abstract: The central theme of this dissertation is to understand the chemical processing science of advanced ceramic materials for biomedicine, including therapy and imaging. The secondary component focuses on the chemical processing of energy materials. Recently, layered double hydroxide (LDH) nanoparticles (NPs) with various intercalated compounds (e.g. fluorescent molecules, radio-labeled ATP, vitamins, DNA, and drugs) have exhibited versatility and promise as a combined therapeutic and diagnostic (i.e. theranostic) vector. However, its eventual acceptance in biomedicine will be contingent on understanding the processing science, reproducibly synthesizing monodispersed NPs with controlled mean particle size (MPS), and ascertaining the efficacy of the NPs for drug delivery and imaging. First, statistical design of experiments were used to optimize the wet chemistry synthesis of (Zn, Al)-LDH NPs. A synthesis model, which allows the synthesis of nearly monodispersed NPs with controlled MPS, was developed and experimentally verified. Also, the evolution of the nanostructure was characterized, from coprecipitation to hydrothermal treatment, to identify the formation mechanisms. Next, the biocompatibility, cellular uptake and drug delivery capability of LDH NPs were studied. In an in vitro study, using cultured pancreatic adenocarcinoma BXPC3 cells, valproate-intercalated LDH NPs showed an improved efficacy (~50 fold) over the sodium valproate alone. Finally, Gd(DTPA)-intercalated LDH NPs were synthesized and characterized by proton (1H) nuclear magnetic resonance. The longitudinal relaxivity (r1) of 28.38 s-1 mM-1, which is over 6 times higher than the clinically approved contrast agent, Gd(DTPA), demonstrated the potential of this vector for use in magnetic resonance imaging. Visible light-transparent single metal-semiconductor junction devices, which convert ultraviolet photon energy into high open circuit voltage (Voc>1.5-2 V), are highly desirable for transparent photovoltaics that can potentially power an electrochromic stack for smart windows. A Schottky junction solar cell, comprised of sputtered ZnO/ZnS heterojunction with Cr/Au contacts, was fabricated and an Voc of <em>f</em>î1.35 V was measured. Also, a low-cost route to form ZnO/ZnS heterojunctions by partial sulfurization of solution-grown ZnO thin films (350 nm-5 <em>f</em>Ým thick; conductivity comparable to phosphorus-doped Si) was demonstrated. A final study was on a cathode material for Li-ion batteries. Phase-pure LiFePO4 powders were synthesized by microwave-assisted sol-gel method and characterized. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2014

This master´s thesis deals with stability of electrolytes and electrodes using electrochemical methods of Li-ion batteries. The first part of the project is devoted to the characteristics of Li-ion batteries, electrochemical reactions and characteristics of electrode materials. Consenquetial part is concentrated on preparation and measurement of elektrolyte EC : DMC with 1M LiPF6. The elektrolyte was investigated using galvanostatic method, cyclic voltammetry and impedance spectroscopy.

No description available.

The Lithium-ion (Li-ion) battery is one of the major topics currently studied as a potential way to help in reducing greenhouse gas emissions. Major car manufacturers are interested in adapting the Li-ion battery in the power trains of Plug-in Hybrid Electric Vehicles (PHEV) to improve fuel efficiency. Materials currently used for Li-ion batteries are LiCoO2 (LCO) and graphite—the first materials successfully integrated by Sony into Li-ion batteries. However, due to the high cost and polluting effect of cobalt (Co), and the low volumetric capacity of graphite, new materials are being sought out. LiFePO4 (LFP) and SnO2 are both good alternatives for the cathode and anode materials in Li-ion batteries. But, to create high-performance batteries, nano-sized carbon-coated particles of LFP and SnO2 are required. The present work attempts to develop a new synthesis method for these materials: organic template-assisted synthesis for three-dimensionally ordered macroporous (3DOM) LFP and porous SnO2. With the newly developed synthesis, highly pure materials were successfully synthesized and tested in Li-ion batteries. The obtained capacity for LFP was 158m Ah/g, which is equivalent to 93% of the theoretical capacity. The obtained capacity for SnO2 was 700 mAh/g, which is equivalent to 90% of the theoretical capacity. Moreover, Hybrid Pulse Power Characterization (HPPC) was used to test LFP and LCO for comparison and feasibility in PHEVs. HPPC is generally used to test the feasibility and capacity fade for PHEVs. It simulates battery use in various driving conditions of PHEVs to study pulse energy consumption and regeneration. In this case, HPPC was conducted on a half-cell battery for the first time to study the phenomena on a single active material, LFP or LCO. Based on the HPPC results, LFP proved to be more practical for use in PHEVs.

No description available.

No description available.

Η παρούσα διπλωματική εργασία, η οποία εκπονήθηκε στο Εργαστήριο Ηλεκτρομηχανικής Μετατροπής Ενέργειας του Τμήματος Ηλεκτρολόγων Μηχανικών και Τεχνολογίας Υπολογιστών της Πολυτεχνικής Σχολής του Πανεπιστημίου Πατρών, πραγματεύεται την κατασκευή ενός ηλεκτρικού δικύκλου. Σκοπός είναι η κατασκευή και ο έλεγχος ενός ηλεκτρικού ποδηλάτου και συγκεκριμένα ο σχεδιασμός και η εγκατάσταση ενός κατάλληλου ηλεκτροκινητήριου συστήματος σε ένα συμβατικό ποδήλατο. Αρχικά γίνεται μια σύντομη περιγραφή των συμβατικών και των ηλεκτρικών ποδηλάτων, η οποία περιλαμβάνει την ιστορική εξέλιξή τους, τα μέρη από τα οποία αποτελούνται, τους τύπους στους οποίους διακρίνονται και τα νομικά πλαίσια που διέπουν τη λειτουργία τους. Στη συνέχεια, περιγράφεται το ηλεκτροκινητήριο σύστημα, το οποίο εγκαταστάθηκε στο πλαίσιο του ποδηλάτου που παραχωρήθηκε για το σκοπό αυτό από την εταιρεία Ideal Bikes Μανιατόπουλος Α.Ε., τα κριτήρια επιλογής του κινητήρα, των ηλεκτροχημικών συσσωρευτών και των επιμέρους στοιχείων που το απαρτίζουν. Ακολουθεί η ανάλυση των Brushless μηχανών, τα κατασκευαστικά χαρακτηριστικά και η αρχή λειτουργίας τους. Το επόμενο βήμα είναι η θεωρητική μελέτη του τριφασικού αντιστροφέα τάσης που απαιτείται για την οδήγηση του κινητήρα. Παρατίθενται τα αποτελέσματα που προέκυψαν από την προσομοίωση της λειτουργίας του ηλεκτροκινητήριου συστήματος μέσω του προγράμματος Matlab/Simulink. Κατόπιν, περιγράφεται η κατασκευή του τριφασικού αντιστροφέα τάσης, τα στοιχεία που τον απαρτίζουν και ο λόγος για τον οποίο επιλέχθηκαν. Δίνεται μια σύντομη περιγραφή του μικροελεγκτή που χρησιμοποιήθηκε, των δυνατοτήτων που παρέχει αλλά και η λογική του ελέγχου που υλοποιεί. Τέλος, ακολουθούν οι πειραματικές μετρήσεις και τα συμπεράσματα που προέκυψαν από τη λειτουργία της κατασκευής. / The purpose of this thesis is the construction of an electric two-wheeled vehicle. The work was conducted in the Laboratory of Electromechanical Energy Conversion, in the Department of Electrical and Computer Engineering at University of Patras. The main aim is the study, the construction and the control of an electric bike. In order to achieve this, it is necessary to design and install a suitable electric motor system to a conventional bicycle. Initially, there is a brief overview of the conventional and the electric bicycles, along with their history, their main parts, the types in which they are divided and the legal frameworks that govern their operation. Secondly, the electric motor system, which was installed in the bicycle frame granted for this purpose by the company Ideal Bikes, Nikos Maniatopoulos S.A., the criteria for the selection of the motor and the batteries are described. In addition, there is a short description of Brushless motors, their types and the principle of their operation. Furthermore, the theoretical study of the three phase inverter required for driving the motor is given. Moreover, the results obtained from the simulation of the operation of the motor system through the Matlab / Simulink are provided. The construction of the three phase inverter, the constituent elements and the reason for their selection are also analyzed. Last but not least, there is a short description of the microcontroller which is used and its capabilities, in order to facilitate the study and design of the structure. Finally, the experimental measurements and the conclusions that derive from the construction and the operation of the electric bike are presented and future improvements concerning the construction are proposed.

The stability of electrode/electrolyte interfaces in Li-ion batteries is crucial to the performance, lifetime and safety of the entire battery system. In this work, interface processes have been studied in LiFePO4/graphite Li-ion battery cells.  The first part has focused on improving photoelectron spectroscopy (PES) methodology for making post-mortem battery analyses. Exposure of cycled electrodes to air was shown to influence the surface chemistry of the graphite. A combination of synchrotron and in-house PES has facilitated non-destructive interface depth profiling from the outermost surfaces into the electrode bulk. A better understanding of the chemistry taking place at the anode and cathode interfaces has been achieved. The solid electrolyte interphase (SEI) on a graphite anode was found to be thicker and more inhomogeneous than films formed on cathodes. Dynamic changes in the SEI on cycling and accumulation of lithium close to the carbon surface have been observed.    Two electrolyte additives have also been studied: a film-forming additive propargyl methanesulfonate (PMS) and a flame retardant triphenyl phosphate (TPP). A detailed study was made at ambient and elevated temperature (21 and 60 °C) of interface aging for anodes and cathodes cycled with and without the PMS additive. PMS improved cell capacity retention at both temperatures. Higher SEI stability, relatively constant thickness and lower loss of cyclable lithium are suggested as the main reasons for better cell performance. PMS was also shown to influence the chemical composition on the cathode surface. The TPP flame retardant was shown to be unsuitable for high power applications. Low TPP concentrations had only a minor impact on electrolyte flammability, while larger amounts led to a significant increase in cell polarization. TPP was also shown to influence the interface chemistry at both electrodes. Although the additives studied here may not be the final solution for improved lifetime and safety of commercial batteries, increased understanding has been achieved of the degradation mechanisms in Li-ion cells. A better understanding of interface processes is of vital importance for the future development of safer and more reliable Li-ion batteries.

Submitted by Bruna Rodrigues (bruna92rodrigues@yahoo.com.br) on 2016-09-21T13:28:03Z No. of bitstreams: 1 TesePCSov.pdf: 3513150 bytes, checksum: 7e2e8d6239392979ea285f15e7463f61 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-21T18:25:23Z (GMT) No. of bitstreams: 1 TesePCSov.pdf: 3513150 bytes, checksum: 7e2e8d6239392979ea285f15e7463f61 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-21T18:25:29Z (GMT) No. of bitstreams: 1 TesePCSov.pdf: 3513150 bytes, checksum: 7e2e8d6239392979ea285f15e7463f61 (MD5) / Made available in DSpace on 2016-09-21T18:25:36Z (GMT). No. of bitstreams: 1 TesePCSov.pdf: 3513150 bytes, checksum: 7e2e8d6239392979ea285f15e7463f61 (MD5) Previous issue date: 2015-07-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this work, studies on the optimization of the LiFePO4 synthesis were performed, aiming to obtain a product, at shorter calcination times, with smaller particle size and promising electrochemical properties for applications as cathode material in lithium ion batteries. Crystalline LiFePO4 was synthesized through the combination of carbothermal reduction and microwave-assisted solid-state reaction. The precursors LiOH.H2O, FePO4.4H2O, glucose and graphite were exposed to carbothermal reduction at 200 ºC during 3 h and subsequently calcined by irradiation with microwaves at 800 W for varying times, from 1 to 5 min. The obtained products were analyzed through thermal analysis using TGADTG and DSC curves. Their structural, morphological and electrochemical properties were investigated by means of X-Ray diffractometry, infrared spectroscopy, scanning electron microscopy and cyclic voltammetry, respectively. The product obtained at 3 min, besides presenting the smallest particle size (100 to 150 nm), was the only one with a crystalline phase and a voltammetric profile characteristic of LiFePO4 between 3,2 and 3,7 V vs. Li/Li+ in a solution of 1 mol L-1 LiClO4 in EC/DMC (1:1 V/V). The electrode was prepared with LiFePO4, acetylene black and PVDF (85:10:5 m/m/m), and the diffusion coefficient of Li ions in the LiFePO4 phase was estimated as 0,29.10–14 cm2 s-1. Galvanostatic charge-discharge tests were performed with this electrode between 3,8 and 3,1 V vs. Li/Li+ under the same experimental conditions as in the cyclic voltammetry. The obtained LiFePO4 presented an initial specific capacity of 100 mA h g-1 at C/4, considering 39,8% of active material. / Neste trabalho foram realizados estudos de otimização da síntese do LiFePO4, buscando obter em menores tempos de calcinação um material com tamanho de partículas menor, com propriedades eletroquímicas promissoras para a aplicação como catodo em baterias de íons lítio, combinando-se uma reação de redução carbotermal à reação em estado sólido assistida por micro-ondas. Uma mistura dos precursores LiOH.H2O, FePO4.4H2O, glicose e grafite foi submetida à redução carbotermal a 200 ºC por 3 h e posteriormente calcinada por radiação de micro-ondas a 800 W, variando-se o tempo de calcinação entre 1 e 5 min. Os produtos obtidos foram investigados por análises térmicas através das curvas de TGA-DTG e DSC. Suas propriedades estruturais, morfológicas e eletroquímicas foram investigadas, respectivamente, por difratometria de Raios X, espectroscopia de infravermelho, microscopia eletrônica de varredura e voltametria cíclica. Dentre os produtos obtidos, o material sintetizado a 3 min, além de apresentar tamanho de partículas menor (100 a 150 nm), foi o único que apresentou a fase cristalina e um perfil voltamétrico característico do LiFePO4 no intervalo de potencial de 3,2 a 3,7 V vs. Li/Li+ em meio de LiClO4 1 mol L-1 em EC/DMC (1:1 V/V), utilizando um eletrodo constituído de fosfato litiado, negro de acetileno e PVDF (85:10:5 m/m/m). O coeficiente de difusão de íons Li no LiFePO4 obtido foi estimado como 0,29.10–14 cm2 s-1. Testes galvanostáticos de carga e descarga foram realizados com este material nas mesmas condições experimentais da voltametria cíclica, com potenciais de corte de 3,8 V e 3,1 V vs. Li/Li+. Valores de capacidade específica inicial de aproximadamente 100 mA h g-1 foram obtidos a C/4, considerando 39,8% de material ativo.

此論文係以商業營運計畫為撰寫架構，希望透過創新的異業整合方式，結合油品銷售業者、整車製造廠、鋰鐵磷電池廠和資、通訊電子業者等跨越不同產業的廠商，以電動車為基礎打造全新的營運模式，並為各領域之廠商在現有事業之外另闢新的產銷契機。 本計畫以在台灣擁有最多加油站數的台灣中油公司為核心，建議由其負責主導與整合，並創設名為「綠寶石電池」的新公司，借重中油的加油站據點等無人可及的實體通路優勢來吸引不同電動車與鋰鐵磷電池的上、下游業者一起共相盛舉，進而共同在即將爆發大成長商機的電動車與鋰鐵磷電池市場獲得領先地位。 中油可將裕隆等整車製造廠、鋰鐵磷電池廠商和資、通訊電子業者視為可提供營運綜效的策略投資與合作夥伴，初期規劃的總資本額為新台幣100億元，由中油負責其中的40~50億元，希望引進的其他投資金額分別由裕隆等數家整車製造廠投資共約30~40億元，以及數家具備優異技術開發與量產能力的鋰鐵磷正極材料廠商共約20~30億元。 綠寶石計畫投入的市場包括依行駛里程收取充電費用，舊鋰鐵磷電池儲電模組轉售，和各種娛樂休閒與商務的資、通訊與網路服務等，自2011年開始營運，預估2011年到2015年的總營收分別為22.85億元、59.82億元、96.78億元、136.95億元和179.11億元。 其中，來自依行駛里程收取充電費用的收入約佔總營收60%，自舊鋰鐵磷電池儲電模組轉售業務所取得的營業收入約佔總營收30%~35%，來自資、通訊網路服務的營業收入則佔總營收的5%~10%左右。 綠寶石預估在2013年即可正式轉虧為盈，稅前淨利達22.92億元，每股獲利可達1.72元，2014年與2015年的營運將更上層樓，稅前獲利分別為43.95億元和77.06億元，每股獲利可達4.40元和7.71元。