance. It was also found that the catalytic, stability and adsorption characteristics of silver did not improve when combining it with iridium (Ir) and ruthenium oxide (RuOx) which resulted in low current generation. The low maximum power density thus achieved at a reduced cost is not feasible. Thus further investigation into improving the catalytic requirements of non Pt based catalyst material combinations is required to achieve results comparable to that of a Pt based PEMFC. / M

Lowering the operating temperature of the high-temperature, solid oxide fuel cell (SOFC) improves both the thermodynamic efficiency and the lifetime of this energy efficient technology. Unfortunately the rate of oxygen-ion transport through the solid electrolyte is temperature dependent, and materials previously employed as electrolytes in the high-temperature SOFC perform poorly at intermediate temperatures. Therefore new oxygen-ion conductors with enhanced ionic conductivity at intermediate temperatures are required. The bulk of the existing literature on high-temperature SOFCs has focussed on zirconia-based binary systems as electrolytes, due to their high ionic conductivity and negligible electronic conductivity. Only select compositions within the zirconia-scandia system have demonstrated acceptable ionic conductivity levels at intermediate temperatures; however unstable phase assemblage and the high economic cost of scandia are clear disadvantages. Ceria-based binary systems have demonstrated improved oxygen-ion conductivity at intermediate temperature compared to many zirconia systems, however significant levels of n-type electronic conductivity are observed at low oxygen partial pressures. Consequently it was thought unlikely that significant increases in ionic conductivity would be found in existing zirconia- and ceria-based binary systems, therefore another approach was required in an attempt to improve the performance of these established fluorite systems. The fluorite systems Zr0.75Ce0.08M0.17O1.92 (M = Nd, Sm, Gd, Dy, Ho, Y, Er, Yb, Sc) were prepared and investigated as possible, intermediate-temperature SOFC electrolytes in an attempt to combine the higher conductivity found in the ceria systems with the low electronic conductivity observed in the zirconia systems. Also it was anticipated that systems containing dopants not previously observed to confer high ionic conductivity in either zirconia- and ceria-based binary systems, might exhibit enhanced ionic conductivity with expansion of the zirconia lattice resulting from the addition of ceria. All the as-fired Zr0.75Ce0.08M0.17O1.92 compositions possessed the face-centred cubic structure and lattice parameter measurements revealed the anticipated unit cell enlargement as the size of the dopant cation increased. No unusual microstructural parameters were identified that could be expected to interfere with the ionic transport properties in the as-fired compositions. The electrical conductivity was found to be influenced by the dopant-ion radius, the presence of ceria, low oxygen partial pressures and, in some compositions, the formation of poorly conducting, ordered-pyrochlore microdomains dispersed amongst the cubic defect-fluorite matrix. In a second approach to the formulation of new oxygen-ion conductors suitable for the intermediate-temperature SOFC, compounds possessing structures other than the fluorite structure were considered. An examination of the literature for oxides having the pyrochlore, scheelite and perovskite structures showed that the Sr+2- and Mg+2-doped LaGaO3 perovskites (LSGM) possessed ionic conductivity equal to the highest conducting, zirconia and ceria binary compounds. Therefore the perovskite systems La0.9Sr0.1Ga(0.8-x)InxMg0.2O2.85 (X = 0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8) (I-LSGM) were prepared and examined, the objective being to favourably influence structural parameters believed responsible for optimal ionic conductivity, namely the unit cell symmetry and volume. It was found that In+3 systematically substituted for Ga+3 on to the B-site of LSGM at least up to the X = 0.4 composition. While In+3 was found to replace the Ga+3 as expected, Mg+2, which occupies the same crystallographic site, was also replaced by In+3. Up to the X = 0.2 composition, at least two trace level secondary phases were observed to form along with the bulk I-LSGM phase. For I-LSGM compositions with X > 0.2, significantly larger concentrations of the secondary phases were identified. Evidence of a strontium-rich, high-temperature liquid phase was observed also near the grain boundaries on as-sintered and thermally etched surfaces in LSGM and I-LSGM compositions. It is believed that the observed, high sintered density in the complex, doped-LaGaO3 systems is due to the formation of this high-temperature liquid phase. Increasing levels of diffuse scatter and superstructure formation were observed in electron diffraction patterns in the I-LSGM bulk phase (up to X = 0.2), indicating a possible decrease in vacancy concentration and reduced, localised unit cell symmetry. The electrical conductivity in the I-LSGM compositions was believed to be influenced by the distortion of the oxygen-ion conduction path, a reduction in vacancy concentration, formation of stronger dopant-vacancy associates at low temperature and the presence of ordered structures. In addition, phase instability, in the form of subtle ordering in specific crystalline planes, was observed to influence the electrical conductivity as a function of time at intermediate temperatures.

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 75-77

The mathematical analysis has been developed by using finite volume method, experimental data from literatures, and solving numerically to predict solid oxide fuel cell performances with different operating conditions and different material properties. The in-house program presents flow fields, temperature distributions, and performance predictions of typical solid oxide fuel cells operating at different temperatures, 1000 C, 800 C, 600 C, and 500 C, and different electrolyte materials, Yttria-Stabilized zirconia (YSZ) and Gadolinia-doped ceria (CGO). From performance predictions show that the performance of an anode-supported planar SOFC is better than that of an electrolyte-supported planar SOFC for the same material used, same electrode electrochemical considerations, and same operating conditions. The anode-supported solid oxide fuel cells can be used to give the high power density in the higher current density range than the electrolyte-supported solid oxide fuel cells. Even though the electrolyte-supported solid oxide fuel cells give the lower power density and can operate in the lower current density range but they can be used as a small power generator which is portable and provide low power. Furthermore, it is shown that the effect of the electrolyte materials plays important roles to the performance predictions. This should be noted that performance comparisons are obtained by using the same electrode materials. The YSZ-electrolyte solid oxide fuel cells in this work show higher performance than the CGO-electrolyte solid oxide fuel cells when SOFCs operate above 756 C. On the other hand, when CGO based SOFCs operate under 756 C, they shows higher performance than YSZ based SOFCs because the conductivity values of CGO are higher than that of YSZ temperatures lower than 756 C. Since the CGO conductivity in this work is high and the effects of different electrode materials, they can be implied that conductivity values of electrolyte and electrode materials have to be improved.

Thesis (Ph.D)--Chemical Engineering, Georgia Institute of Technology, 2010. / Committee Chair: Fuller, Thomas; Committee Member: Beckham, Haskell; Committee Member: Hess, Dennis; Committee Member: Koros, William; Committee Member: Meredith, Carson. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (M.S.)--West Virginia University, 2003. / Title from document title page. Document formatted into pages; contains xii, 100 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references (p. 85-90).