Thesis (M.S.)--Rochester Institute of Technology, 1991. / Typescript. Includes bibliographical references.

Thesis (M.S.)--Rochester Institute of Technology, 2008. / Typescript. Includes bibliographical references (leaves 56-58).

Thesis (Ph. D.)--University of Canterbury, 2008. / Typescript (photocopy). "November 2008." Includes bibliographical references (p. [144]-149). Also available via the World Wide Web.

Thesis (M.S.)--Rochester Institute of Technology, 2004. / Typescript. Includes bibliographical references (leaves 74-76).

Um detector de catodo quente é construído. As características de operação foram medidas e estabelecido o ponto ótimo de operação na detecção de átomos de sódio. Uma aplicação do detector desenvolvido foi feita com experimentos de deflexão de feixe atômico por luz. Os casos para deflexão por onda caminhante e onda estacionária foram investigados. A dependência com a dessintonia entre a freqüência do laser &#969&#8747 e a freqüência da transição 3S1/2 (F=2, m=2) &#8594 3P3/2 (F=3, m=3) do átomo de sódio foi analisada para todos os casos. / A hot wire detector has been constructed. The operational characteristics were measured and the optimum operational point was established in sodium atoms detection experiment. An application of the developed detector was made with atomic beams deflections by light. The cases for running wave and standing wave were also investigated. The detuning dependence between the laser frequency &#969&#8747 and the transition frequency 3S1/2 (F=2, m=2) &#8594 3P3/2 (F=3, m=3) of the sodium atom was analyzed for all cases.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16396号 / 工博第3477号 / 新制||工||1525(附属図書館) / 29027 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 乾 晴行, 准教授 宇田 哲也 / 学位規則第4条第1項該当

>Magister Scientiae - MSc / Architecturally enhanced electrode materials for lithium ion batteries (LIB) with permeable morphologies have received broad research interests over the past years for their promising properties. However, literature based on modified porous nanoparticles of lithium manganese phosphate (LiMnPO₄) is meagre. The goal of this project is to explore lithium manganese phosphate (LiMnPO₄) nanoparticles and enhance its energy and power density through surface treatment with transition metal nanoparticles. Nanostructured materials offer advantages of a large surface to volume ratio, efficient electron conducting pathways and facile strain relaxation. The material can store lithium ions but have large structure change and volume expansion during charge/discharge processes, which can cause mechanical failure. LiMnPO₄ is a promising, low cost and high energy density (700 Wh/kg) cathode material with high theoretical capacity and high operating voltage of 4.1 V vs. Ag/AgCl which falls within the electrochemical stability window of conventional electrolyte solutions. LiMnPO₄ has safety features due to the presence of a strong P–O covalent bond. The LiMnPO₄ nanoparticles were synthesized via a sol-gel method followed by coating with gold nanoparticles to enhance conductivity. A magnesium oxide (MgO) nanowire was then coated onto the LiMnPO₄/Au, in order to form a support for gold nanoparticles which will then form a thin film on top of LiMnPO₄ nanoparticles crystals. The formed products will be LiMnPO₄/Mg-Au composite. MgO has good electrical and thermal conductivity with improved corrosion resistance. Thus the electronic and optical properties of MgO nanowires were sufficient for the increase in the lithium ion diffusion. The pristine LiMnPO₄ and LiMnPO₄/Mg-Au composite were examined using a combination of spectroscopic and microscopic techniques along with cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Microscopic results revealed that the LiMnPO₄/Mg-Au composite contains well crystallized particles and regular morphological structures with narrow size distributions. The composite cathode exhibits better reversibility and kinetics than the pristine LiMnPO₄ due to the presence of the conductive additives in the LiMnPO₄/Mg-Au composite. This is demonstrated in the values of the diffusion coefficient (D) and the values of charge and discharge capacities determined through cyclic voltammetry. For the composite cathode, D= 2.0 x 10⁻⁹ cm²/s while for pristine LiMnPO₄ D = 4.81 x 10⁻¹⁰ cm2/s. The charge capacity and the discharge capacity for LiMnPO₄/Mg-Au composite were 259.9 mAh/g and 157.6 mAh/g, respectively, at 10 mV/s. The corresponding values for pristine LiMnPO₄ were 115 mAh/g and 44.75 mAh/g, respectively. A similar trend was observed in the results obtained from EIS measurements. These results indicate that LiMnPO₄/Mg-Au composite has better conductivity and will facilitate faster electron transfer and therefore better electrochemical performance than pristine LiMnPO₄. The composite cathode material (LiMnPO₄/Mg-Au) with improved electronic conductivity holds great promise for enhancing electrochemical performances, discharge capacity, cycle performance and the suppression of the reductive decomposition of the electrolyte solution on the LiMnPO₄ surface. This study proposes an easy to scale-up and cost-effective technique for producing novel high-performance nanostructured LiMnPO₄ nanopowder cathode material.

Philosophiae Doctor - PhD / Direct methanol fuel cells (DMFCs) are attractive power sources as they offer high conversion efficiencies with low or no pollution. One of the major advantages DMFCs has over PEMFCs is that methanol is a liquid and can be easily stored where in the case for PEMFCs storing hydrogen requires high pressures and low temperatures. However, several challenging factors especially the sluggish oxygen reduction reaction (ORR) and the high cost of Pt catalysts, prolong their commercialization. With the aim to search for more active, less expensive more active ORR catalysts and methanol tolerant catalysts than pure Pt, this dissertation focuses on the development of low loading Pt electrocatalyst and the understanding of their physical and electrochemical properties. Pt-Sn/C electrocatalsyts have been synthesized by a modified polyol reduction method. The effect of temperature, pH, water, sonication and addition of carbon form were studied before a standard polyol method was established. From XRD patterns, the Pt-Sn/C peaks shifted slightly to lower 2Ө angles when compared with commercial Pt/C catalyst, suggesting that Sn is alloying with Pt. Based on HRTEM data, the Pt-Sn/C nanoparticles showed small particle sizes well-dispersed onto the carbon support with a narrow particle distribution. The particle sizes of the different as-prepared catalysts were found to be between 2-5 nm. The Pt-Sn/C HA Slurry pH3 catalysts was found to be the best asprepared catalyst and was subjected to heat-treatment in a reducing atmosphere at 250-600 °C which led to agglomeration yielding nanoparticles of between 5-10 nm. The Methanol Oxidation Reaction (MOR) on the as-prepared Pt-Sn/C HA Slurry pH3 catalyst appeared at lower currents (+7.11 mA at 860 mV vs. NHE) compared to the commercial Pt/C (+8.25 mA at +860 mV vs. NHE) suggesting that the Pt-Sn/C catalyst has „methanol tolerance capabilities‟. Pt-Sn/C HA Slurry pH3 and Pt-Sn/C 250 °C catalysts showed better activity towards the ORR than commercial Pt/C with specific and mass activities higher than Pt/C at +0.85 V vs NHE. The Tafel slopes of Pt-Sn/C HA Slurry pH3 catalyst was -62 and -122 mV dec-1 for the low and high current regions respectively and suggests that the ORR mechanism is similar to that of commercial Pt/C indicating that the ORR kinetics was not negatively influenced by the addition of tin. It was found that the electrochemical oxidation reduction reaction follows first order kinetics of a multi-electronic (n=4ē) charge transfer process producing water. All the Pt-Sn/C catalysts showed resistance towards MOR and it was found for the heat-treated catalysts that an increase in temperature resulted in an increase in methanol tolerance. The synthesized Pt-Sn/C HA Slurry pH3 catalysts were also tested in a fuel cell environment. Electrodes were prepared by either spraying on Toray carbon paper with the Asymtek machine or by VI spraying directly on the membrane with a hand spray gun the catalysts coated membrane (CCM) technique. Polarization curves obtained in DMFC with CCM showed superior performance than electrode prepared by spraying on the carbon paper with the machine. In our study, the Pt-Sn/C catalyst appears to be a promising methanol tolerant catalyst with activity towards the ORR in the DMFC.

>Magister Scientiae - MSc / Fuel cells are widely considered to be efficient and non-polluting power source offering much higher energy density. This study is aimed at developing oxygen reduction reactions (ORR) catalysts with reduced platinum (Pt) loading. In order to achieve this aim, monometallic Pd and Pt nanostructured catalysts were electrodeposited on a substrate (carbon paper) by surface limited redox replacement using electrochemical atomic layer deposition (ECALD) technique. Pd:Pt bimetallic nanocatalysts were also deposited on carbon paper. Pd:Pt ratios were (1:1, 2.1 and 3:1). The prepared mono and bimetallic catalysts were characterized using electrochemical methods for the ORR in acid electrolyte. The electrochemical characterization of these catalysts includes: Cyclic Voltammetry (CV) and linear sweep voltammetry (LSV). The physical characterization includes: scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) for Morphology and elemental composition, respectively. The deposition of copper (Cu) on carbon paper was done by applying a potential of -0.05 V at 60s, 90s and 120s. 8x cycles of Pt or Pd showed better electrochemical activity towards hydrogen oxidation reaction. Multiples of eight were used in this work to deposit Pt: Pd binary catalyst. Cyclic voltammetry showed high electroactive surface area for Pt24Pd24/Carbon-paper while LSV showed high current density and positive onset potential. HRSEM also displayed small particle size compared to other Pt:Pd ratios.

Orientadores: Claudia Longo, Ennio Peres da Silva / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T05:12:29Z (GMT). No. of bitstreams: 1 Rapelli_RubiaMunhoz_M.pdf: 19025999 bytes, checksum: de01222afac6e67c3ed6789e8e3c5baa (MD5) Previous issue date: 2012 / Resumo: Com a motivação de aumentar a eficiência de catodos para a eletrólise alcalina da água, investigaram-se as propriedades de eletrodos de níquel fosco e níquel-zinco poroso na reação de desprendimento de hidrogênio (RDH). O eletrodo de Ni fosco foi preparado pela eletrodeposição de um filme de Ni em substrato de aço carbono. No eletrodo de Ni-Zn, depositou-se inicialmente um filme de ca. 5 mm de Ni fosco e a seguir um codepósito de Ni-Zn. A seguir, os eletrodos foram mantidos por 24 h em solução aquosa de NaOH. Os filmes resultantes, com espessura de ca. 20 mm, apresentaram estrutura cristalina e superfície uniforme. Análises por microscopia eletrônica de varredura (MEV) revelaram que o filme de Ni era constituído por grãos piramidais; no filme de Ni-Zn, identificaram-se partículas arredondadas em uma superfície porosa e com rachaduras. A superfície porosa resultou da remoção parcial do Zn, confirmada em mapeamento por energia dispersiva de raios X (EDS), devido à formação de hidróxidos solúveis durante o tratamento alcalino. As propriedades eletroquímicas, investigadas a 25 °C em solução aquosa de KOH por voltametria cíclica, medidas de Tafel e espectroscopia de impedância eletroquímica revelaram que, comparado ao eletrodo de Ni, o eletrodo de Ni-Zn poroso apresentou maiores valores de constante de transferência de carga (0,34 e 0,46) e densidade de corrente de troca (1,4 e 5,5 mA cm), além de menores valores para a resistência à transferência de carga (120 e 85 W ) e sobrepotencial para a RDH. O desempenho dos eletrodos como catodos na eletrólise alcalina da água foi avaliado sob controle galvanostático a -100 mA cm, em modo intermitente, por 88 h (ciclos de 8 h em 11 dias). Inicialmente, os potenciais de operação corresponderam a -1,5 e -1,3 V para os eletrodos de Ni e de Ni-Zn poroso; o sobrepotencial para a RDH variou no período, e, após 88 h, resultou em -1,53 e -1,43 V respectivamente. Análises por MEV revelaram alterações na morfologia dos filmes, principalmente para o eletrodo poroso; no mapeamento por EDS, observou-se menor teor de Zn e identificou-se a presença de óxidos. De modo geral, conclui-se que o eletrodo de Ni-Zn poroso pode ser considerado um catodo promissor para aplicação em eletrolisadores, por apresentar menor gasto de energia que o eletrodo de Ni para manter uma dada produção de hidrogênio / Abstract: Motivated to improve the efficiency of cathodes for alkaline water electrolysis, the properties of nickel Watts and porous nickel-zinc electrodes for hydrogen evolution reaction (HER) were investigated. The Ni Watts electrode was prepared by electrodepositing a Ni film on a carbon steel substrate. Preparation of the Ni-Zn electrode comprised firstly the deposition of a Ni film (5 mm thick) followed by the co-deposition of Ni-Zn. The electrodes were then maintained for 24 h at NaOH aqueous solution. The resulting films, ca. 20 mm thick, exhibited crystalline structure and uniform surface. Scanning electron microscopy (SEM) revealed that the Ni film consisted of pyramidal grains; for the Ni-Zn film, rounded particles were identified in a porous surface with cracks. The porous surface resulted from the partial Zn removal, as confirmed by mapping energy dispersive X-ray (EDS), due to the production of soluble hydroxides during the alkaline treatment. The electrochemical properties, investigated at 25 °C in aqueous KOH solution by cyclic voltammetry, Tafel measurements and electrochemical impedance spectroscopy revealed that, compared to the Ni Watts electrode, the porous Ni-Zn electrode exhibited higher values for the charge transfer constant (0.34 and 0.46) and exchange current density (1.4 and 5.5 mA cm), and lower values for the resistance to charge transfer (120 and 85 W) and overpotential for the HER. The electrodes performance as cathodes in alkaline water electrolysis was evaluated under galvanostatic control at -100 mA cm, in intermittent mode, for 88 h (8 h cycles, 11 days). Initially, the operating potential corresponded to -1.5 and -1.3 V for Ni and Ni-Zn porous electrodes; the HER overpotential varied in the period and, after 88 h, resulted in -1.53 and -1, 43 V respectively. SEM analysis revealed morphological changes for the films surface, mainly for the porous electrode. From EDS mapping, a lower Zn concentration was observed; also, oxides were identified. Thus, the porous Ni-Zn electrode can be considered a promising cathode for electrolyzers since, when compared to the Ni Watts electrode, lower energy is necessary to maintain the hydrogen production under galvanostatic control / Mestrado / Físico-Química / Mestra em Química