| 1. |
- Forsberg, Viviane, 1981-
(författare)
-
Liquid Exfoliation of Molybdenum Disulfide for Inkjet Printing
- 2016
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Since the discovery of graphene, substantial effort has been put toward the synthesis and production of 2D materials. Developing scalable methods for the production of high-quality exfoliated nanosheets has proved a significant challenge. To date, the most promising scalable method for achieving these materials is through the liquid-based exfoliation (LBE) of nanosheetsin solvents. Thin films of nanosheets in dispersion can be modified with additives to produce 2D inks for printed electronics using inkjet printing. This is the most promising method for the deposition of such materials onto any substrate on an industrial production level. Although well-developed metallic and organic printed electronic inks exist on the market, there is still a need to improve or develop new inks based on semiconductor materials such as transition metal dichalcogenides (TMDs) that are stable, have good jetting conditions and deliver good printing quality.The inertness and mechanical properties of layered materials such as molybdenum disulfide (MoS2) make them ideally suited for printed electronics and solution processing. In addition,the high electron mobility of the layered semiconductors, make them a candidate to become a high-performance semiconductor material in printed electronics. Together, these features make MoS2 a simple and robust material with good semiconducting properties that is also suitable for solution coating and printing. It is also environmentally safe.The method described in this thesis could be easily employed to exfoliate many types of 2D materials in liquids. It consists of two exfoliation steps, one based on mechanical exfoliation of the bulk powder utilizing sand paper, and the other inthe liquid dispersion, using probe sonication to liquid-exfoliate the nanosheets. The dispersions, which were prepared in surfactant solution, were decanted, and the supernatant was collected and used for printing tests performed with a Dimatix inkjetprinter. The printing test shows that it is possible to use the MoS2 dispersion as a printed electronics inkjet ink and that optimization for specific printer and substrate combinations should be performed. There should also be advances in ink development, which would improve the drop formation and break-off at the inkjet printing nozzles, the ink jetting and, consequently, the printing quality.
|
|
| 2. |
- Li, Changle, 1992-
(författare)
-
First-Principles Investigation of Bulk and Interfacial Properties of Cu-Co Binary System
- 2021
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Due to the complex nature of phase interfaces, acquiring precise interfacial energies is usually a big challenge for both experimental measurements and computational modelings. In this thesis, we put forward an efficient route for assessing the temperature dependence of the interfacial energy using density functional theory (DFT). For our investigations, we select the Cu-Co binary system as a model with large miscibility gap. Most of the first-principles calculations presented here are carried out using the exact muffin-tin orbitals (EMTO) method in combination with the coherent potential approximation (CPA), but other alternative DFT methods are also included in the various stages of the project.The first step is to acquire an accurate thermodynamical description of the Cu-Co binary system. We assess the quality of the predicted thermodynamic properties by an effort to reproduce the phase diagram for the entire range of composition using first-principles calculations and alloy theory. The calculations are performed for the random Cu-Co alloys with face-centered cubic (fcc) structure at both ferromagnetic (FM) and paramagnetic (PM) states, depending on the composition. We demonstrate that the equilibrium volumes and magnetic states are crucial for the proper description of the magnetic entropy of the Cu-Co system at elevated temperatures. More specifically, the contribution of magnetic entropy to the free energy in the Cu-rich region obtained for the PM state turns out to be critical. Furthermore, the adopted equilibrium volumes strongly affect the contribution of the vibrational entropy to the free energy. When all effects are properly accounted for, we find that the ab initio phase diagram of the Cu-Co system agrees well with the Thermo-Calc phase diagram and the experimental observations.The Cu-Co system has a large miscibility gap. The interface between the decomposed Cu-rich and Co-rich phases plays critical roles in the precipitation nucleation and growth, therefore having huge effects on the physical and mechanical properties of the alloys. Therefore, adopting the thermodynamical properties of the bulk Cu-Co alloys successfully obtained by our ab initio calculations, we go further and investigate the interfacial properties of the Cu-Co alloys using a coherent interface model. The chemical, magnetic, and strain energy contributions to the formation energy of the interfaces are analyzed separately. We find that the chemical interfacial energies generally decrease with increasing concentrations, namely when the compositions accross the interface become more homogenous. We identify a sizable contribution to the interfacial energies from the magnetic effects. The temperature dependence of the interfacial energy is estimated, to the first-order approximation, through considering how the equilibrium compositions of the two phases vary at different temperatures. Our results show that the temperature dependence of the interfacial energy originates primarily from the temperature-induced increase of the mutual solubility of the alloy constituents and the loss of the magnetic long range order near the Curie temperature. Our ab initio results are compared with the experimental data as well as with those extracted from Thermo-Calc modeling. The present thesis provides an atomic-level description of the bulk and interfacial properties of the Cu-Co binary system using quantum mechanics simulations. This approach is believed to be useful for a complete thermodynamical description of other similar immiscible alloy systems as well from first-principles.
|
|
| 3. |
- Li, Jiajia, 1995-
(författare)
-
Constructing Poly(Ionic Liquid)s-Based Composite Solid State Electrolytes and Application in Lithium Metal Batteries
- 2023
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The pursuit of reliable and high-performance batteries has fueled extensive research into new battery chemistries and materials, aiming to enhance the current lithium-ion battery technologies in terms of energy density and safety. Among the potential advancements, solid-state batteries (SSBs) have captured significant attention as the next-generation energy storage technology. One key factor contributing to their appeal is the utilization of solid-state electrolytes (SSEs) with a wide electrochemical stability window (ESW), making SSBs compatible with high-voltage cathodes. The energy density of SSBs can be further improved by employing the “holy-grail” anode, Li-metal, which boasts the lowest working voltage (-3.04 V vs. Li+/Li) and an ultrahigh theoretical capacity (3860 mAh g−1). Consequently, these batteries are referred to as lithium metal batteries (LMBs). However, realizing the full potential of LMBs presents formidable challenge, including the low ionic conductivity of current SSEs, large interfacial resistance between SSE and electrodes, uncontrollable interfacial reactions, and the growth of Li dendrites. Typically, SSEs can be categorized into three types. Among these, solid composite electrolytes (SCEs) are considered the most promising choice for solid-state LMBs due to their combination of high ionic conductivity and excellent mechanical strength from inorganic solid electrolytes (ISEs) and the flexibility and good interface compatibility provided by solid polymer electrolytes (SPEs). Polymeric ionic liquids (PolyILs), which contain both ionic liquid-like moieties and polymer frameworks, have emerged as highly attractive alternatives to traditional polymers in SCEs. The overall objective of this thesis was to develop PolyIL-based SCEs with enhanced ionic conductivity, wide ESW, high Li+ transference number, and reduced electrodes/electrolyte interface resistance. The main progress achieved in this thesis is as follows:1. We selected three F-based Li-salts to prepare SPEs using poly(ethylene oxide) and polyimide. The investigation focused on assessing the impact of molecular size, F content, and chemical structures (F-connecting bonds) of these Li-salts. Additionally, we aimed to uncover the formation process of LiF in the solid electrolyte interphase (SEI). The result revealed that the F-connecting bond plays a more significant role than the molecular size and F element content, resulting in slightly better cell performance using LiPFSI compared to LiTFSI and substantially better performance compared to LiFSI. The preferential breakage of bonds in LiPFSI was found to be related to its position to Li anode. Consequently, we proposed the LiPFSI reduction mechanism based on these findings.2. Using the template method, we synthesized a monolayer SCE with enhanced Li+ transference number and high ionic conductivity. In this study, boron nitride (BN) nanosheets with a high specific surface area and richly porous structure were employed as inert inorganic filler. These BN nanosheets played a crucial role in homogenizing the Li+ flux and facilitating the Li+ transmission to suppress Li dendrite growth. When integrated into a LiFePO4//Li cell with the optimized SCE, the assembled battery demonstrated remarkable cycling performance. 3. A monolayer GSCE with multifunctionality was synthesized via a natural sedimentation and subsequent UV-curing polymerization technique. This innovative method capitalizes on intrinsic gravity, allowing for the integration of multiple functions within a single layer, thereby eliminating the additional interlayer resistance. The developed GSCE provides an optimum Li+ transportation path and enhanced Li+ transference number, leading to an enhanced ionic conductivity and a long cycle life of Li//Li cells and SSLMBs. Compared with the monolayer uniform SCEs, the gradient structure also alleviates the uncoordinated thermal expansion between fillers and PolyIL, avoiding increased stress during the cycle and battery capacity fade.
|
|
| 4. |
- Zhang, Pimin, 1990-
(författare)
-
Oxidation behaviour of MCrAlX coatings : effect of surface treatment and an Al-activity based life criterion
- 2018
-
Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- MCrAlY coatings (M=Ni and/or Co) have been widely used for the protection of superalloy components against oxidation and hot corrosion in the hot sections of gas turbines. The drive to improve engine combustion efficiency while reducing emissions by increasing the operation temperature brings a big challenge for coating design. As a result, the need for improvement of MCrAlY coatings for better oxidation resistance is essential.Formation of a stable, dense, continuous, and slow-growing α-Al2O3 layer, on the MCrAlY coating surface, is the key to oxidation protection, since the protective α-Al2O3 scale offers superior oxidation resistance due to its lower oxygen-diffusion rate as compared with other oxides. The ability of a MCrAlY coating to form and maintain such a protective scale depends on the coating composition and microstructure, and can be improved through optimization of deposition parameters, modification of coating surface conditions, and so on. Part of this thesis work focuses on studying the effect of post-deposition surface treatments on the oxidation behavior of MCrAlX coatings (X can be yttrium and/or other minor alloying elements). The aim is to gain fundamental understanding of alumina scale evolution during oxidation which is important for achieving improved oxidation resistance of MCrAlX coatings. Oxide scale formed on coatings at initial oxidation stage and the effect of surface treatment were investigated by a multi-approach study combining photo-stimulated luminescence, microstructural observation and weight gain. Results showed that both mechanically polished and shot-peened coatings exhibited superior performance due to rapid formation of α-Al2O3 fully covering the coating and suppressing growth of transient alumina, assisted by the high density of α-Al2O3 nuclei on surface treatment induced defects. The early development of a two-layer alumina scale, consisting of an inward-grown inner α-Al2O3 layer and an outer layer transformed from outward-grown transient alumina, resulted in a higher oxide growth rate of the as-sprayed coating. The positive effect of the surface treatments on retarding oxide scale growth and suppressing formation of spinel was also observed in oxidation test up to 1000 hrs.As the oxidation proceeds to the close-to-end stage, a reliable criterion to estimate the capability of coating to form α-Al2O3 is of great importance to accurately evaluate coating lifetime, which is the aim of the other part of the thesis work. Survey of published results on a number of binary Ni-Al and ternary Ni-Cr-Al, Ni-Al-Si systems shows that the empirical Al-concentration based criterion is inadequate to properly predict the formation of a continuous α-Al2O3 scale. On the other hand, correlating the corresponding Al-activity data, calculated from measured chemical compositions using the Thermo-Calc software, to the experimental oxidation results has revealed a temperature dependent, critical Al-activity value for forming continuous α-Al2O3 scale. To validate the criterion, long-term oxidation tests were performed on five MCrAlX coatings with varying compositions and the implementation of the Al-activity based criterion on these coatings successfully predicted α-Al2O3 formation, showing a good agreement with experiment results.
|
|
| 5. |
|
|
