<p>The direct methanol fuel cell (DMFC) is a very promisingpower source for low power applications. High power and energydensity, low emissions, operation at or near ambientconditions, fast and convenient refuelling and a potentiallyrenewable fuel source are some of the features that makes thefuel cell very promising. However, there are a few problemsthat have to be overcome if we are to see DMFCs in our everydaylife. One of the drawbacks is the low performance of the DMFCanode. In order to make a better anode, knowledge about whatlimits the performance is of vital importance. With theknowledge about the limitations of the anode, the flow field,gas diffusion layer and the morphology of the electrode can bemodified for optimum performance.</p><p>The aim of this thesis is to elucidate the limiting factorsof the DMFC anode. A secondary goal is to create a model of theperformance, which also has a low computational cost so that itcan be used as a sub model in more complex system models. Toreach the primary goal, to elucidate the limiting factors, amodel has to be set up that describes the most importantphysical principles occurring in the anode.</p><p>In addition, experiments have to be performed to validatethe model. To reach the secondary goal, the model has to bereduced to a minimum. A visual DMFC has been developed alongwith a methodology to extract two-phase data. This has provento be a very important part of the understanding of thelimiting factors. Models have been developed from a detailedmodel of the active layer to a two-phase model including theentire three-dimensional anode.</p><p>The results in the thesis show that the microstructure inthe active layer does not limit the performance. Thelimitations are rather caused by the slow oxidation kineticsand, at concentrations lower than 2 M of methanol, the masstransport resistance to and inside the active layer. Theresults also show that the mass transfer of methanol to theactive layer is improved if gas phase is present, especiallyfor higher temperatures since the gas phase then contains moremethanol.</p><p>It is concluded that the mass transport resistance lower theperformance of a porous DMFC anode at the methanolconcentrations used today. It is also concluded that masstransfer may be improved by making sure that there is gas phasepresent, which can be done by choosing flow distributor and gasdiffusion layer well.</p><p>Keywords: direct methanol fuel cell, fuel cell, DMFC, anode,model</p>

Direct Methanol Fuel Cells (DMFC) provide an exciting alternative to current energy storage technologies for powering small portable electronic devices. For applications with sufficiently long durations of continuous operation, DMFC’s offer higher energy density, the ability to be refueled instead of recharged, and easier fuel handling and storage than devices that operate with hydrogen. At present, materials and manufacturing challenges impede performance and have prevented the entry of these devices to the marketplace. Higher-performing, cost-effective materials and efficient manufacturing processes are needed to enable the commercialization of DMFC. In a DMFC, the methanol-rich fuel stream and the oxidant are isolated from one another by a proton-conducting and electrically insulating membrane. Catalysts in the electrodes on either side of the Membrane Electrode Assembly (MEA) promote the two simultaneous half-reactions which allow the chemical energy carried in the fuel and oxidant to be converted directly into electricity. The goal of this research effort is to develop a continuous manufacturing process for the fabrication of effective DMFC MEAs. Based on the geometry of the electrode and materials used in the MEA, we propose a roll-to-roll process in which electrodes are coated onto a suitable substrate and subsequently assembled to form a MEA. Appropriate coating methods for electrode fabrication were identified by evaluating the requirements of continuous manufacturing processes; an appropriate set of these processes was then reduced to practice on a custom-designed flexible test bed designed explicitly for this project. After establishing baseline capabilities for several candidate methods, a spraying process was selected and a continuous manufacturing process concept was proposed. Finally, key control parameters of the spraying process were identified and their influence tested on actual MEAs to define optimal operating conditions. / text

<p>The direct methanol fuel cell or DMFC is emerging as a promising alternative energy source for many applications. Developed and developing countries, through research, are fast seeking a cheap and stable supply of energy for an ever-increasing number of energy-consuming portable devices. The research focus is to have DMFCs meeet this need at an affordable cost is problematic. There are means and ways of making this a reality as the DMFC is found to be complementary to secondary batteries when used as a trickle charger, full charger, or in some other hybrid fuel cell combination. The core functioning component is a catalyst containing MEA, where when pure platinum is used, carbon monoxide is the thermodynamic sink and poisons by preventing further reactions at catalytic sites decreasing the life span of the catalyst if the CO is not removed. Research has shown that the bi-functional mechanism of a platinum-ruthenium catalyst is best because methanol dehydrogenates best on platinumand water dehydrogenation is best facilitated on ruthenium. It is also evident that the addition of other metals to that of PtRu/C can make the catalyst more effective and effective and increase the life span even further. In addition to this, my research has attempted to reduce catalyst cost for DMFCs by developing a low-cost manufacturing technique for catalysts, identify potential non-noblel, less expensive metallic systems to form binary, ternary and quarternary catalysts.</p>

Philosophiae Doctor - PhD / The direct methanol fuel cell or DMFC is emerging as a promising alternative energy source for many applications. Developed and developing countries, through research, are fast seeking a cheap and stable supply of energy for an ever-increasing number of energy-consuming portable devices. The research focus is to have DMFCs meeet this need at an affordable cost is problematic. There are means and ways of making this a reality as the DMFC is found to be complementary to secondary batteries when used as a trickle charger, full charger, or in some other hybrid fuel cell combination. The core functioning component is a catalyst containing MEA, where when pure platinum is used, carbon monoxide is the thermodynamic sink and poisons by preventing further reactions at catalytic sites decreasing the life span of the catalyst if the CO is not removed. Research has shown that the bi-functional mechanism of a platinum-ruthenium catalyst is best because methanol dehydrogenates best on platinumand water dehydrogenation is best facilitated on ruthenium. It is also evident that the addition of other metals to that of PtRu/C can make the catalyst more effective and effective and increase the life span even further. In addition to this, my research has attempted to reduce catalyst cost for DMFCs by developing a low-cost manufacturing technique for catalysts, identify potential non-noblel, less expensive metallic systems to form binary, ternary and quarternary catalysts. / South Africa

As the world begins to focus more and more on new and more effective means of energy production, fuel cells become increasingly more popular. While different fuel cells are already found in industry today, the direct methanol fuel cell (DMFC) is becoming an increasingly more probable means for portable power production. In such applications a passive air breathing direct methanol fuel cell would be ideal. However, successful use of the passive DMFC in such applications requires that the fuel cell be capable of operating at various temperatures and relative humidities. A passive air breathing direct methanol fuel cell was developed and manufactured for this study. This work studied the effects of varying relative humidity and temperature over a probable range of operating conditions for small scale portable power applications on the performance of the fuel cell, both in relation to power production and fuel consumption. Potentiostatic, electrochemical impedance spectroscopy, and polarization tests were performed in order to characterize the performance of the fuel cell. Additionally, a one dimensional steady state isothermal mass transport model was developed to provide insight to the behavior of the fuel cell. The experimental data and model results show that increasing the fuel cell temperature and decreasing the ambient relative humidity increases the current production capabilities of the fuel cell. Further, the experimental data suggests that the major problem hindering current production in passive air breathing direct methanol fuel cells is flooding of the cathode diffusion layer. / Master of Science

Thesis (M. Tech. Engineering: Electrical--Vaal University of Technology) / The air-breathing Direct Methanol Fuel Cell (DMFC) and Zinc Air Fuel Cell (ZAFC)were experimentally studied in a climate chamber in order to investigate the impact of climatic environmental parameters such as varying temperature and relative humidity conditions on their performance. The experimental results presented in the form of polarization curves and discharge characteristic curves indicated that these parameters have a significant effect on the performance of these fuel cells. The results showed that temperature levels below 0ºc are not suitable for the operation of these fuel cells. Instead, it was found that air-breathing DMFC is favored by high temperature conditions while both positive and negative effects were noticed for the air-breathing ZAFC. The results of the varying humidity conditions showed a negative impact on the air-breathing DMFC at a lower temperature level but a performance increase was noticed at a higher temperature level. For air-breathing ZAFC, the effect of humidity on the performance was also found to be influence by the operating temperature. Furthermore, common atmospheric air pollutants such as N20, S02, CO and N02 were experimentally investigated on the air-breathing DMFC and ZAFC. At the concentration of 20 ppm, these air contaminants showed to have a negative effect on the performance of both air-breathing DMFC and ZAFC. For both air-breathing DMFC and ZAFC, performance degradations were found to be irreversible. It is therefore evident from this research that the performance of the air-breathing fuel cell will be affected in an application situated in a highly air-polluted area such as Vaal Triangle or Southern Durban. It is recommended the air-breathing fuel cell design include air filters to counter the day-to-day variations in concentration of air pollutants.

Magister Scientiae - MSc / Fuel cells convert chemical energy from a fuel into electricity through chemical reaction with oxygen. This possesses some challenges like slow oxygen reduction reaction (ORR), overpotential, and methanol fuel cross over in a direct methanol fuel cell (DMFC). These challenges cause inefficiency and use of higher amounts of the expensive platinum catalyst.Several binary catalysts with better ORR activity have been reported. In this study we investigate the best catalyst with better ORR and MOR performances and lower over-potentials for PEMFC and DMFC applications by comparing the in-house catalysts (10%Pt/C, 20%Pt/C,30%Pt15%Ru/C, 40%Pt20%Ru/C, 30%PtCo/C, 20%Pt20%Cu/C and 20%PtSn/C) with the commercial platinum based catalysts (10%Pt/C, 20%Pt/C, 20%Pt10%Ru/C, 20%PtCo/C,20%PtCu/C and 20%PtSn/C) using the cyclic voltammetry and the rotating disk electrode to determine their oxygen reduction reaction and methanol tolerance. HRTEM and XRD techniques were used to determine their particle size, arrangement and the atomic composition. It was observed that the 20%Pt/C in-house catalyst gave the best ORR activity and higher methanol oxidation current peaks compared to others catalysts followed by 20%Pt10%Ru/C commercial catalyst. The 20%PtCo/C commercial, 30%PtCo/C in-house and 20%PtSn/C in-house catalysts were found to be the most methanol tolerant catalysts making them the best catalysts for ORR in DMFC. It was observed that the ORR activity of 20%PtCo/C commercial and 30%PtCo/C inhouse catalysts were enhanced when heat treated at 350 0C. From XRD and HRTEM studies, the particle sizes were between 2.72nm to 5.02nm with little agglomeration but after the heat treatment, the particles were nicely dispersed on the carbon support.

In this research the effects of the fabrication processes of MEA on the output power of a DMFC stack are studied by changing hot-pressing conditions including pressure, temperature and time. Additionally, the effects of the various treatments of the MEAs on the output voltage and power are also studied after the hot-pressing process of MEA is finished. In the first experimental study the catalyst of cathode is 4.0mg/cm unsupported HP Pt black, Anode is 4.0mg/cm 80% HP Pt-Ru Alloy (1: 1), membrane is Nafion 117, and bipolar plates is heterogeneous carbon fiber bipolar plate developed by our fuel cell laboratory. The MEA for single cell includes the area of membrane 3*3 cm2 the active area of electrode 1.5*1.5 cm2. Under the hot-pressing conditions 120 oC, 100 bar and 90s, the maximum power density can reach a value of 18 mW/cm2 at the conditions of methanol concentration 3 M, air-breathing, and room temperature After several experiments, we observed that performances of MEAs decayed with time. So we designed a series of experiments to inspect the various possible reasons and try to solve this problem. The cylindrical DMFC is one of the most important developments in our lab. However, the MEAs made for plate-type DMFC do not fit the cylindrical DMFC stack properly. The electrodes easily pealed off from the membrane and the contact resistance increases after certain periods. So the hot-pressing device had been redesigned to fit the cylindrical DMFC stack. After that the total power of the 6-cell stack with total active area 15 cm2 can reach a value 135 mW. If the performance of each cell of the 6-cell stack is uniform, we expect that the total power of this stack can reach a higher value 195 mW, which can be applied to some portable electronic products.

Membrane electrode assembly (MEA) is the foundation of the single cell as well as the core of the fuel cell when generating electricity. Its work efficiency is the key factor for single cell performance. This study aims to understand the variation between the conventional method and the decal method during the MEA process. By observing the microstructure morphology of electrode and the performance of single cell, as well as analyzing internal resistance and its stabilization, the advantages and disadvantages of MEA in the two methods is analyzed. The decal condition is 135¢XC, 15 kg/cm , 2.5 min at a high temperature (50¢XC 3M methanol), in air-breathing under atmosphere system. The maximum power density is approximately 22.5 mW/cm which is very close to the result of conventional method. The decal method is better than the conventional method particularly in regards to the high current density performance. It shows that there is an efficient influence of the decal method on the methanol mass transfer and it also improves its polarization and enlarges the current. If the single cell is operated in the high temperature, the fuel mass transfer can be advanced in the decal method and its performance can be raised. However, in the manufacturing process, more time has to be spent when producing the MEA. This experiment can be used as a reference on the single cell operation environment and manufacturing time for future studies.

Proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are two types of low-temperature fuel cells (LTFCs) that operate at temperatures less than 100 °C and are appealing for portable, transportation, and stationary applications. However, commercialization has been hampered by several problems such as cost, efficiency, and durability. New electrocatalysts must be developed that have higher oxygen reduction reaction (ORR) activity, lower precious metal loadings, and improved durability to become commercially viable. This dissertation investigates the development and use of new electrocatalysts for the ORR. Core-shell (shell@core) Pt@Pd[subscript x]Cu[subscript y]/C electrocatalysts, with a range of initial compositions, were synthesized to result in a Pt-rich shell atop a Pd[subscript x]C[subscript y]-rich core. The interaction between core and shell resulted in a delay in the onset of Pt-OH formation, accounting in a 3.5-fold increase in Pt-mass activity compared to Pt/C. The methanol tolerance of the core-shell Pt@PdCu₅/C was found to decrease with increasing Pt-shell coverage due to the negative potential shift in the CO oxidation peak. It was discovered that Cu leached out from the cathode has a detrimental effect on membrane-electrode assembly performance. A spray-assisted impregnation method was developed to reduce particle size and increase dispersion on the support in a consistent manner for a Pd₈₈W₁₂/C electrocatalyst. The spray-assisted method resulted in decreased particle size, improved dispersion and more uniform drying compared to a conventional method. These differences resulted in greater performance during operation of a single DMFC and PEMFC. Additionally, Pd₈₈W₁₂/C prepared by spray-assisted impregnation showed DMFC performance similar to Pt/C with similar particle size in the kinetic region while offering improved methanol tolerance. Pd₈₈W₁₂/C also showed comparable maximum power densities and activities normalized by cost in a PEMFC. Lastly, the activation of aluminum as an effective reducing agent for the wet- chemical synthesis of metallic particles by pitting corrosion was explored along with the control of particle morphology. It was found that atomic hydrogen, an intermediate, was the actual reducing agent, and a wide array of metals could be produced. The particle size and dispersion of Pd/C produced using Al was controlled using PVP and FeCl₂ as stabilizers. The intermetallic Cu₂Sb was similarly prepared with a 20 nm crystallite size for potential use in lithium-ion battery anodes. Lastly, it was found that the shape of Pd produced with Al as a reducing agent could be controlled to prepare 10 nm cubes enclosed by (100) facets with potentially high activity for the ORR. / text