Use of welded titanium alloy to aluminium alloy structures in the aerospace industry has a number of potential benefits for both cost and weight saving by enabling titanium to be used only in the most critical parts, with the cheaper and lighter aluminum alloy making up the rest of the structure. However, due to the formation of brittle intermetallic compounds (IMC) at interface and the enormous gap in melting point, the welding of titanium to aluminium remains a major challenge. Solid state welding processes are most likely to be successful since they do not involve any melting, and so issues associated with the large difference in melting point and the high reaction rate of the liquid phase are avoided. In this study, an emerging low energy input solid state welding process - high-power ultrasonic spot welding (USW) was applied to weld Al and Ti (AA6111-T4/Ti6Al4V and AA2139-T8/Ti6Al4V combinations). No obvious intermetallic reaction layer was observed on the Al/Ti interface even using transmission electron microscopy. As a result, the maximum joint strength measured reached the same level as similar Al-Al (AA6111) welds and greatly exceeded those observed in Al-Fe and Al-Mg joints made using the same technique, in which a brittle reaction layer forms rapidly. However, the Al/Ti welds always failed at the weld interface after natural ageing, which is not desirable due to the low fracture energy associated with interfacial fracture mode. By using high resolution STEM-EDS, residual oxides and Si segregation were detected on the as-welded Al/Ti interface, which are thought to be factors that result in the no reaction layer Al/Ti interface. The Si segregation is predicted to be able to increase the weld interface cohesion through thermodynamic calculation. A series of prolonged heat treatment experiments were performed to understand the Al-Ti reaction layer growth kinetics and to explain the lack of reaction layer in as-welded Al-Ti joint. Al3Ti (D022 structure) was the only Al-Ti intermetallic phase observed in the reaction layer (IMC layer). In pure Al/Ti joints, it is found that the very long slow-growth stage of IMC layer is probably caused by the residual oxides on the interface. Calculations show that grain boundary (GB) diffusion makes the major contribution to the effective diffusion coefficient in the Al3Ti layer. In AA2139/Ti joints, the IMC layer growth is significantly slower than that in pure Al/Ti joints. The effects of alloying elements on the IMC layer growth was studied in detail. Cu was observed to segregate on both the Al3Ti grain boundaries and the Al3Ti/Ti interface. Si also segregated on the the Al3Ti/Ti interface and enriched in the Al3Ti layer. Both Cu and Si are thought to retard IMC layer growth. Interestingly small patches of Al were found trapped in the IMC layer; its formation mechanism is discussed. In pure Al/Ti6Al4V joints, the IMC layer growth rate did not change significantly. The presence of V greatly retarded the Al3Ti grain growth at high annealing temperature (630 °C) and suppressed the anisotropic growth of Al3Ti at 600 °C. Overall this study successfully joined Al/Ti by USW and systematically investigated the grain size effect and alloying effects on the Al3Ti layer growth. The present study for the first time: (a) observed the no-IMC-layer Al/Ti weld interface; (b) observed Cu segeration on Al3Ti GBs; (c) quantitatively studied the grain size effect on Al3Ti layer growth kinetics; (d) observed the orientation relationship between trapped Al islands and the adjacent Al3Ti grains; (e) observed that V greatly retarded the anisotropic growth of Al3Ti grains.

Microfibrillated cellulose (MFC) is an alternative material that has been widely studied to enhance the mechanical properties of a polymer matrix due to a number of perceived advantages over traditional plant fibre forms. Mechanical properties of MFC networks were found to depend on parameters such as the modulus of fibrils, bonding strength, porosity, degree of crystallinity, contact area of fibrils and possibly the modulus of the cellulose crystals of the raw materials (cellulose I or II). Even though the longer processing time used to produce MFC was found to yield networks with fewer fibre aggregates, finer fibrils and higher density, some properties, for instance thermal stability and degree of crystallinity, decreased due to the degradation of fibrils caused by the harsh treatment. The aims of this thesis were to assess the mechanical properties and interfaces of composites produced using of a range of MFC materials, prepared using different treatments and from different sources. Raman spectroscopy has been used to detect the molecular orientation of cellulose chains within an MFC network, and to monitor the deformation micromechanics of MFC networks. The Raman band initially located at ~1095 cm-1 obtained from MFC networks was observed to shift towards a lower wavenumber position upon the application of tensile deformation. The intensity of this band as a function of rotation angle of MFC networks was similar, indicating randomly oriented networks of fibrils. From the Raman band shift rate data, the effective moduli of MFC single fibrils produced from pulp were estimated to be in the range of 29-41 GPa. Poly(lactic acid) (PLA) composites reinforced with MFC networks were prepared using compression moulding. Enhanced mechanical properties of MFC reinforced composites were reported, compared to neat PLA films. The mechanical properties of these composites were found to mainly depend on the interaction of the PLA matrix and the reinforcement phase. The mechanical properties of the composites reinforced with dense networks were shown to be dominated by the network properties (fibril-fibril interactions), while matrix-fibril interactions played a major role where more opened networks were used to reinforce a polymer matrix. The penetration of the matrix into the network was found to depend on the pore sizes, fibre width and porosity within the network. It was found that the matrix easily penetrates into the network with a range of mean fibril dimensions, rather than for networks with only fine fibrils present. The stress-transfer process in MFC reinforced PLA composites was monitored using Raman spectroscopy. Greater Raman band shift rates with respect to tensile deformation for the composites were observed compared to pure MFC networks. This indicates that stress is transferred from the PLA matrix to MFC fibrils, supporting the enhancement of the mechanical properties of the composites.

Lithium Ion Batteries (LIBs) are important in today's society, powering cars and mobile devices. LIBs consist of a negative anode commonly made of graphite, and a positive cathode commonly made from transition metal oxides. Between these electrodes are separators and organic solvent based electrolyte. Due to the high potential of LIBs the electrolyte is reduced at the anode. The electrolyte reduction results in the formation of a layer called the Solid Electrolyte Interphase (SEI), which prohibits the further breakdown of the electrolyte. Despite being researched for over50 years, the composition formation of the SEI is still poorly understood. The aim of this project is to develop strategies for efficient identification and classification of various active and intermediate components in the SEI, to, in turn, gain an understanding of the reactions taking place, which will help find routes to stabilize and tailor the composition of the SEI layer for long-term stability and optimal battery performance. For a model gold/li-ion battery electrolyte system, Raman spectra will be obtained using Surface Enhanced Raman Spectroscopy (SERS) in a spectroelectrochemical application where the voltage of the working gold electrode is swept from high to low potentials. Spectra of common components of the SEI as well as similar compounds will be simulated using Density Functional Theory (DFT). The DFT data is also used to calculate the spontaneity of reactions speculated to form the SEI. The simulated data will be validated by comparing it to experimental spectra from pure substances. The spectroelectrochemical SERS results show a clear formation of Li-carbonate at the SERS substrate, as well as the decomposition of the electrolyte into other species, according to the simulated data. It is however shown that there are several issues when modelling spectra, that makes it harder to correlate the simulated spectra with the spectroelectrochemical spectra. These issues include limited knowledge of the structure of the compounds thought to form on the anode surface, and incorrect choices in simulational parameters. To solve these issues, more work is needed in these areas, and the spectroelectrochemical methods used in this thesis needs to be combined with other experimental methods to narrow down the amount of compounds to be modelled. More work is also needed to avoid impurities in the electrolyte. Impurities leads to a thick inorganic layer which prohibits the observation of species in the organic layer.

Diploma thesis is aimed at deposition of thin films on glass fibers using plasma-enhanced chemical vapor deposition from tetravinylsilane as a monomer. Such surface modified glass fibers were used as reinforcements for fabrication of polymer composites with unsaturated polyester resin as a matrix. Chemical and optical properties of prepared thin films were characterized using infared spectroscopy and spectroscopic ellipsometry. An influence of deposited thin films on the shear strength of composite material was observed using short-beam shear test.

Les accumulateurs commerciaux à base de lithium-ion (LIB) utilisent des matériaux à base de carbone (graphite) comme électrode négative; cependant, la technologie atteint sa limite en raison de la faible capacité spécifique théorique. L'objectif de cette thèse est d'étudier le comportement électrochimique de trois nouvelles anodes à haute capacité (SnSb microsturé, Ti3SiC2 anodisé et nanotubes de Si poreux) comme alternatives au graphite, d'identifier les principaux paramètres responsables de la perte de capacité et de proposer une solution commune pour améliorer leurs performances électrochimiques. Ces matériaux d'électrode présentent une bonne performance électrochimique qui les rend prometteurs pour remplacer le carbone en tant qu'électrode négative pour batteries au Li-ion. Cependant, ils présentent une perte de capacité initiale importante qui doit être résolue avant la commercialisation. Les limitations observées sont attribuées à de nombreux facteurs, et en particulier à la formation et la croissance d’une SEI à la surface des matériaux. En raison de la forte perte de la capacité et du manque d’études détaillées sur les matériaux à base d’étain, en particulier le SnSb, nous avons concentré la suite du travail à la formation et la croissance de la SEI sur cette électrode négative. L'évolution des propriétés électriques, de la composition chimique et de la morphologie du SnSb microstructuré a été étudiée en détail pour comprendre son comportement électrochimique. Pour limiter l’effet de la SEI, nous avons proposé d’appliquer un film protecteur à la surface de l'électrode. / Currently, commercial lithium ion batteries (LIBs) use carbon based materials as negative electrode; however the technology is reaching its limit because of the low theoretical specific capacity. The objective of this thesis is to study the electrochemical behaviour of three different new high capacity anodes (SnSb alloy, anodized Ti3SiC2, and Si nanotubes) as alternative to graphite, identify the main parameters responsible for the capacity fading, and propose a versatile solution to improve their electrochemical performance. These electrode materials exhibit good electrochemical performance which makes them promising candidates to replace carbon as a negative electrode for LIBs. However, their limitation due to capacity fading and the large initial irreversible capacity loss must be resolved before commercialization. The observed limitations are attributed to many factors, and particularly, to the formation and growth of SEI layer which is the common factor for all the three electrode materials. Because of the strong capacity fade and lack of many detailed studies on the Sn-based materials, specifically SnSb, we focus our study to investigate the formation and growth of SEI layer on SnSb electrode. The evolution of the electrical, compositional, and morphological properties have been investigated in detail to understand the electrochemical behavior of micron-sized SnSb. To limit the capacity fade, we propose the use of a protective film on the electrode surface. The electrochemical performance of micron-sized SnSb electrode coated with thermoplastic elastomer protective film, namely poly(styrene-b-2-hydroxyethyl acrylate) PS-b-PHEA has been achieved.

No description available.

This study sought to improve the performance of Si-based anodes through the use of hierarchically structured electrodes to provide the nanoscale framework needed to accommodate large volume changes while controlling the interfacial area – which affects solid-electrolyte interphase (SEI) formation. To accomplish this, electrodes were fabricated from vertically aligned carbon nanotubes (VACNT) infiltrated with silicon. On the nanoscale, these electrodes allowed us to adjust the surface area, tube diameter, and silicon layer thickness. On the micro-scale, we have the ability to control the electrode thickness and the incorporation of micro-sized features. Treatment of the interfacial area between the electrolyte and the electrode by encapsulating the electrode controls the stabilization and reduction of unstable SEI. Si-VACNT composite electrodes were prepared by first synthesizing VACNTs on Si wafers using photolithography for catalyst patterning, followed by aligned CNT growth. Nano-layers of silicon were then deposited on the aligned carbon nanotubes via LPCVD at 200mTorr and 535°C. A thin copper film was used as the current collector. Electrochemical testing was performed on the electrodes assembled in a CR2025 coin cell with a metallic Li foil as the counter electrode. The impact of the electrode structure on the capacity at various current densities was investigated. Experimental results demonstrated the importance of control over the superficial area between the electrolyte and the electrode on the performance of silicon-based electrodes for next generation lithium ion batteries. In addition, the results show that Si-VACNT height does not limit Li transport for the range of the conditions tested.

Lithium ion batteries (LIBs) are widely used for storing and converting chemical energy into electrical energy. During battery operation, lithium ions move between electrode materials, enabling energy storage. However, aging mechanisms like lithium plating can negatively impact battery performance and lifetime. Lithium plating occurs when lithium ions are reduced to metallic lithium on the graphite electrode. The undesired Li plating in LIBs leads to dendrite formation that may puncture the separator, causing internal short-circuit and ultimately thermal runaway. This study aims to investigate the internal processes of LIBs during charge and discharge. Two analysis methods are employed: online electrochemical mass spectrometry (OEMS) and acoustic emission monitoring (AEM). OEMS is a gas analysis technique that combines electrochemical measurements with mass spectrometry to provide real-time testing of cells. OEMS allows identifying and quantifying gas evolution/consumption of chemical species. AE is a diagnostic tool, offering monitoring the health of LIBs through detection and characterisation of stress waves produced by parasitic mechano-electrochemical events. The results indicates that the formation of SEI thin film layer, generated gases like hydrogen and ethylene, while consuming carbon dioxide. During induced lithium plating, hydrogen and carbon dioxide were consumed, and ethylene gas was produced, due to new SEI film formation process. The acoustic emission analysis indicated that lithium plating was an active process, whereas SEI formation was less AE active. Further research is needed to understand the relationships and significance of these processes for battery performance and safety. Overall, this study highlighted the importance of investigating aging mechanisms in LIBs to enhance their performance and longevity. By combining OEMS and AE, it was possible to analyse the batteries behaviour during cycling. The evolution of gas and acoustic signals provided insights into the reactions and processes occurring inside the battery during cycling.

Silicon (Si) has been considered as a promising negative electrode material for lithium ion batteries (LIBs) because of its high theoretical capacity, low discharge voltage, and low cost. However, the utilization of Si electrode has been hampered by problems such as slow ionic transport, large stress/strain generation, and unstable solid electrolyte interphase (SEI). These problems severely influence the performance and cycle life of Si electrodes. In general, ionic conduction determines the rate performance of the electrode, while electron leakage through the SEI causes electrolyte decomposition and, thus, causes capacity loss. The goal of this thesis research is to design Si electrodes with high current efficiency and durability through a fundamental understanding of the ionic and electronic conduction in Si and its SEI. Multi-scale physical and chemical processes occur in the electrode during charging and discharging. This thesis, thus, focuses on multi-scale modeling, including developing new methods, to help understand these coupled physical and chemical processes. For example, we developed a new method based on ab initio molecular dynamics to study the effects of stress/strain on Li ion transport in amorphous lithiated Si electrodes. This method not only quantitatively shows the effect of stress on ionic transport in amorphous materials, but also uncovers the underlying atomistic mechanisms. However, the origin of ionic conduction in the inorganic components in SEI is different from that in the amorphous Si electrode. To tackle this problem, we developed a model by separating the problem into two scales: 1) atomistic scale: defect physics and transport in individual SEI components with consideration of the environment, e.g., LiF in equilibrium with Si electrode; 2) mesoscopic scale: defect distribution near the heterogeneous interface based on a space charge model. In addition, to help design better artificial SEI, we further demonstrated a theoretical design of multicomponent SEIs by utilizing the synergetic effect found in the natural SEI. We show that the electrical conduction can be optimized by varying the grain size and volume fraction of two phases in the artificial multicomponent SEI.

This dissertation is focus on the study of solid-electrolyte interphases (SEIs) on advanced lithium ion battery (LIB) anodes. The purposes of this dissertation are to a) develop a methodology to study the properties of SEIs; and b) provide guidelines for designing engineered SEIs. The general knowledge gained through this research will be beneficial for the entire battery research community.