Within the framework of this thesis, three innovative electrochemical devices have been studied. A part of the work is devoted to an already existing device, laminates which are debonded by the application of a voltage. This type of material can potentially be used in a wide range of applications, including adhesive joints in vehicles to both reduce the total weight and to simplify the disassembly after end-of-life, enabling an inexpensive recycling process. Although already a functioning device, the development and tailoring of this process was slowed by a lack of knowledge concerning the actual electrochemical processes responsible for the debonding. The laminate studied consisted of an epoxy adhesive, mixed with an ionic liquid, bonding two aluminium foils. The results showed that the electrochemical reaction taking place at the releasing anode interface caused a very large increase in potential during galvanostatic polarization. Scanning electron microscopy images showed reaction products growing out from the electrode surface into the adhesive. These reaction products were believed to cause the debonding through swelling of the anodic interface so rupturing the adhesive bond. The other part of the work in this thesis was aimed at innovative lithium ion (Li‑ion) battery concepts. Commercial Li-ion batteries are two-dimensional thin film constructions utilized in most often mechanically rigid products. Two routes were followed in this thesis. In the first, the aim was flexible batteries that could be used in applications such as bendable reading devices. For this purpose, nano-fibrillated cellulose was used as binder material to make flexible battery components. This was achieved through a water-based filtration process, creating flexible and strong papers. These paper-based battery components showed good mechanical properties as well as good rate capabilities during cycling. The drawback using this method was relatively low coulombic efficiencies believed to originate from side-reactions caused by water remnants in the cellulose structure. The second Li-ion battery route comprised an electrochemical process to coat carbon fibers, shown to perform well as negative electrode in Li-ion batteries, from a monomer solution. The resulting polymer coatings were ~500 nm thick and contained lithium ions. This process could be controlled by mainly salt content in the monomer solution and polarization time, yielding thin and apparently pin-hole free coatings. By utilizing the carbon fiber/polymer composite as integrated electrode and electrolyte, a variety of battery designs could possibly be created, such as three-dimensional batteries and structural batteries. / <p>QC 20130403</p>

This paper aims on the study of developing the firmware program for the monitor chips designed inside the battery set of a Notebook power management system, with the function of monitoring safety during battery charge/discharge via the chips; meanwhile, to estimate the residual capacity of the battery. Owing to the chemistry properties of the battery, whose residual capacity will be affected by the current flow during charge/discharge, high/low of the ambient temperature, fatigue of the battery, as a result, variations of the residual capacity will be presented in non-linear. Therefore, in estimation of the battery residual capacity, using the curve learned from the practical experiment on the battery charge/discharge to be the basis for us to find out the appropriate parameters under the relevant influence factors for revision. It will be more accurate in estimation of the battery residual capacity. At the same time, the battery signal can be transmitted to the managing end of the Notebook power management system via the system management interface, which may enable the system to operate more efficiently.

Natural graphite from cheap and abundant natural sources is an attractive anode material for lithium ion batteries. We report on modifications of such a common natural graphite, whose electrochemical performance is very poor, with solutions of (NH4)2S2O8, concentrated nitric acid, and green chemical solutions such of e.g. hydrogen peroxide and ceric sulfate. These treatments resulted in markedly im-proved electrochemical performance (reversible capacity, coulombic efficiency in the first cycle and cycling behavior). This is attributed to the effective removal of active defects, formation of a new dense surface film consisting of oxides, improvement of the graphite stability, and introduction of more nanochannels/micropores. These changes inhibit the decomposition of electrolyte solution, pre-vent the movement of graphene planes along a-axis direction, and provide more passage and storage sites for lithium. The methods are mild, and the uniformity of the product can be well controlled. Pilot experiments show promising results for their application in industry.

Utilization of amorphous metallic alloy has received much attention for use in numerous microelectronic and electrochemical devices since they provide unique electrical, thermal conductivity, and magnetic properties. To develop these functional properties, it is essential to understand the amorphous structure and the property relationships. First principles calculations provide insight into the structure, thermodynamic stability, electronic and magnetic properties of amorphous alloys. For Ru- and Co-based alloys, the thermodynamic stability was examined by calculating the mixing energy along with those of crystalline counterparts. The amorphous RuP, CoP, RuB, and CoB alloys, become energetically more favorable than their crystalline counterparts at moderate P(B) content. The atomistic structures have well-defined local structures depending on the atomic size ratio and electronic interactions between constituent elements. Their local ordering is attributed to strong p-d hybridization, which contributes to stabilizing the Ru(Co)-P(B) alloys. Surface segregation of P(B) and interfacial adhesion with copper were also studied. Li-X (X: Si, Ge, and Sn) were examined when 1 or 2 Li atoms are inserted into the interstitial sites. Li insertion in the tetrahedral site, which is the most preferable site in the diamond matrix, causes outward displacement and charge localization around the X neighbors, thereby weakening of the covalent bonds leading to destabilization of the host matrix. We present the energetics, structure, electronic and mechanical properties of crystalline and amorphous Li-X (X: Si, Ge, Sn, and Si+Sn) alloys. Our calculations show that the incorporation of Li leads to disintegration of the tetrahedrally-bonded X network into small clusters of various shapes. Electronic structure analysis highlights that the charge transfer leads to weakening or breaking of X bonds with the growing splitting between s and p states, and consequently the Li-X alloys softens with increasing Li content. / text

Today’s information-centered world leads the ever-increasing consumer demand for more powerful, multifunctional portable devices. Additionally, recent developments on long-lasting energy sources and compliant, flexible systems, have introduced new required features to the portable devices industry. For example, wireless sensor networks are in urgent need of self-sustainable, easy-to-deploy, mobile platforms, wirelessly interconnected and accessible through a cloud computing system. The objective of my doctoral work is to develop integration strategies to effectively fabricate mechanically flexible, energy-independent systems, which could empower sensor networks for a great variety of new exciting applications. The first module, flexible electronics, can be achieved through several techniques and materials. Our main focus is to bring mechanical flexibility to the state-of-the-art high performing silicon-based electronics, with billions of ultra-low power, nano-sized transistors. Therefore, we have developed a low-cost batch fabrication process to transform standard, rigid, mono-crystalline silicon (100) wafer with devices, into a thin (5-20 m), mechanically flexible, optically semi-transparent silicon fabric. Recycling of the remaining wafer is possible, enabling generation of multiple fabrics to ensure lowcost and optimal utilization of the whole substrate. We have shown mono, amorphous and poly-crystalline silicon and silicon dioxide fabrics, featuring industry’s most advanced high-/metal-gate based capacitors and transistors. The second module consists on the development of efficient energy scavenging systems. First, we have identified an innovative and relatively young technology, which can address at the same time two of the main concerns of human kind: water and energy. Microbial fuel cells (MFC) are capable of producing energy out the metabolism of bacteria while treating wastewater. We have developed two micro-liter MFC designs, one with carbon nanotubes (CNT)-based anode and the second with a more sustainable design and easy to implement. Power production ranges from 392 to 100 mW/m3 depending on design. Additionally we have explored a flexible thermoelectric generator (0.139 μW/cm2) and a lithium-ion battery (~800 μAh/m2) for back-up energy generation and storage. Future work includes the implementation of a self-powered System-on-Package which gathers together energy generation, storage and consumption. Additionally we are working to demonstrate Complementary Metal-Oxide-Semiconductor (CMOS) circuitry on our flexible platform, as well as memory systems.

Applications of biotechnology in drug delivery and medical instrumentation and energy storage have been gaining popularity. Especially, utilization of biotechnology for energy storage is attracting attention due to its environmentally friendly nature and cost efficiency. In this project, a filamentous bacteriophage, M13, to fabricate metal oxide battery electrodes. M13 phage is 6.5 nm wide and 800 nm long, and can act as a template to produce nano-sized metal oxide particles. A method to prepare manganese oxide electrodes was developed, where the phage is integrated with the oxide into a nanocomposite. The composite material was used to make a high capacity electrode for lithium ion batteries. The M13 templated manganese oxide, Mn3O4, could deliver a high initial capacity of 766 mAh/g, and recorded a stabilized discharge capacity of ~800 mAh/g even after 60 cycles.

Al based alloy powders (Al₈₅Ni₅Y₆Co₂Fe₂) are produced by spray atomization method. High energy ball milling is done to modify the surface topology and particle size for better electrochemical performance. X ray diffraction (XRD), differential scanning calorimeter (DSC), scanning electron microscope (SEM) and transmission electron microscope (TEM) were conducted to characterize the microstructure of the alloys after ball milling. It is found that 5 hours ball milling gives the minimum crystallization and structure change. Thin film sample is also deposited on stainless steel substrate by pulsed laser deposition (PLD) method for electrochemical test. The capacity and reversibility for different samples are compared and discussed. A capacity of 200mAh/g is obtained for the battery with thin film sample as anode and a capacity of 140mAh/g is obtained for that with electrode from powder sample. Both of the batteries give up to 94% capacity retention after 20 cycles. / Singapore-MIT Alliance (SMA)

abstract: The wide-scale use of green technologies such as electric vehicles has been slowed due to insufficient means of storing enough portable energy. Therefore it is critical that efficient storage mediums be developed in order to transform abundant renewable energy into an on-demand source of power. Lithium (Li) ion batteries are seeing a stream of improvements as they are introduced into many consumer electronics, electric vehicles and aircraft, and medical devices. Li-ion batteries are well suited for portable applications because of their high energy-to-weight ratios, high energy densities, and reasonable life cycles. Current research into Li-ion batteries is focused on enhancing its energy density, and by changing the electrode materials, greater energy capacities can be realized. Silicon (Si) is a very attractive option because it has the highest known theoretical charge capacity. Current Si anodes, however, suffer from early capacity fading caused by pulverization from the stresses induced by large volumetric changes that occur during charging and discharging. An innovative system aimed at resolving this issue is being developed. This system incorporates a thin Si film bonded to an elastomeric substrate which is intended to provide the desired stress relief. Non-linear finite element simulations have shown that a significant amount of deformation can be accommodated until a critical threshold of Li concentration is reached; beyond which buckling is induced and a wavy structure appears. When compared to a similar system using rigid substrates where no buckling occurs, the stress is reduced by an order of magnitude, significantly prolonging the life of the Si anode. Thus the stress can be released at high Li-ion diffusion induced strains by buckling the Si thin film. Several aspects of this anode system have been analyzed including studying the effects of charge rate and thin film plasticity, and the results are compared with preliminary empirical measurements to show great promise. This study serves as the basis for a radical resolution to one of the few remaining barriers left in the development of high performing Si based electrodes for Li-ion batteries. / Dissertation/Thesis / Appendix H - Movies (zipped) / M.S. Mechanical Engineering 2011

Orientador: Dayse Iara dos Santos / Banca: Manuel Henrique Leite / Banca: Alejandra Hortencia Miranda González / Resumo: Materiais nanoestruturados vêm sendo amplamente estudados pela comunidade científica, devido às suas propriedades únicas obtidas com o controle da síntese dos materiais. Por meio do controle experimental, esses materiais podem ser utilizados em numerosas áreas, tais como na eletrônica e na fotônica. Dentre os vários métodos químicos, o processo poliol vem sendo utilizado devido à fácil obtenção de nanopartículas de óxidos e metais na sua forma elementar. O presente trabalho teve como objetivo a síntese do óxido de zinco nanoestruturado por meio do método poliol. Diferentes precursores metálicos, tais como acetato de zinco dihidratado, nitrato de zinco hexahidratado, sulfato de zinco monohidratado e cloreto de zinco anidro e diferentes tempos de permanência da síntese foram utilizados para verificar possíveis interferências dos ânions precursores na síntese e na morfologia do óxido de zinco quando obtido. Os materiais obtidos das sínteses foram caracterizados por difração de raios X (DRX), análises térmicas (TG/DTA), medidas de adsorção de gás nitrogênio, microscopia eletrônica de varredura (MEV), microscopia eletrônica de varredura de alta resolução (MEV-FEG) e cronopotenciometria. Por meio destas técnias mostrou-se a viabilidade da obtenção do óxido de zinco nanoestruturado dd maneira direta a partir do acetato de zinco, através de refluxo em etilenoglicol por 2, 4 e 8 horas seguido de lavagem e centrifugação. A menor nanoestrutura encontrada apresentou partículas com dimensão de aproximadamente 25 nm e formato poliédrico, as quais foram observadas pelo FEG. A técnica de cronopotenciometria, representada por meio das curvas de carga/descarga mostraram que a utilização do compósito contendo o óxido de zinco sintetizado apresenta melhores resultados quando comparados ao uso... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Nanostructered materials have been extensively studied by the scientific community due to their unique properties obtained by controlled synthesis of materials. By means of the control of parameters, this new materials can be used in a number of applications in electronic and photonic technology. Among the several methods to obtain nanoparticles or nanostructured materials, the polyol method has been applied because it shows easy procedures to produce nanostructured oxides and elemental metals. The aim of this work is the synthesis of nanostructured zinc oxide, one of the most multifunctional oxides, by the polyol method. Different precursors salts like zinc acetate dihydrate, zinc nitrate hexahydrate, zinc sulfate monohydrate and zinc chloride anhydrate, as well as several times of reflux, were used to investigate the influence of the precursos anions on the synthesis and on the morphology of the crystals of zinc oxide whenever produced. The obtained powders were characterized by X-ray diffraction (DRX), thermal analyses (TG/DTA), and measurements of 'N IND. 2' gas adsorption, scanning electronic and field emission microscopy (MEV and FEG) and chronopotentiometry. These techniques showed the possibility of producing nanostructured zinc oxide in direct way from the reflux in etylenglycol for 2, 4 and 8 hours, followed by washing and centrifugation. The smallest nanostructure observed by FEG presented around 25 nm polyhedral particles. The chronopotentiometry, present charge/discharge curves showing better results for the electrode made of polimer composite containing ZnO nanoparticles than the obtaining results for the oxide alone. The best results showed reversibility of the lithium-ion cell upon 20 cycles, applying 3 μΑ electric current and showing a charge potential up to 4.2 V. / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Mestre

abstract: Origami and Kirigami are two traditional art forms in the world. Origami, from ‘ori’ meaning folding, and ‘kami’ meaning paper is the art of paper folding. Kirigami, from ‘kiri’ meaning cutting, is the art of the combination of paper cutting and paper folding. In this dissertation, Origami and kirigami concepts were successively utilized in making stretchable lithium ion batteries and three-dimensional (3D) silicon structure which both provide excellent mechanical characteristics. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016