<p>In the pursuit to develop safe and reliable lithium-ion batteries, it is imperative to understand all the variabilities that revolve around electrodes. Current cutting-edge physics-based simulations employ an image-based technique. This technique uses images of electrodes to extract effective properties that are used in these physics-based simulations or employ the simulation on the structure itself. Though the electrode images have spatial variability, various particle morphology, and aberrations that need to be accounted for. This work seeks out to help quantify these variabilities and pinpoint uncertainties that arise in image-based simulations by using machine learning and other data analytic techniques. First, we looked at eighteen graphite electrodes with various particle morphologies to gain a better understanding on how heterogeneity and anisotropy interplay with each other. Moreover, we wanted to see if higher anisotropic particles led to greater heterogeneity, and a higher propensity for changes in effective properties. Multiple image-based algorithms were used to extract tortuosity, conductivity, and elucidate particle shape without the need for segmentation of individual particles. What was found is highly anisotropic particles induces greater heterogeneity in the electrode images, but also tightly packed isotropic particles can do the same. These results arise from porous pathways becoming bottlenecked, resulting in greater likelihood to change values with minimal changes in particle arrangement. Next, a model was deployed to see how these anisotropies and heterogeneities impact electrochemical performance. The thought of whether particle morphology and directional dependencies would have impact on plating energy and heat generation, leading to poor electrochemical performance. By using a pseudo-2D model, we elucidated that the larger the tortuosity the greater the propensity to plate and generate heat. Throughout these studies, it became clear that the segmentation of the greyscale images became the origin for subjectiveness to appear in these studies. We sought to quantify this through machine learning techniques, which employed a Bayesian convolutional neural network. By doing so we aimed to see if image quality impacts uncertainties in our effective properties, and whether we might be able to predict this from image characteristics. Being able to predict effective property uncertainty through image quality did not prove possible, but the ability to predict physics properties based on geometric was able to be done. With the largest uncertain particles occurring at the phase boundaries, morphologies that have a large specific surface area presented with the highest structural uncertainty. Lastly, we wanted to see the impact carbon binder domain morphology uncertainty impacts our effective properties. By using a set of sixteen NMC electrodes, which specify the carbon binder domain weight percentage, we can see how uncertainties in morphology, segmentation, spatial variability, and manufacturing variability impact effective properties. We expected there to be an interplay on which uncertainty impacts various effective properties, and if manufacturing variability plays a large role in determining this. By using surrogate models and statistical methods, we show that there is an eb and flow in uncertainties and effective properties are dependent on which uncertainty is being changed.</p>

<p dir="ltr">Building cooling and ventilation account for nearly 10% of the global electricity consumption. In fact, a recent study even showed that, globally, dehumidification consumes more energy than sensible cooling. One high-efficiency dehumidification technology is selective membrane dehumidification. Selective membranes allow water vapor transport but block air transport. There are two overarching gaps in the literature that are addressed in this dissertation: (1) vacuum membrane dehumidification (VMD) has been rigidly defined as an isothermal process and (2) literature on one of the most efficient VMD system designs, which I will refer to as the “dual module humidity pump,” is limited to ideal thermodynamic modeling (no experimental demonstration or practical system modeling in the current literature).</p><p dir="ltr">This work presents a novel system concept, referred to as the “Active Membrane Energy Exchanger” (AMX), which specifically couples VMD and air cooling into one process to provide the first non-isothermal VMD system concept. The present study provides a wholistic understanding of the benefits and limitations of the AMX approach through both thermodynamic system modeling and experimental protype development and demonstration.</p><p dir="ltr">System models developed in Engineering Equation Solver were used to compare the energy performance of the AMX to other HVAC technologies. These models showed that the AMX could achieve up to 25% annual cooling electricity savings in commercial buildings and up to 60% annual cooling electricity savings in 100% outdoor air applications. Experiments showed that combining cooling and dehumidification increased membrane permeance by up to 40% and increased dehumidification performance by 3-6%. Further demonstration showed the prototype could remove up to 45% of the humidity in the humid air flow but struggled to reject all of that vapor to the exhaust air (mass transfer imbalance). This discovery enabled a practical thermofluid model to estimate theoretical and practical COP limits, which were approximately 40 and 10, respectively. Additionally, a global sensitivity analysis on the new model showed that mechanical design is far more limiting to the performance than material design.</p><p dir="ltr">In summary, this dissertation develops and demonstrates a novel air conditioning technology, from system modeling to prototype demonstration. This work was funded and guided by industry partners, and the results of this dissertation are a major step towards real-world implementation.</p>

<p>Radiative thermal management has become increasingly more relevant within the past few decades due to the avocation for higher efficiency buildings, increases in</p> <p>power densities with decreases in form factors, and cutting-edge technologies for space exploration. This research focuses on engineering coatings with spectrally selective optical properties to achieve ultra-efficient thermal management via passive radiative cooling of both terrestrial and extraterrestrial applications. Terrestrial radiative cooling is a phenomenon of passively cooling exterior surfaces below ambient temperatures by engineering coatings to exhibit low absorptance in the solar spectrum (0.25 μm< λ <2.5 μm), such that a minimal amount of solar irradiation is absorbed, and high emittance in the transmissive portion of the atmosphere (8 μm< λ <13μm), i.e. the sky window, to lose heat to deep-space for a net cooling effect. Deep-space is considered to be an infinite heat sink at 3 K. Extraterrestrial radiative cooling requires the same criteria as terrestrial radiative cooling, however, there is no atmosphere to block a portion of the solar irradiation or the emission from the surface. A key requirement for achieving passive radiative cooling for an ideal emitter during daytime is a total solar reflection >85%, and every 1% above this threshold results in ≈10 W/m2 gain in cooling power. Here, recognizing the broadband nature of solar irradiation, we propose and test a new concept of enhancing solar reflection at a given particle volume concentration by using hierarchical particle sizes, which we hypothesize to scatter each band of the solar spectrum, i.e. VIS, NIR and UV effectively. The hypothesis is tested using a TiO2 nanoparticle-acrylic system. Using the Mie Theory, the scattering and absorption efficiencies and asymmetric parameter</p> <p>of nanoparticles with different sizes and combinations are calculated, then the Monte Carlo Method is used to solve the Radiative Transfer Equation. An overall total solar</p> <p>reflection of ≈91%, which is higher than the ≈78% and ≈88% for 100 nm and 400 nm single particle sizes, respectively was achieved from our hypothesis.</p> <p>With increasingly better RC materials being demonstrated in literature, there is a growing need to understand the real-world utility and benefit of RC with regards</p> <p>to energy savings. A fundamental limit of current radiative cooling systems is that only the top surface facing deep-space can provide the radiative cooling effect, while</p> <p>the bottom surface cannot. Here, we propose and experimentally demonstrate a concept of “concentrated radiative cooling” by nesting a radiative cooling system in a mid-infrared reflective trough, so that the lower surface, which does not contribute to radiative cooling in previous systems, can radiate heat to deep-space via the reflective</p> <p>trough. Field experiments show that the temperature drop of a radiative cooling pipe with the trough is more than double that of the standalone radiative cooling</p> <p>pipe. Furthermore, by integrating the concentrated radiative cooling system as a preconditioner in an air conditioning system, we predict electricity savings of > 75% in Phoenix, AZ, and > 80% in Reno, NV, for a single-story commercial building. We further look into unique applications of radiative cooling for outdoor enclosures</p> <p>of electrical equipment, as demonstrated with a case study of coating pole-type distribution transformers. Utilizing RC paint on the exterior of the case would allow further dissipation of heat to deep-space, as well as, increase the solar reflectance to lessen the heat load on the case. A single 25 kVA pole-type transformer is modeled</p> <p>via CFD with two different exterior case coatings, the standard grey coatings commonly utilized and an RC coating, BaSO4 paint, is analyzed under different operating loads. The RC coating demonstrates great benefits from a thermal management perspective</p> <p>and a gain in the lifetime of the windings. The RC coating cooled a 25 kVA distribution transformer’s core by > 11oC when compared to the standard case and even shows below ambient cooling of the case under minimal heat generations. The lifetime of the distribution transformers was increased by a minimum of 55% when comparing the standard case to the case with a radiative cooling paint based on the Aging Acceleration Factor. A more traditional application of radiative cooling paints is to utilize them on the exterior of buildings to offset the cooling energy demand for air conditioning. This work develops a high-fidelity RC model which accounts for pertinent weather factors including precipitable water, sky clearness, and dynamic convective heat transfer coefficients based on wind speed to further understand the energy savings. We implement our RC model on a single-story residential building to study the impact of RC in every unique ASHRAE climate zone in the United States using the 16 DOE recommended representative cities. Our results show > 7% and > 12% cooling energy savings across the United States for NREL’s building and typical buildings, respectively. Furthermore, warm climates yield the greatest cooling energy savings of up to 22% and 46% for the NREL and the Typical building, respectively. Extraterrestrial radiative thermal management is becoming increasingly pertinent with the development of new space technologies and the need to discover what is beyond</p> <p>our world. Space presents extreme thermal environments for radiative transfer, from a total eclipse case where the body radiates to deep space at 3 K to a full solar load where 1400 W/m2 is radiated onto the surface and a hybrid of both situations. The goal of this work is to engineer micropatterned Lanthanum Strontium Manganite</p> <p>(LSM) Barium Sulfate (BaSO4) coatings as efficient variable emissivity coatings (VECs). The photon transport through the micropatterned system is modeled using</p> <p>geometric optics and Monte Carlo coupled with geometric optics to obtain the coatings reflectivity, transmissivity, and emissivity to predict the ideal reflectivity and</p> <p>emissivity of the micropatterns. Then the micropatterned LSM coatings are experimentally fabricated using screen printing on a BaSO4 paint layer. The coatings are</p> <p>characterized by their temperature-dependent variable emissivity and solar absorptivity from the dual-layer micropatterned coatings. Furthermore, a computational model for a body-mounted cylindrical radiator was developed to investigate the real implications a VEC can have on crewed space vehicles, as well as define some target guidelines for VEC’s to achieve in future technologies.</p>

Nuclear physics tells us a lot about astrophysics, particularly the energy generation in stars. The present work is a thesis in experimental nuclear physics, reporting the results of 30S radioactive beam development for a future experiment directly measuring data to extrapolate the 30S(α,p) stellar reaction rate in Type I X-ray bursts, a phenomena where nuclear explosions occur repeatedly on the surface of accreting neutron stars. On the astrophysics side, the work details basic stellar physics and stellar reaction formalism in Chapter 1, the behaviour of compact stars in Chapter 2, and a full literature review of Type I X-ray bursts in Chapter 3. Nuclear experiments are non-trivial, and the results reported here were not accomplished by the author alone. Stable-beam experiments are technically challenging and involved, but for the case at hand, the halflife of 30S is a mere 1.178 seconds, and in order to measure reaction cross-sections, we must make a beam of the radionuclide 30S in situ and use these rare nuclei immediately in our measurement. Particle accelerator technology and radioactive ion production are treated in Chapter 4, and the experimental facility and nuclear measurement techniques are discussed in some detail in Chapter 5. In order to perform a successful future experiment which allows us to calculate the stellar 30S(α, p) reaction rate, calculations indicate we require a 30S beam of ~ 10^5 particles per second at ~ 32 MeV. Based on our recent beam development experiments in 2006 and 2008, it is believed that such a beam may be fabricated in 2009 according to the results presented in Chapters 6 and 7. We plan to measure the 4He(30S,p) cross-section at astrophysical energies in 2009, and some remarks on the planned (α,p) technique are also elucidated in Chapters 5, 6 and 7. / Thesis / Master of Science (MSc)

The point absorber is one of the most popular types of ocean wave energy converter (WEC) that harvests energy from the ocean. Often such a WEC is deployed in an ocean location with tidal currents or ocean streams, or serves as a mobile platform to power the blue economy. The shape of the floating body, or buoy, of the point absorber type WEC is important for the wave energy capture ratio and for the current drag force. In this work, a new approach to optimize the shape of the point absorber buoy is developed to reduce the ocean current drag force on the buoy while capturing more energy from ocean waves. A specific parametric modeling is constructed to define the shape of the buoy with 12 parameters. The implementation of neural networks significantly reduces the computational time compared to solving hydrodynamics equations for each iteration. And the optimal shape of the buoy is solved using a genetic algorithm with multiple self-defined functions. The final optimal shape of the buoy in a case study reduces 68.7% of current drag force compared to a cylinder-shaped buoy, while maintaining the same level of energy capture ratio from ocean waves. The method presented in this work has the capability to define and optimize a complex buoy shape, and solve for a multi-objective optimization problem. / Master of Science / The marine kinetic energy includes ocean waves power, tidal power, ocean current power, ocean thermal power and river power. The total potential marine kinetic energy in 2021 is 2300 TWh/year, where 1400 TWh/year is from the ocean wave power. To discover and harvest the huge potential power from the marine, researchers have been developed for different types of WECs for several decades. One of the most successful concepts is the point absorber typed WEC, which can extract waver energy from the heaving vibration motion of a floating body and convert the kinetic energy into electrical energy. This thesis presents an optimization strategy to optimize the shape of the floating body to improve power extraction and reduce the installation cost by implementing the machine learning tool and genetic algorithm. Compared with the state-of-the-art optimization strategies, the proposed optimization method allows the floating body to have more parameters in shape changes and reduces the computational cost from minutes to milliseconds. The final optimized floating body shape performs extraordinarily compared to the other two state-of-the-art floating body shapes.

Yes / This study investigates the physical and mechanical properties of 12 biomass wood pellet samples utilised in a power generation, focusing on their implications for energy release and carbon emissions during combustion. Through comprehensive analysis involving bulk density measurements, compression tests, moisture analysis, calorimetry and controlled burning experiments, significant correlations among key properties are identified. Pellets with densities above 1100 kg/m3 demonstrate superior mechanical durability and strength, achieving maximum strengths of 0.6 to 0.8 kN with durability exceeding 99.4%. Optimal moisture content, typically between 6 and 7% is crucial for maximising density, bulk density, mechanical durability and fracture resistance, ensuring robust pellet structure and performance. The research underscores the impact of pellet dimensions, highlighting those longer lengths, > 12 mm enhance durability, while larger diameters > 8 mm exhibit reduced durability. Elemental analysis focusing on calcium, silicon and potassium plays a critical role in predicting and managing combustion system fouling, potentially reducing operational costs. Moreover, the study emphasises the significant influence of oxygen levels during combustion on CO2 emissions, achieving optimal results with moisture content in the 7–8% range for maximum higher heating value (HHV). The moisture content in the 14–15% range represents the lowest CO2 emission. The findings underscore the intricacy of the system and the interplay of parameters with one another. In accordance with the priority of each application, the selection of parameters warrants careful consideration. / This work was supported by the UK Carbon Capture and Storage Research Community (UKCCSRC) and the Engineering and Physical Sciences Research Council (EPSRC) through the UKCCSRC Flexible Funding Call 2022.

<p dir="ltr">Energy storage has become a promising solution to stabilize renewable energy outputs and to solve the peak/off-peak issues of the power grid. Redox flow battery (RFB) possesses separated energy and power, high capacity, long cycle life and safety, and therefore is regarded as a potential candidate of energy storage. In this thesis, we have researched the degradation pathway of TEMPO derivative redoxmers, obtained long-time stable cycling of a non-aqueous RFB with synthetic redoxmers and permselective ceramic membranes, and extended the redox flow approach to the field of water desalination.</p><p dir="ltr">The properties of redoxmers are the main elements that affect RFB performance. Organic redoxmers come to sight due to their facile property improvement based on structural diversity and molecular tailorability. But the majority of reported redoxmers are anolytes; catholytes are less developed. Also, the mechanism of limited long-time cycling stability is still not well understood. In our experiment, we have progressively unraveled a series of degradation mechanisms of TEMPO-based redoxmers, including oxidation, crossover, ring-opening and possibly deoxygenation. The initial candidate, 4-hydro-TEMPO (TEMPOL), presents combined decomposition pathways. The charged oxoammonium species oxidizes the alcohol group (-OH) in its structure to a ketone (C=O) bond and also undergoes a protonation-induced ring-opening side reaction forming an alkene structure, evidenced by the characteristic 13C NMR chemical shifts of C=O and C=C groups. Due to its non-ionic structure, crossover through the anion exchange membrane used in flow cells is another issue that causes capacity loss. A hydroxyl-free TEMPO derivative bearing an anionic sulfonate group (‒SO3‒) also suffers from deprotonation-induced ring opening. By eliminating nucleophilic moiety, we have designed the third TEMPO derivative that has a cationic tetraalkylammonium end group. This molecule exhibits greatly improved cycling stability in flow cells, yet still with slow capacity fading that may hypothetically be a result of parasitic deoxygenation reaction. With the carefully designed analyses, the obtained mechanistic understanding of molecular decomposition has paved the way for rationale structural design toward stable TEMPO catholyte candidates.</p><p dir="ltr">Nonaqueous RFBs hold promise for higher cell voltage and energy density given their wider electrochemically stable voltage windows, but their performance is often plagued by the crossover of redox compounds. In this study, we used permselective lithium superionic conducting (LiSICON) ceramic membranes to enable reliable long-term cycling of organic redox molecules in nonaqueous flow cells. With different solvents on each side, enhanced cell voltages were obtained for a flow battery using viologen-based negolyte and TEMPO-based posolyte molecules. The thermoplastic assembly of the LiSICON membrane realized leakless cell sealing, thus overcoming the mechanical brittleness challenge. As a result, stable cycling was achieved in the flow cells, which showed good capacity retention over an extended test time (e.g. two months).</p><p dir="ltr">Desalination of saline water is becoming an increasingly critical strategy to overcome the global challenge of drinkable water shortage, but current desalination methods are often plagued with major drawbacks of high energy consumption, high capital cost, or low desalination capacity. To address these drawbacks, we have developed a unique continuous-mode redox flow desalination approach capitalizing on the characteristics of redox flow batteries. The operation is based on shuttled redox cycles of very dilute Fe2+/Fe3+ chelate redoxmers with ultralow cell overpotentials. The air instability of Fe2+ chelate is naturally compensated for by its in situ electrochemical generation, making the desalination system capable of operations with electrolytes at any specified state of charge. Under unoptimized conditions, fast desalination rates up to 404.4 mmol·m−2·h−1 and specific energy consumptions as low as 7.9 Wh·molNaCl−1 have been successfully achieved. Interestingly, this desalination method has offered an opportunity of sustainable, distributed drinkable water supplies through direct integration with renewable energy sources such as solar power. Therefore, our redox flow desalination design has demonstrated competitive desalination performance, promising to provide an energy-saving, high-capacity, robust, cost-effective desalination solution.</p>

<p dir="ltr">This research presents a comprehensive study of a 3D Perovskite Solar Cell model using Finite Element Analysis (FEA) and Machine Learning (ML). The research aims (i) to understand how material properties impact solar cell’s performance by applying basic semiconductor physics principles (ii) to investigate how interfacial delamination affects the performance of Perovskite solar cells (iii) to determine the optimum thickness of different layers of the solar cell (iv) to determine the fatigue life cycle of Perovskite layer.</p>

The flow velocity in a river is three-dimensional (3D), turbulent, and varies in time and space. Capturing this variability in field measurements to support studies of river processes has proven particularly challenging. While originally developed to measure discharge, boat-mounted acoustic Doppler current profilers (ADCP) are increasingly used in field studies to quantify flow features including mean velocity, boundary shear stress, and sediment motion. Two survey procedures are typically employed with an ADCP. Moving-vessel (MV) measurements provide spatially-rich velocity data while temporally-rich data are obtained with fixed-vessel (FV) procedures. Given the relative ease of MV measurements, recent work has focused on developing MV procedures that produce comparable results to FV measurements. At the present, results of this work are inconclusive. Additionally, there is a lack of reported data and procedures for FV measurements. This work seeks to develop techniques to present 3D velocity data obtained in natural rivers in a unified framework. This framework is based on a stream-fitted coordinate system defined by the flow direction at a cross section and allows for 3D velocity to be decomposed into streamwise, spanwise, and vertical components. Procedures are developed to assure that the velocity profiles measured at fixed locations are (1) not negatively impacted by the inevitable motion of the ADCP, (2) statistically stationary, and (3) of sufficient record length to determine the mean velocity. The coordinate system allows time-averaged velocity from FV procedures to be compared with spatially-averaged velocity from MV vessels. Significant differences are found between the two survey procedures, particularly for secondary velocity components. Ultimately, integrating results of the two survey procedures leads to an improved representation of the mean flow field. The techniques are applied to data obtained on a study reach on the lower Roanoke River, located in eastern North Carolina. / Ph. D.

<p dir="ltr">This study investigates the electrochemical behavior of molybdenum disulfide (MoS₂) when utilized as an anode material in Li-ion batteries, particularly focusing on the intriguing phenomenon of extra capacity observed beyond theoretical expectations and the unique discharge curve of the first cycle. Employing a robust suite of advanced characterization methods such as in situ and ex situ X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM), the research unravels the complex structural and chemical evolution of MoS₂ throughout its cycling process. A pivotal discovery of the research is the identification of a distinct lithium intercalation mechanism in MoS₂, which leads to the formation of reversible Li_xMoS₂. These phases play a crucial role in contributing to the extra capacity observed in the MoS₂ electrode. Additionally, density functional theory (DFT) calculations have been utilized to explore the potential for overlithiation within MoS₂, suggesting that Li₅MoS₂ could be the most energetically favorable phase during the lithiation-delithiation process. This study also explores the energetics of a Li-rich phase forming on the surface of Li₄MoS2, indicating that this configuration is energetically advantageous and could contribute further to the extra capacity. The incorporation of reduced graphene oxide (RGO) as a conductive additive in MoS₂ electrodes, demonstrating that RGO notably improves the electrochemical performance, rate capability, and durability of the electrodes. These findings are supported by experimental observations and are crucial for advancing the understanding of MoS₂ as a high-capacity anode material. The implications of this research are significant, offering a pathway to optimize the design and composition of electrode materials to exceed traditional performance and longevity limits in Li-ion batteries.</p>