MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.

Nano-Engineering of Densely Packed Electrochemical Energy Storage Architectures by Atomic Layer Deposition

Nanostructures are highly attractive for future electrical energy storage devices because they enable large surface area and short ion transport time through thin electrode layers for high power devices. Significant enhancement in power density of batteries has been achieved by nano-engineered structures, particularly anode and cathode nanostructures spatially separated far apart by a porous membrane and/or a defined electrolyte region. A self-aligned nanostructured battery fully confined within a single nanopore presents a powerful platform to determine the rate performance and cyclability limits of nanostructured storage devices. Atomic layer deposition (ALD) has enabled us to create and evaluate such structures, comprised of nanotubular electrodes and electrolyte confined within anodic aluminum oxide (AAO) nanopores. The V2O5- V2O5 symmetric nanopore battery displays exceptional power-energy performance and cyclability when tested as a massively parallel device (~2billion/cm2), each with ~1m3 volume (~1fL). Cycled between 0.2V and 1.8V, this full cell has capacity retention of 95% at 5C rate and 46% at 150C, with more than 1000 charge/discharge cycles. These results demonstrate the promise of ultrasmall, self-aligned/regular, densely packed nanobattery structures as a testbed to study ionics and electrodics at the nanoscale with various geometrical modifications and as a building block for high performance energy storage systems[1, 2]. Further increase of full cell output potential is also demonstrated in asymmetric full cell configurations with various low voltage anode materials. The asymmetric full cell nanopore batteries, comprised of V2O5 as cathode and prelithiated SnO2 or anatase phase TiO2 as anode, with integrated nanotubular metal current collectors underneath each nanotubular storage electrode, also enabled by ALD. By controlling the amount of lithium ion prelithiated into SnO2 anode, we can tune full cell output voltage in the range of 0.3V and 3V. This asymmetric nanopore battery array displays exceptional rate performance and cyclability. When cycled between 1V and 3V, it has capacity retention of approximately 73% at 200C rate compared to 1C, with only 2% capacity loss after more than 500 charge/discharge cycles. With increased full cell output potential, the asymmetric V2O5-SnO2 nanopore battery shows significantly improved energy and power density. This configuration presents a more realistic test - through its asymmetric (vs symmetric) configuration – of performance and cyclability in nanoconfined environment. This dissertation covers (1) Ultra small electrochemical storage platform design and fabrication, (2) Electron and ion transport in nanostructured electrodes inside a half cell configuration, (3) Ion transport between anode and cathode in confined nanochannels in symmetric full cells, (4) Scale up energy and power density with geometry optimization and low voltage anode materials in asymmetric full cell configurations. As a supplement, selective growth of ALD to improve graphene conductance will also be discussed[3]. References: 1. Liu, C., et al., (Invited) A Rational Design for Batteries at Nanoscale by Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 23-30. 2. Liu, C.Y., et al., An all-in-one nanopore battery array. Nature Nanotechnology, 2014. 9(12): p. 1031-1039. 3. Liu, C., et al., Improving Graphene Conductivity through Selective Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 133-138.

Understanding Co-translational Protein Targeting and Lithium Dendrite Formation through Free Energy Simulations and Coarse-Grained Models

We describe the application of alchemical free energy methods and coarse-grained models to study two key problems: (i) co-translational protein targeting and insertion to direct membrane proteins to the endoplasmic reticulum for proper localization and folding, (ii) lithium dendrite formation during recharging of lithium metal batteries. We show that conformational changes in the signal recognition particle, a central component of the protein targeting machinery, confer additional specificity during the the recognition of signal sequences. We then develop a three-dimensional coarse-grained model to study the long-timescale dynamics of membrane protein integration at the translocon and a framework for the calculation of binding free energies between the ribosome and translocon. Finally, we develop a coarse-grained model to capture the dynamics of lithium deposition and dissolution at the electrode interface with time-dependent voltages to show that pulse plating and reverse pulse plating methods can mitigate dendrite growth.

CO-ELECTROPHORETIC DEPOSITION OF LIQUID METAL AND SILICON FOR LITHIUM-ION BATTERY APPLICATION

A low cost electrophoretic deposition (EPD) process was successfully used for liquid metal thin film deposition with a high depositing rate of 0.6 µ/min. Furthermore, silicon nano-powder and liquid metal were then simultaneously deposited as the negative electrode of lithium-ion battery by a technology called co-EPD. The liquid metal was hoping to act as the matrix for silicon particles during lithium ion insertion and distraction. Half-cell testing was performed using as prepared co-EPD sample. An initial discharge capacity of 1500 mAh/g was reported for nano-silicon and galinstan electrode, although the capacity fading issue of these samples was also observed.

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

A NOVEL MODELING AND STATE OF CHARGE ESTIMATION SCHEME FOR LITHIUM-ION BATTERIES

Lithium Ion (Li-Ion) batteries have got attention in recent decades because of their undisputable advantages over other types of batteries. They are used in so many our devices which we need in our daily life such as cell phones, lap top computers, cameras, and so many electronic devices. They also are being used in smart grids technology, stand-alone wind and solar systems, Hybrid Electric Vehicles (HEV), and Plug in Hybrid Electric Vehicles (PHEV). Despite the rapid increase in the use of Lit-ion batteries, the existence of limited battery models also inadequate and very complex models developed by chemists is the lack of useful models a significant matter. A battery management system (BMS) aims to optimize the use of the battery, making the whole system more reliable, durable and cost effective. Perhaps the most important function of the BMS is to provide an estimate of the State of Charge (SOC). SOC is the ratio of available ampere-hour (Ah) in the battery to the total Ah of a fully charged battery. The Open Circuit Voltage (OCV) of a fully relaxed battery has an approximate one-to-one relationship with the SOC. Therefore, if this voltage is known, the SOC can be found. However, the relaxed OCV can only be measured when the battery is relaxed and the internal battery chemistry has reached equilibrium. This thesis focuses on Li-ion battery cell modelling and SOC estimation. In particular, the thesis, introduces a simple but comprehensive model for the battery and a novel on-line, accurate and fast SOC estimation algorithm for the primary purpose of use in electric and hybrid-electric vehicles, and microgrid systems. The thesis aims to (i) form a baseline characterization for dynamic modeling; (ii) provide a tool for use in state-of-charge estimation. The proposed modelling and SOC estimation schemes are validated through comprehensive simulation and experimental results.

Self-healing thermal annealing: surface morphological restructuring control of GaN nanorods

With advances in nanolithography and dry etching, top-down methods of nanostructuring have become a widely used tool for improving the efficiency of optoelectronics. These nano dimensions can offer various benefits to the device performance in terms of light extraction and efficiency, but often at the expense of emission color quality. Broadening of the target emission peak and unwanted yellow luminescence are characteristic defect-related effects due to the ion beam etching damage, particularly for III–N based materials. In this article we focus on GaN based nanorods, showing that through thermal annealing the surface roughness and deformities of the crystal structure can be “self-healed”. Correlative electron microscopy and atomic force microscopy show the change from spherical nanorods to faceted hexagonal structures, revealing the temperature-dependent surface morphology faceting evolution. The faceted nanorods were shown to be strain- and defect-free by cathodoluminescence hyperspectral imaging, micro-Raman, and transmission electron microscopy (TEM). In-situ TEM thermal annealing experiments allowed for real time observation of dislocation movements and surface restructuring observed in ex-situ annealing TEM sampling. This thermal annealing investigation gives new insight into the redistribution path of GaN material and dislocation movement post growth, allowing for improved understanding and in turn advances in optoelectronic device processing of compound semiconductors.

Synthesis and characterization of defective PBAs electrode material

Sodium manganese hexacyanoferrate (NaMnHCF) and its derivatives have been synthesized by simple co-precipitation method with addition of the citric and ascorbic acids respectively. The correspondent crystal structure, water content, chemical formula and a deep structural investigation of prepared samples have been performed by means of the combination of the laboratory and synchrotron techniques (PXRD, FT-IR, TGA, MP-AES and XAS). Electrochemical tests have been done using three-electrode system in sodium nitrate solution at different concentration. From cyclic voltammetry curves, Fe3+/2+ redox peak has been observed, whereas Mn3+/2+ peak was not always evident. Structural stability of the cycled samples has then been tested using 2D XRF imaging and Transmission X-ray microscopy (TXM) techniques. The intercalation of NaMnHCF after 20 cycles has been found by micro-XANES analysis of the highlighted spots which have been found in the XRF images. TXM has also confirmed the appearance of the intercalated particles after 50 cycles comparing the spectra between charged and discharged materials at three different edges (Mn, Fe and N). However, by comparison with lithium samples, it seems obvious that sodium samples are more homogeneous and intercalation is at the very beginning indicating the relative structural stability of sodium manganese hexacyanoferrate electrode material.

Graphite for lithium-ion batteries: mineral analysis and global Material Flow Analysis

Graphite is a mineral commodity used as anode for lithium-ion batteries (LIBs), and its global demand is doomed to increase significantly in the future due to the forecasted global market demand of electric vehicles. Currently, the graphite used to produce LIBs is a mix of synthetic and natural graphite. The first one is produced by the crystallization of petroleum by-products and the second comes from mining, which causes threats related to pollution, social acceptance, and health. This MSc work has the objective of determining compositional and textural characteristics of natural, synthetic, and recycled graphite by using SEM-EDS, XRF, XRD, and TEM analytical techniques and couple these data with dynamic Material Flow Analysis (MFA) models, which have the objective of predicting the future global use of graphite in order to test the hypothesis that natural graphite will no longer be used in the LIB market globally. The mineral analyses reveal that the synthetic graphite samples contain less impurities than the natural graphite, which has a rolled internal structure similar to the recycled one. However, recycled graphite shows fractures and discontinuities of the graphene layers caused by the recycling process, but its rolled internal structure can help the Li-ions’ migration through the fractures. Three dynamic MFA studies have been conducted to test distinct scenarios that include graphite recycling in the period 2022-2050 and it emerges that - irrespective of any considered scenario - there will be an increase of synthetic graphite demand, caused by the limited stocks of battery scrap available. Hence, I conclude that both natural and recycled graphite is doomed to be used in the LIB market in the future, at least until the year 2050 when the stock of recycled graphite production will be enough to supersede natural graphite. In addition, some new improvement in the dismantling and recycling processes are necessary to improve the quality of recycled graphite.

Hemorrhagic Shock Secondary To Button Battery Ingestion.

Button battery ingestion is a frequent pediatric complaint. The serious complications resulting from accidental ingestion have increased significantly over the last two decades due to easy access to gadgets and electronic toys. Over recent years, the increasing use of lithium batteries of diameter 20 mm has brought new challenges, because these are more detrimental to the mucosa, compared with other types, with high morbidity and mortality. The clinical complaints, which are often nonspecific, may lead to delayed diagnosis, thereby increasing the risk of severe complications. A five-year-old boy who had been complaining of abdominal pain for ten days, was brought to the emergency service with a clinical condition of hematemesis that started two hours earlier. On admission, he presented pallor, tachycardia and hypotension. A plain abdominal x-ray produced an image suggestive of a button battery. Digestive endoscopy showed a deep ulcerated lesion in the esophagus without active bleeding. After this procedure, the patient presented profuse hematemesis and severe hypotension, followed by cardiorespiratory arrest, which was reversed. He then underwent emergency exploratory laparotomy and presented a new episode of cardiorespiratory arrest, which he did not survive. The battery was removed through rectal exploration. This case describes a fatal evolution of button battery ingestion with late diagnosis and severe associated injury of the digestive mucosa. A high level of clinical suspicion is essential for preventing this evolution. Preventive strategies are required, as well as health education, with warnings to parents, caregivers and healthcare professionals.

Effect Of Platform Connection And Abutment Material On Stress Distribution In Single Anterior Implant-supported Restorations: A Nonlinear 3-dimensional Finite Element Analysis.

Although various abutment connections and materials have recently been introduced, insufficient data exist regarding the effect of stress distribution on their mechanical performance. The purpose of this study was to investigate the effect of different abutment materials and platform connections on stress distribution in single anterior implant-supported restorations with the finite element method. Nine experimental groups were modeled from the combination of 3 platform connections (external hexagon, internal hexagon, and Morse tapered) and 3 abutment materials (titanium, zirconia, and hybrid) as follows: external hexagon-titanium, external hexagon-zirconia, external hexagon-hybrid, internal hexagon-titanium, internal hexagon-zirconia, internal hexagon-hybrid, Morse tapered-titanium, Morse tapered-zirconia, and Morse tapered-hybrid. Finite element models consisted of a 4×13-mm implant, anatomic abutment, and lithium disilicate central incisor crown cemented over the abutment. The 49 N occlusal loading was applied in 6 steps to simulate the incisal guidance. Equivalent von Mises stress (σvM) was used for both the qualitative and quantitative evaluation of the implant and abutment in all the groups and the maximum (σmax) and minimum (σmin) principal stresses for the numerical comparison of the zirconia parts. The highest abutment σvM occurred in the Morse-tapered groups and the lowest in the external hexagon-hybrid, internal hexagon-titanium, and internal hexagon-hybrid groups. The σmax and σmin values were lower in the hybrid groups than in the zirconia groups. The stress distribution concentrated in the abutment-implant interface in all the groups, regardless of the platform connection or abutment material. The platform connection influenced the stress on abutments more than the abutment material. The stress values for implants were similar among different platform connections, but greater stress concentrations were observed in internal connections.

Synthesis And Antitumor Activity Of Novel 1-substituted Phenyl 3-(2-oxo-1,3,4-oxadiazol-5-yl) β-carbolines And Their Mannich Bases.

A series of novel 1-(substituted phenyl)-3-(2-oxo-1,3,4-oxadiazol-5-yl) β-carbolines (4a-e) and the corresponding Mannich bases 5-9(a-c) were synthesized and evaluated for their in vitro antitumor activity against seven human cancer cell lines. Compounds of 4a-e series showed a broad spectrum of antitumor activity, with GI50 values lower than 15μM for five cell lines. The derivative 4b, having the N,N-dimethylaminophenyl group at C-1, displayed the highest activity with GI50 in the range of 0.67-3.20μM. A high selectivity and potent activity were observed for some Mannich bases, particularly towards resistant ovarian (NCI-ADR/RES) cell lines (5a, 5b, 6a, 6c and 9b), and ovarian (OVCAR-03) cell lines (5b, 6a, 6c, 9a, 9b and 9c). In addition, the interaction of compound 4b with DNA was investigated by using UV and fluorescence spectroscopic analysis. These studies indicated that 4b interact with ctDNA by intercalation binding.

Hyperhoneycomb Iridate β-li_{2}iro_{3} As A Platform For Kitaev Magnetism.

A complex iridium oxide β-Li_{2}IrO_{3} crystallizes in a hyperhoneycomb structure, a three-dimensional analogue of honeycomb lattice, and is found to be a spin-orbital Mott insulator with J_{eff}=1/2 moment. Ir ions are connected to the three neighboring Ir ions via Ir-O_{2}-Ir bonding planes, which very likely gives rise to bond-dependent ferromagnetic interactions between the J_{eff}=1/2 moments, an essential ingredient of Kitaev model with a spin liquid ground state. Dominant ferromagnetic interaction between J_{eff}=1/2 moments is indeed confirmed by the temperature dependence of magnetic susceptibility χ(T) which shows a positive Curie-Weiss temperature θ_{CW}∼+40  K. A magnetic ordering with a very small entropy change, likely associated with a noncollinear arrangement of J_{eff}=1/2 moments, is observed at T_{c}=38  K. With the application of magnetic field to the ordered state, a large moment of more than 0.35  μ_{B}/Ir is induced above 3 T, a substantially polarized J_{eff}=1/2 state. We argue that the close proximity to ferromagnetism and the presence of large fluctuations evidence that the ground state of hyperhoneycomb β-Li_{2}IrO_{3} is located in close proximity of a Kitaev spin liquid.

Utilização de um monitor de vídeo como fonte de alta tensão para eletroforese capilar

This article describes the use of a conventional CRT monitor as a high voltage power supply for capillary electrophoresis. With this monitor, a 23-kV high voltage with a ripple of 1.32% was observed. The reproducibility of the applied high voltage was evaluated by measuring the standard deviations of peak area and migration time for five consecutive injections of a test mixture containing potassium, sodium, and lithium cations at 50 mmol L-1. The errors were about 2.5% and 0.6% for peak area and migration time, respectively. The maximum current tested was about 180 mA, which covers most capillary electrophoresis applications. This system has been successfully used for several months, maintaining the desired level of performance.