Multiwall carbon nanotubes (CNTs) were synthesized by catalytic chemical vapor deposition of acetylene and used as templates to prepare CNT-Sb and CNT-SnSb₀.₅ nanocomposites via the chemical reduction of SnCl₂ and SbCl₃ precursors. SEM and TEM imagings show that the Sb and SnSb₀.₅ particles were uniformly dispersed in the CNT web and on the outside surface of CNTs. These CNT-metal composites are active anode materials for lithium ion batteries, showing improved cyclability compared to unsupported Sb and SnSb particles; and higher reversible specific capacities than CNTs. The improvement in cyclability may be attributed to the nanoscale dimensions of the metal particles and CNT’s role as a buffer in containing the mechanical stress arising from the volume changes in electrochemical lithium insertion and extraction reactions. / Singapore-MIT Alliance (SMA)

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. 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. 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. 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. 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. Keywords: direct methanol fuel cell, fuel cell, DMFC, anode,model

This study highlights the importance of the anion in the electrochemical uptake of lithium by metal phosphides. It is shown through a variety of <em>in-situ</em> and <em>ex-situ</em> analytical techniques that the redox active centers in three different systems (MnP<i>₄</i>, FeP<i>₂</i>, and CoP<i>₃</i>) are not necessarily cationic but can rest almost entirely upon the anionic network, thanks to the high degree of covalency of the metal-phosphorus bond and strong P-character of the uppermost filled electronic bands in the phosphides. The electrochemical mechanism responsible for reversible Li uptake depends on the transition metal, whether a lithiated ternary phase exists in the phase diagram with the same M:P stoichiometry as the binary phase, and on the structure of the starting phase. When both binary and lithiated ternary phases of the transition metal exist, as in the case of MnP<i>₄</i> and Li<i>₇</i>MnP<i>₄</i>, a semi-topotactic phase transformation between binary and ternary phases occurs upon lithium uptake and removal. When only the binary phase exists two different behaviours are observed. In the FeP<i>₂</i> system, lithium uptake leads to the formation of an amorphous material in which short-range order persists; removal of lithium reforms some the long-range order bonds. In the case of CoP<i>₃</i>, lithium uptake results in phase decomposition to metallic cobalt plus lithium triphosphide, which becomes the active material for the subsequent cycles.

This study highlights the importance of the anion in the electrochemical uptake of lithium by metal phosphides. It is shown through a variety of <em>in-situ</em> and <em>ex-situ</em> analytical techniques that the redox active centers in three different systems (MnP<i>₄</i>, FeP<i>₂</i>, and CoP<i>₃</i>) are not necessarily cationic but can rest almost entirely upon the anionic network, thanks to the high degree of covalency of the metal-phosphorus bond and strong P-character of the uppermost filled electronic bands in the phosphides. The electrochemical mechanism responsible for reversible Li uptake depends on the transition metal, whether a lithiated ternary phase exists in the phase diagram with the same M:P stoichiometry as the binary phase, and on the structure of the starting phase. When both binary and lithiated ternary phases of the transition metal exist, as in the case of MnP<i>₄</i> and Li<i>₇</i>MnP<i>₄</i>, a semi-topotactic phase transformation between binary and ternary phases occurs upon lithium uptake and removal. When only the binary phase exists two different behaviours are observed. In the FeP<i>₂</i> system, lithium uptake leads to the formation of an amorphous material in which short-range order persists; removal of lithium reforms some the long-range order bonds. In the case of CoP<i>₃</i>, lithium uptake results in phase decomposition to metallic cobalt plus lithium triphosphide, which becomes the active material for the subsequent cycles.

<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>

Since their commercialization in 1990, the electrodes of the lithium-ion battery have remained fundamentally the same. While energy density improvements have come from reducing the cell packaging, higher capacity electrodes are needed to continue this trend. A lithium metal anode, where the negative electrode half reaction is the plating and stripping of metallic lithium, is explored as an alternative to current graphite anodes. The specific capacity of the lithium metal anode is over ten times that of the graphite anode, making it a serious candidate to further improve the energy density of lithium batteries. Electrodeposited lithium metal forms dendrites, sharp needles that can grow across the separator and short circuit the battery. Thus, a chief goal is to alter lithium’s plating morphology. This was achieved in two separate ionic liquid electrolytes by co-depositing lithium with sodium. The co-deposited sodium is thought to block dendritic sites, leading to a granular deposit. A nucleation study confirmed that metal deposits from the ionic liquid electrolyte containing sodium, prevented dendritic growth from nucleation on, and not after dendrites had already grown. A model based on the geometry of the nuclei was used to gain insight into the effect of the solid electrolyte interface (SEI) that forms on freshly deposited lithium metal. In addition to sodium, the effect of alkaline earth metals on the lithium deposit morphology was also explored. While these metals did not deposit from the ionic liquid electrolyte, their addition also resulted in granular, dendrite free, deposits. The alkaline earth additives generally increased the overpotential for nucleating on the substrate and lowered the current density achievable. Strontium and barium showed the least of these negative effects while still providing a dendrite free deposit. A second hurdle for lithium metal anodes is the instability between the electrolyte and lithium metal. A protective SEI layer that prevents undesired side reactions is difficult to form because of the large volume change associated with cycling. Formation of a better SEI on lithium metal was attempted through the addition vinylene carbonate, which greatly improved the coulombic efficiency of lithium metal plating and stripping. The effect of gases, such as oxygen, nitrogen and carbon dioxide, on the SEI layer was also investigated. It was found that the presence of nitrogen and oxygen improved the coulombic efficiency by facilitating a thinner SEI layer. This work presents attempts at improving the lithium metal anode both by increasing the coulombic efficiency of the redox process and by eliminating dendrite growth. The coulombic efficiency was improved through the bubbling of gases and addition of organic additives but work remains to increase this value further. Dendritic growth, which poses a safety hazard, was completely eliminated by two methods: 1) co-deposition and 2) adsorption of a foreign metal. Both methods could potentially be applied to different electrolytes, making them promising methods for preventing dendritic growth in future lithium metal anodes.

Interest in high performance portable energy devices for electronics and electric vehicles is the basis for a significant level of activity in battery research in recent history. Li-ion batteries are of particular interest due to their high energy density, decreasing cost, and adaptable form factor. A common goal of researchers is to develop new materials that will lower the cost and weight of Li-ion batteries while simultaneously improving the performance. There are several approaches to facilitate improved battery system-level performance including, but not limited to, the development of new material structures and/or chemistries, manufacturing techniques, and cell management. The performed research sought to enhance the understanding of structure-property relationships of carbon-containing composite anode materials in a Li-ion cell through extensive materials and anode performance characterization. The approach was to focus on the development of new electrode material designs to yield higher energy and power characteristics, as well as increased thermal and electrical conductivities or mechanical strength, using techniques that could be scaled for large volume manufacturing. Here, three different electrode architectures of nanomaterial composites were synthesized and characterized. Each electrode structure consisted of a carbon substrate that was conformally coated with a high Li capacity material. The dimensionality and design for each structure was unique, with each offering different advantages. The addition of an external coating to further increase the stability of high capacity materials was also investigated.

Silicon (Si)-based materials have recently emerged as a promising candidate for anodes in lithium-ion batteries because they exhibit much higher energy-storage capacities than the conventional graphite anode. However, the practical use of Si is hampered by its poor cycleability; during lithiation, Si forms alloys with Li and undergoes significant structural and volume changes, which can cause severe cracking/pulverization and consequent capacity fading arising from the loss of electrical contacts. To overcome these drawbacks, many innovative approaches have been explored with encouraging results; however, many fundamental aspects of the lithiation behavior remain ambiguous. Hence, the focus of this work is to develop a better understanding of the lithiation process at the atomistic scale using quantum mechanical calculations. In addition, based on the improved understanding, we attempt to address the fundamental mechanisms behind the successful approaches to enhance the anode performance. To lay a foundation for the investigation of alloy-type anodes, in Chapter 3, we first examine how lithiation occurs in Si and the formation of crystalline and amorphous LixSi alloys (0 ≤ x ≤ 4); followed by assessing the lithiation-induced changes in the energetics, atomic structure, electronic and mechanical properties, and Li diffusivity. The same approach is then extended to analyze the lithiation behavior of germanium (Ge) and tin (Sn) for developing a generalized understanding on the Group IV alloy-type anodes. Along this comparative study, we notice a few distinguishing features pertain only to Si (or Ge), such as the facile Li diffusion in Ge and facet-dependent lithiation in Si, which are discussed in Chapter 4. Beyond the fundamental research, we also look into factors that may contribute to the improved anode performance, including (i) finetuning of the oxidation effects in Si-rich oxides, [alpha] -SiO [subscript 1/3] (Chapter 5), (ii) maximizing the surface effects through nano-engineered structures (Chapters 6 & 7), and finally (iii) the role of interface in Si-graphene (carbon) composites (Chapter 8).

This thesis presents a study of a pulsed distributed arc plasma deposition method that has been developed to produce highly ionized pulsed plasma plumes of metallic species in the presence of a low-pressure inert or reactive gas glow discharge. A pulse-forming network (PFN) is used to form a transient electrical discharge in a hollow electrode which is triggered by two different methods; a pulsed CO2 laser or a pulsed high voltage glow discharge. With the PFN charged to a voltage of 70 - 100 VDC, current pulses with peak currents up to 3 kA and pulse widths as long 3.7 milliseconds have been reached. A detailed treatment of the influence of process parameters, such as the PFN discharge energy and ambient gas pressure and type, on the plasma properties is presented. These experiments also demonstrated a higher on-axis growth rate of carbon in an ambient of nitrogen than in argon. The higher argon mass leads to broader plasma expansion producing broader deposition profiles which results in lower on-axis growth rates. Deposition rates of 3.5 angstrom/pulse for carbon and 2.1 angstrom/pulse for titanium have been achieved. Thickness profiles and the morphology of carbon films and titanium films deposited by this method, which utilize the energetic advantage of ions in film formation allowing reduced substrate temperatures and good adhesion, are presented.

Transportation sector CO2 emissions contribute to global warming. Methanol generated from clean energy sources has been proposed as a transportation fuel as an alternative to gasoline or diesel to reduce emissions. Catalytic methanol-steam reformers can be combined with high temperature polymer electrolyte membrane (HTPEM) fuel cell systems to create compact electrical power modules which run on liquid methanol. These modules combine the efficiency of a fuel cell system with the convenience of using a traditional, liquid hydrocarbon fuel. Catalytic methanol-steam reformers require a heat source as the methanol-steam reforming process is endothermic. The heat source for this system will initially be from the catalytic combustion of either pure methanol, during startup, or from HTPEM fuel cell anode waste gas during system operation. Efficient use of catalyst requires effective premixing of the fuel and air. This study will investigate parameters affecting premixing and their effect on temperature distributions and emissions.