abstract: This work describes the investigation of novel cathode and anode materials. Specifically, several mixed polyanion compounds were evaluated as cathodes for Li and Na-ion batteries. Clathrate compounds composed of silicon or germanium arranged in cage-like structures were studied as anodes for Li-ion batteries. Nanostructured Cu4(OH)6SO4 (brochantite) platelets were synthesized using polymer-assisted titration and microwave-assisted hydrothermal methods. These nanostructures exhibited a capacity of 474 mAh/g corresponding to the full utilization of the copper redox in an conversion reaction. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) studies were preformed to understand the mechanism and structural changes. A microwave hydrothermal synthesis was developed to prepare a series compounds based on jarosite, AM3(SO4)2(OH)6 (A = K, Na; M = Fe, V). Both the morphology and electrochemical properties showed a compositional dependence. At potentials >1.5 V vs. Li/Li+, an insertion-type reaction was observed in Na,Fe-jarosite but not in K,Fe-jarosite. Reversible insertion-type reactions were observed in both vanadium jarosites between 1 – 4 V with capacities around 40 - 60 mAh/g. Below 1 V vs. Li/Li+, all four jarosite compounds underwent conversion reactions with capacities ~500 mAh/g for the Fe-jarosites. The electrochemical properties of hydrogen titanium phosphate sulfate, H0.4Ti2(PO4)2.4(SO4)0.6 (HTPS), a new mixed polyanion material with NASICON structure was reported. A capacity of 148 mAh/g corresponding to2 Li+ insertion per formula unit was observed. XRD and XPS were used to characterize the HTPS before and after cycling and to identify the lithium sites. Evaluation of the HTPS in Na-ion cell was also performed, and a discharge capacity of 93 mAh/g was observed. A systematic investigation of the role of the processing steps, such as ball-milling and acid/base etching, on the electrochemical properties of a silicon clathrate compound with nominal composition of Ba8Al16Si30 was performed. According to the transmission electron microscope (TEM), XPS, and electrochemical analysis, very few Li atoms can be electrochemically inserted, but the introduction of disorder through ball-milling resulted in higher capacity, while the oxidation layer made by the acid/base treatment prevented the reation. The electrochemical property of germanium clathrate was also investigated, unlike the silicon clathrate, the germanium one underwent a conversion reaction. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2017

The aim of this thesis is to investigate pyroborates, M2B2O5, and orthoborates, M3(BO3)2, where M = Mg, Mn, Co, Ni, as high capacity and high voltage Li- and Mg-ion cathode materials. We explore the layered orthoborates (M3(BO3)2 which, to our knowledge, have not been previously considered as Li- or Mg-ion cathodes, perhaps due to the lack of Li analogues. Structural analysis shows that mixed metal orthoborates form a solid solution, with cation order driven by the presence of directional d orbitals. Electrochemical studies show that Mg can be removed from the structure and replaced with Li in a 1:1 ion ratio. In the compound Mg2Mn(BO3)2 removal of 1 Mg is achieved giving a capacity of 209.9 mAh g 1. The pyroborates (M2B2O5) are an unexplored family of borate polyanions, which offer higher theoretical capacities and voltages than LiMBO3 due to their more condensed frameworks. There are no known Li containing pyroborates, we use electrochemical ion exchange, with the aim of replacing each Mg with 2 Li to form LixMB2O¬5. The stoichiometry can be varied to alter the redox couple utilised and the Mg available for removal. MgxM2-xB2O5 has been synthesised for M = Mn, Co, Fe and Ni and all forms have been shown to form a solid solution with cation ordering over the two M sites. In MgMnB2O5 we have shown that Mg can be fully removed while retaining the pyroborate structure. Subsequently up to 1.1 Li can be inserted giving discharge capacities of 240 mAhg-1 above 1.5 V. After 100’s of cycles 2 Li can be reversibly cycled. The insertion of Li has been confirmed by 7Li NMR and the oxidation state changes in Mn have been investigated by SQUID magnetometry and XANES spectroscopy. Electrochemical studies in materials where M = Fe, Co, and Ni show high voltage plateaus ( > 3.5 V) but limited capacity at room temperature. Increased temperatures improves cycling, with Co and Fe based compounds reaching full theoretical capacities ( > 200 mAhg-1). As Mg can be removed from the structure, the pyroborates could be of interest in Mg-ion batteries, which offer benefits in energy density, cost, and safety. Mg-ion battery research is still in its infancy, therefore here we develop methods to reliably test Mg-ion cathodes and electrolytes. We demonstrate that despite significant side reactions, Mg can be reversibly cycled in the MgMnB2O5 system in a full Mg-ion cell, showing that pyroborates are a promising family of materials for high capacity, high voltage Mg-ion cathodes. This study shows that the pyroborates and orthoborates are a promising family of materials for Li- and Mg-ion cathodes, with the light weight structure leading to high specific capacities. The ability to replace Mg for Li in polyanion materials without disrupting the crystal structure opens a new way to search for novel, high energy density, Li-ion cathodes.

Orientador: Watson Loh / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-12T12:43:41Z (GMT). No. of bitstreams: 1 Bernardes_JulianadaSilva_D.pdf: 3716800 bytes, checksum: 697cfd08d77b6bb1c1d45598c8324907 (MD5) Previous issue date: 2008 / Resumo: Polieletrólitos associam-se fortemente com surfatantes de carga oposta em meio aquoso, levando a uma separação de fases que resulta em uma fase concentrada, rica em polieletrólito e surfatante, em equilíbrio com uma fase diluída constituída pelos contra-íons. A fase concentrada pode ser constituída de interessantes estruturas supramoleculares advindas das propriedades de auto-organização destes sistemas, que aliadas à possibilidade de modificaremse a geometria da mesofase e as distâncias entre os agregados, tornam estes sistemas ferramentas importantes em processos de fabricação de estruturas micro e mesoporosas e em sistemas de liberação controlada de drogas. O estudo do equilíbrio de fases de sistemas constituídos por polieletrólitos e surfatantes de cargas opostas em água não é tão simples devido ao grande número de componentes presentes no sistema, porém é possível reduzir a quantidade de componentes através da síntese do sal complexo ¿puro¿ (polieletrólito-surfatante), facilitando dessa forma a análise dos diagramas de fases gerados. Neste trabalho o comportamento de fases de sais complexos formados pelo íon surfatante hexadeciltrimetilaônio (CTA) e pelo polieletrólito (PA) em água e na presença de diferentes solventes orgânicos foi investigado. Três efeitos principais foram analisados: efeito da natureza do solvente orgânico; efeito da adição de uma série homóloga de álcoois e efeito da hidrofobicidade do contra-íon polimérico. Os resultados obtidos indicam que a polaridade do solvente orgânico utilizado influencia intensamente nas estruturas formadas pelo sal complexo. Em geral, observou-se a predominância de estruturas lamelares em sistemas contendo co-surfatantes (n-álcoois) e a predominância de estruturas hexagonais em sistemas contendo p-xileno e ciclohexano. A hidrofobicidade do contra-íon polimérico não gerou mudanças significativas nos diagramas de fases obtidos. / Abstrat: Association between charged polymers and oppositely charged surfactants in aqueous solutions may lead to phase separation forming a concentrated phase rich in polyions and surfactant ions, and a more dilute phase, which mostly contains simple ions. The concentrated phases may display a variety of supramolecular structures with diverse and interesting features due to self-assembling properties of these systems, which have found applications in the field of controlled drug delivery and in templating the synthesis of materials with tailored geometries. A complete description of the phase equilibrium in these systems is quite demanding, because addition of polyelectrolyte and oppositely charged surfactant to water leads to the formation of several components, however it is possible to reduce the number of the components by the preparation of the pure complex-salt, which allows to analyze the phase equilibrium in a controlled manner. In this work the phase behavior of complex salts formed by the surfactant ion hexadecyltrimethylammonium (CTA) and the polyacrylate (PA) in water and with different organic solvents were investigated. Three principal effects were analyzed: the effect of the organic solvent nature; the effect of n-alcohol carbon chain length and the effect of the polyelectrolyte hidrophibicity. The obtained results revealed that the organic solvent nature has a strong influence in the structure assumed by the complex salt. From the general analysis, systems containing co-surfactants (n-alcohols) a predominance of lamellar structures was observed, and in systems containing p-xylene and ciclohexane a predominance of hexagonal structures was detected. The polyelectrolyte hidrophobicity did not display significant changes in the obtained phase diagrams. / Doutorado / Físico-Química / Doutor em Ciências

Inhalt der Arbeit ist die Synthese und Charakterisierung von Hydrogelen auf Stärkebasis mit dem Ziel, diese für unterschiedliche Anwendungszwecke, insbesondere jedoch als Kontaktmedium in der medizinischen Ultraschalldiagnostik, einsetzen zu können. Um Stärke zur Ausbildung stabiler, wässriger Gele zu befähigen, werden mehrere Funktionalisierungsschritte vollzogen. Die Einführung von Carboxymethylfunktionen mittels Williamson-Reaktion erhöht den ionischen Charakter und damit die Hydrophilie des Biopolymers. Zur kinetischen Beschreibung der Carboxymethylierung am Stärkekorn in Suspension wird ein Dreiphasenmodell eingeführt. Der Aufbau eines für Gelstrukturen charakteristischen, dreidimensionalen Netzwerks erfolgt durch inter- und intramolekulare Verknüpfung einzelner Polymerstränge über kovalente Etherbrücken. Durch Eliminierung der nach Substitution und Vernetzung löslich verbliebenen Polymeranteile können die Materialeigenschaften des gequollenen Hydrogels erheblich verbessert werden. Rheologische Messungen und bildgebende Untersuchungen mit Gewebephantomen qualifizieren Stärke-Gele als in anwendungstechnischer Hinsicht geeignetes Kontaktmedium in der medizinischen Ultraschalldiagnostik. Mit speziellen Tests wird die pharmakologisch-toxikologische Unbedenklichkeit der Produkte nachgewiesen.

京都大学 / 0048 / 新制・課程博士 / 博士(人間・環境学) / 甲第19071号 / 人博第724号 / 新制||人||174(附属図書館) / 26||人博||724(吉田南総合図書館) / 32022 / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 内本 喜晴, 教授 田部 勢津久, 准教授 藤原 直樹 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DGAM