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ADVANCED MATERIALS ENABLED BY ATOMIC LAYER DEPOSITION FOR HIGH ENERGY DENSITY RECHARGEABLE BATTERIES
Title
ADVANCED MATERIALS ENABLED BY ATOMIC LAYER DEPOSITION FOR HIGH ENERGY DENSITY RECHARGEABLE BATTERIES
Creator
Chen, Lin
Date
2017, 2017-05
Description
In order to meet the ever increasing energy needs of society and realize the US Department of Energy (DOE)’s target for energy storage,...
Show moreIn order to meet the ever increasing energy needs of society and realize the US Department of Energy (DOE)’s target for energy storage, acquiring a fundamental understanding of the chemical mechanisms in batteries for direct guidance and searching novel advanced materials with high energy density are critical. To realize rechargeable batteries with superior energy density, great cathodes and excellent anodes are required. LiMn2O4 (LMO) has been considered as a simpler surrogate for high energy cathode materials like NMC. Previous studies demonstrated that Al2O3 coatings prepared by atomic layer deposition (ALD) improved the capacity of LMO cathodes. This improvement was attributed to a reduction in surface area and diminished Mn dissolution. However, here we propose a different mechanism for ALD Al2O3 on LMO based on in-situ and ex-situ investigations coupled with density functional theory calculations. We discovered that Al2O3 not only coats the LMO, but also dopes the LMO surface with Al leading to changes in the Mn oxidation state. Different thicknesses of Al2O3 were deposited on nonstoichiometric LiMn2O4 for electrochemical measurements. The LMO treated with one cycle of ALD Al2O3 (1×Al2O3 LMO) to produce a sub-monolayer coating yielded a remarkable initial capacity, 16.4%higher than its uncoated LMO counterpart in full cells. The stability of 1×Al2O3 LMO is also much better as a result of stabilized defects with Al species. Furthermore, 4×Al2O3 LMO demonstrates remarkable capacity retention. Stoichiometric LiMn2O4 was also evaluated with similar improved performance achieved. All superior results, accomplished by great stability and reduced Mn dissolution, is thanks to the synergetic effects of Al-doping and ALD Al2O3 coating.Turning our attention to the anode, we again utilized aluminum oxide ALD to form conformal films on lithium. We elaborately designed and studied, for the first time, the growth mechanism during Al2O3 ALD on lithium metal in-situ quart crystal microbalance (QCM) measurements and found larger growth than expected during the initial cycles. Besides, we discovered that electrolytes show much enhanced wettability on Li with Al2O3 coating, leading to uniform and dense solid electrolyte interphase formation as well as less electrolyte required for battery operations. Also, we achieved more than 2 times longer cycling life with protected Li and obtained Coulombic efficiencies as high as ~98% at a practical current rate of 1 mA/cm2, compared to bare Li. More significantly, when the electrolyte volume is limited (10 μL and 5 μL), the cycling life is about 4 times longer. X-ray photoelectron spectroscopy (XPS) for electrodes after cycles and in-situ transmission electron microscopy (TEM) demonstrate that most of lithium is deposited beneath the film. The more uniform Al2O3 coated lithium after cycling observed by scanning electron microscopy (SEM) verifies that ALD Al2O3 isexceptionally effective to prevent lithium dendrite formation. These results demonstrate that ALD Al2O3 coatings offer a promising route towards energy storage devices that utilize lithium metal anodes, such as Li-S batteries.
Ph.D. in Materials Science and Engineering, May 2017
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SYNTHESIS AND APPLICATION OF ORGANOMETALLIC PRECURSORS FOR TUNGSTEN AND MOLYBDENUM SULFIDE
Title
SYNTHESIS AND APPLICATION OF ORGANOMETALLIC PRECURSORS FOR TUNGSTEN AND MOLYBDENUM SULFIDE
Creator
Liu, Bo
Date
2021
Description
Transition metal chalcogenides (TMCs) have unique properties. They are promising materials for the next generation electrical devices due to...
Show moreTransition metal chalcogenides (TMCs) have unique properties. They are promising materials for the next generation electrical devices due to their suitable band gap, outstanding electron mobility, and controllable atomic thickness. In the last few decades, atomic layer deposition (ALD) has been one of the hottest research frontiers for the fabrication of TMCs films. Signification progress has been made on the varieties of material grown by ALD and the improvement of ALD equipment. However, the fast-evolving microelectronic industry set higher requirements for the ALD application. In the potential electronic fabrication process, low-temperature preparation and non-corrosive procedure are critical for the advanced device architecture. Thus the novel precursor development and the investigation of reaction mechanism are necessary. In addition, as the comprehensive research of film deposition, the prevailing crystallographic defects on the as-prepared films are another appealing thing for us to think about and try to eliminate for better film quality. Therefore, this dissertation will describe the precursor ligand design and its effect on the morphology, the development of W/Mo precursors for tungsten/molybdenum disulfide, and the defect passivation of tungsten diselenide films.In chapter 2, a series of heteroleptic tungsten precursors of tetrathiotungstates (WS42-) were prepared through the facile ligand transfer method. Ligand variation has a significant effect on the crystallinity of the resulting tetrathiotungstate products. Crystalline tetrathiotungstates with preferred orientation were prepared from the reaction of synthesized precursors with H2S at room temperature. Results indicated the morphologies and crystallinities of the tetrathiotungstates can be well controlled by their ligand behaviors which give us a better understanding of the growth mechanism. Chapters 3 and 4 focus on the development of W and Mo precursors for W/Mo disulfide and their performance in wet chemistry reactions and ALD. WS2 can be synthesized at the ambient temperature in solution by the non-redox reaction. WS2 film growth can be achieved at the exciting low temperature of 125°C by ALD. Based on the performance of the tungsten precursor, a new molybdenum dimer precursor with improved reactivity was synthesized, and MoSx can be prepared at the ambient temperature in seconds. X-ray absorption spectroscopy (XAS) was also utilized to investigate the interaction between the organometallic precursor and the SiO2 surface. Chapter 5 will focus on the defect passivation of WSe2 films for the improvement of their electrical performance. Precursors were synthesized, and the wet chemistry method was designed for oxidation removal and vacancy healing. Raman spectroscopy was used as the express characterization method to reveal the treatment results. A promising healing reagent was screened out, and the repaired films were fabricated to field-effect transistors (FETs) for electrical measurements. The final results showed the electrical performance of the WSe2 films was improved after the convenient chemical treatment.
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ATOMIC LAYER DEPOSITION STUDIES OF GOLD AND TUNGSTEN DISULFIDE
Title
ATOMIC LAYER DEPOSITION STUDIES OF GOLD AND TUNGSTEN DISULFIDE
Creator
Liu, Pengfei
Date
2020
Description
In the last few decades, atomic layer deposition (ALD), as a vapor deposition technique and a powerful thin film fabrication method, has...
Show moreIn the last few decades, atomic layer deposition (ALD), as a vapor deposition technique and a powerful thin film fabrication method, has received more and more attention in many fields. A variety of materials can be made by ALD; however, the progress of ALD application is still necessary. Meanwhile, in the process of film fabrication by ALD, the interfacial chemistry is interesting and well worth studying. This dissertation mainly described the process of exploring two materials, gold and tungsten disulfide, fabrication and related content.For the portion of applying ALD in gold thin film deposition, a relatively comprehensive process was explored, studied, analyzed and discussed. Start with the synthesis of the gold precursor, Me2Au(S2CNEt2), the synthetic reaction was explored. By modified the conditions, such as solvent system, twice the yield as previously reported in the literature were achieved. Next, the application of in situ microbalance and infrared spectroscopic technique illuminate the organometallic chemistry during the gold thermal ALD process with Me2Au(S2CNEt2) and ozone. In situ quartz crystal microbalance (QCM) studies give an explanation for the nucleation delay and island growth of gold on a freshly prepared aluminum oxide surface. In situ infrared spectroscopy provides insight to study the surface chemistry during the process, which supports an oxidized gold surface mechanism. The epitaxy of gold thin film was explored by X-ray diffraction. The thermal ALD gold on various substrates reveals out-of-plane orientation, however, in-plane orientation was only existed in the gold film on mica. For the portion of applying ALD in tungsten disulfide fabrication, the early work started with studying the effect of interfaces upon crystallinity. The sulfuration of indium thin film with different interface was explored. Then the idea of “interfaces” was brought into the process of tungsten compounds fabrication. Due to this “indirect” method which made tungsten disulfide by sulfurizing ALD made tungsten compounds (eg. tungsten oxide and tungsten nitride) could not reduce the reaction temperature of tungsten disulfide synthesis to less than 400 °C. Sequently, the “direct” way of tungsten disulfide fabrication which directly utilized tungsten precursor and H2S in ALD system was tested and explored. With the tungsten precursors developed by our group, finally, tungsten disulfide could be fabricated at the temperature as low as 125 °C.
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