A Search for Muon Neutrinos in Coincidence with Gamma-Ray Bursts in the Southern Hemisphere Sky Using the IceCube Neutrino Observatory

The origin of observed ultra-high energy cosmic rays (UHECRs, energies in excess of $10^{18.5}$ eV) remains unknown, as extragalactic magnetic fields deflect these charged particles from their true origin. Interactions of these UHECRs at their source would invariably produce high energy neutrinos. As these neutrinos are chargeless and nearly massless, their propagation through the universe is unimpeded and their detection can be correlated with the origin of UHECRs. Gamma-ray bursts (GRBs) are one of the few possible origins for UHECRs, observed as short, immensely bright outbursts of gamma-rays at cosmological distances. The energy density of GRBs in the universe is capable of explaining the measured UHECR flux, making them promising UHECR sources. Interactions between UHECRs and the prompt gamma-ray emission of a GRB would produce neutrinos that would be detected in coincidence with the GRB’s gamma-ray emission. The IceCube Neutrino Observatory can be used to search for these neutrinos in coincidence with GRBs, detecting neutrinos through the Cherenkov radiation emitted by secondary charged particles produced in neutrino interactions in the South Pole glacial ice. Restricting these searches to be in coincidence with GRB gamma-ray emis- sion, analyses can be performed with very little atmospheric background. Previous searches have focused on detecting muon tracks from muon neutrino interactions fromthe Northern Hemisphere, where the Earth shields IceCube’s primary background of atmospheric muons, or spherical cascade events from neutrinos of all flavors from the entire sky, with no compelling neutrino signal found. Neutrino searches from GRBs with IceCube have been extended to a search for muon tracks in the Southern Hemisphere in coincidence with 664 GRBs over five years of IceCube data in this dissertation. Though this region of the sky contains IceCube’s primary background of atmospheric muons, it is also where IceCube is most sensitive to neutrinos at the very highest energies as Earth absorption in the Northern Hemisphere becomes relevant. As previous neutrino searches have strongly constrained neutrino production in GRBs, a new per-GRB analysis is introduced for the first time to discover neutrinos in coincidence with possibly rare neutrino-bright GRBs. A stacked analysis is also performed to discover a weak neutrino signal distributed over many GRBs. Results of this search are found to be consistent with atmospheric muon backgrounds. Combining this result with previously published searches for muon neutrino tracks in the Northern Hemisphere, cascade event searches over the entire sky, and an extension of the Northern Hemisphere track search in three additional years of IceCube data that is consistent with atmospheric backgrounds, the most stringent limits yet can be placed on prompt neutrino production in GRBs, which increasingly disfavor GRBs as primary sources of UHECRs in current GRB models.

MEMS SENSOR PLATFORMS FOR IN SITU CHARACTERIZATION OF LI-ION BATTERY ELECTRODES

Lithium-ion batteries provide high energy density while being compact and light-weight and are the most pervasive energy storage technology powering portable electronic devices such as smartphones, laptops, and tablet PCs. Considerable efforts have been made to develop new electrode materials with ever higher capacity, while being able to maintain long cycle life. A key challenge in those efforts has been characterizing and understanding these materials during battery operation. While it is generally accepted that the repeated strain/stress cycles play a role in long-term battery degradation, the detailed mechanisms creating these mechanical effects and the damage they create still remain unclear. Therefore, development of techniques which are capable of capturing in real time the microstructural changes and the associated stress during operation are crucial for unravelling lithium-ion battery degradation mechanisms and further improving lithium-ion battery performance. This dissertation presents the development of two microelectromechanical systems sensor platforms for in situ characterization of stress and microstructural changes in thin film lithium-ion battery electrodes, which can be leveraged as a characterization platform for advancing battery performance. First, a Fabry-Perot microelectromechanical systems sensor based in situ characterization platform is developed which allows simultaneous measurement of microstructural changes using Raman spectroscopy in parallel with qualitative stress changes via optical interferometry. Evolutions in the microstructure creating a Raman shift from 145 cm−1 to 154 cm−1 and stress in the various crystal phases in the LixV2O5 system are observed, including both reversible and irreversible phase transitions. Also, a unique way of controlling electrochemically-driven stress and stress gradient in lithium-ion battery electrodes is demonstrated using the Fabry-Perot microelectromechanical systems sensor integrated with an optical measurement setup. By stacking alternately stressed layers, the average stress in the stacked electrode is greatly reduced by 75% compared to an unmodified electrode. After 2,000 discharge-charge cycles, the stacked electrodes retain only 83% of their maximum capacity while unmodified electrodes retain 91%, illuminating the importance of the stress gradient within the electrode. Second, a buckled membrane microelectromechanical systems sensor is developed to enable in situ characterization of quantitative stress and microstructure evolutions in a V2O5 lithium-ion battery cathode by integrating atomic force microscopy and Raman spectroscopy. Using dual-mode measurements in the voltage range of the voltage range of 2.8V – 3.5V, both the induced stress (~ 40 MPa) and Raman intensity changes due to lithium cycling are observed. Upon lithium insertion, tensile stress in the V2O5 increases gradually until the α- to ε-phase and ε- to δ-phase transitions occur. The Raman intensity change at 148 cm−1 shows that the level of disorder increases during lithium insertion and progressively recovers the V2O5 lattice during lithium extraction. Results are in good agreement with the expected mechanical behavior and disorder change in V2O5, highlighting the potential of microelectromechanical systems as enabling tools for advanced scientific investigations. The work presented here will be eventually utilized for optimization of thin film battery electrode performance by achieving fundamental understanding of how stress and microstructural changes are correlated, which will also provide valuable insight into a battery performance degradation mechanism.

OBSERVATIONS AND EMISSIONS OF ENERGY-ASSOCIATED OZONE PRECURSORS IN THE MID-ATLANTIC UNITED STATES

Surface ozone is formed in the presence of NOx (NO + NO2) and volatile organic compounds (VOCs) and is hazardous to human health. A better understanding of these precursors is needed for developing effective policies to improve air quality. To evaluate the year-to-year changes in source contributions to total VOCs, Positive Matrix Factorization (PMF) was used to perform source apportionment using available hourly observations from June through August at a Photochemical Assessment Monitoring Station (PAMS) in Essex, MD for each year from 2007-2015. Results suggest that while gasoline and vehicle exhaust emissions have fallen, the contribution of natural gas sources to total VOCs has risen. To investigate this increasing natural gas influence, ethane measurements from PAMS sites in Essex, MD and Washington, D.C. were examined. Following a period of decline, daytime ethane concentrations have increased significantly after 2009. This trend appears to be linked with the rapid shale gas production in upwind, neighboring states, especially Pennsylvania and West Virginia. Back-trajectory analyses similarly show that ethane concentrations at these monitors were significantly greater if air parcels had passed through counties containing a high density of unconventional natural gas wells. In addition to VOC emissions, the compressors and engines involved with hydraulic fracturing operations also emit NOx and particulate matter (PM). The Community Multi-scale Air Quality (CMAQ) Model was used to simulate air quality for the Eastern U.S. in 2020, including emissions from shale gas operations in the Appalachian Basin. Predicted concentrations of ozone and PM show the largest decreases when these natural gas resources are hypothetically used to convert coal-fired power plants, despite the increased emissions from hydraulic fracturing operations expanded into all possible shale regions in the Appalachian Basin. While not as clean as burning natural gas, emissions of NOx from coal-fired power plants can be reduced by utilizing post-combustion controls. However, even though capital investment has already been made, these controls are not always operated at optimal rates. CMAQ simulations for the Eastern U.S. in 2018 show ozone concentrations decrease by ~5 ppb when controls on coal-fired power plants limit NOx emissions to historically best rates.

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.