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320 records · Page 18

Electrical Analysis of Pulsed Laser Annealed Poly-Si: Ga/SiOx Passivating Contacts

In this contribution, we examine Ga hyper-doped poly-Si/SiOx contacts realized by pulsed laser melting (PLM). Here, we use Ga as a novel p-type dopant and B as a conventional dopant to induce non-equilibrium doping using an excimer laser. We perform simulations to visualize the maximum melt depth profiles within the poly-Si, with a goal of distributing dopants close to the tunneling oxide, but at the same time preserving the passivation. Hall measurements show that sheet resistance for B is lower than Ga due to its higher solid solubility limit in Si. After comparing the Hall active dopant concentration with the chemical concentration obtained by SIMS measurement, we show nearly 100% activation B activation reaching 10^21 cm-3, while only ~20% activation for Ga. Nevertheless, we achieve active doping concentrations of Ga in poly-Si six times higher than its solid solubility limit in Si (~10^19 cm-3). We compare our Hall mobilities with values in the literature for c-Si and show that B mobilities in laser-treated poly-Si are close to that of the literature value for B, while Ga mobilities are lower, possibly due to additional scattering channels within grain boundaries and deformed lattice. We also compare our results on PLM samples with conventional furnace annealed samples, and we show much higher percent activation and mobilities. Previously, we showed a low contact resistivity of 35.5 +/- 2.4 m..omega..cm2. Here, we further confirm this result by scanning spreading resistance microscopy and Kelvin force nanoprobe microscopy. We demonstrate that our poly-Si: Ga/nCz contact exhibits large drift and diffusion currents under normal cell operating voltage, which widens the laser processing window for a good metal/poly-Si/c-Si contact.

high-efficiency solar cells↗

A Low-Voltage Layered Na 2 TiGeO 5 Anode for Lithium-Ion Battery

Titanium-based anode materials have achieved much progress with the wide studies in lithium-ion batteries. However, these known materials usually possess high discharge voltage platforms and limited energy densities. In this work, a titanium-based oxide of Na 2 TiGeO 5 with layered structure, two-dimensional lamellar frame and exposed highly active (001) facet, exhibiting good electrochemical performance in terms of high capacity (410 mAh g –1 with a current density of 50 mA g –1 ), excellent rate capability and cycling stability with no obvious capacity attenuation after 4000 cycles, is reported. The appropriate discharge voltage plateau at around 0.2 V endows the Na 2 TiGeO 5 anode material high security compared with graphite and high energy density compared with spinel Li 4 Ti 5 O 12 . Combining the electrochemical tests and the density functional theory calculations, the Li + storage mechanism of Na 2 TiGeO 5 is elucidated and the conversion reaction process is revealed. More importantly, this study provides a way to develop low-voltage and high-capacity titanium-based anode materials for efficient energy storage.

25 ENERGY STORAGE↗

Activating Opportunity Zones for Rapid Solar+Storage Deployment in Low Income Communities (Final Report)

Millions of Texans choose their own power provider, giving them the option to have low-cost and even renewable energy delivered through their retail electric plan. However, Texans with less disposable income often pay more for electricity and have limited access to green energy and emergency backup power even though the costs of solar and wind power are at record lows and continue to decline. The Powered for Good initiative aimed to help deliver clean, affordable, 100% renewable electricity to low-income households in Texas’s Competitive Retail Areas, where households can choose their electricity provider. Objectives: The primary goal of this project was to develop and validate one or more affordable solar+storage products (i.e., priced less than of $0.14/kWh) that Retail Electricity Providers (REP) can offer to LI households. The team achieved three objectives: 1. Investigate how to best reduce electricity costs and increase availability of emergency power for LI customers; 2. Build momentum for, and facilitate an approach to, a Texas-based pilot deployment of such solar+storage products, with a goal of greatly expanding this approach to a large segment of the LI population in Texas; 3. Provide the structural framework, finance model, and roadmap to potentially increase investment of solar+storage projects in LI communities across U.S. states when modified to meet their state-specific laws and regulations. The team evaluated the market of viable solutions for low-income Texans through interviews and focus groups with professionals and residents with lived experience. The team then piloted a low-cost retail electric product. Following the pilot, the team developed educational materials, including fact sheets, a Go Green Save Green interactive guide, and an Electricity Bill Analysis Tool. The team is now working to increase power resilience and reduce energy insecurity with micro solar and storage in partnership with local entities in the Harris County area. Key Findings: Informed by Powered for Good research, including the experiences on Texas residents and electricity system experts, the Powered for Good team developed a pilot that was implemented by Energy Well Texas, a new company formed in late 2020. The pilot featured a combination of a 100% clean residential energy offering delivered through the electrical grid plus a selection of batteries, lights and a solar panel that provided participants with varying levels of backup power. For the 8 customers who submitted previous bills, the Energy Well Texas pilot reduced energy bills by about 30%. In Houston, residents earning less than 30% of Area median Income (AMI) spend an average 13% of their income on energy or about $1,555 per year. Repeating the pilot results for these residents could yield $466 in savings per customer or about 4% of their income. While this will not end energy poverty, it is a big step toward that goal. The Powered for Good and Energy Well Texas teams are currently planning their post-pilot phase of service offerings.

14 SOLAR ENERGY↗

Near Room Temperature Solvothermal Growth of Ferroelectric CsPbBr 3 Nanoplatelets with Ultralow Dark Current

CsPbBr 3 exhibits outstanding optoelectronic properties and thermal stability, making it a coveted material for detectors, light-emitting diodes, and solar cells. Despite observations of ferroelectricity in CsPbBr 3 quantum dots, synthesizing bulk ferroelectric CsPbBr 3 crystals has remained elusive, hindering its potential in next-generation optoelectronic devices like optical switches and ferroelectric photovoltaics. Here, a breakthrough is reported: a novel solvothermal technique enabling the growth of ferroelectric CsPbBr 3 nanoplatelets with lateral dimensions in the tens of micrometers. This represents a significant step toward achieving large-area ferroelectric CsPbBr 3 crystals. Unlike traditional methods, this approach allows for growth and crystallization of CsPbBr 3 in alcohol solutions by enhancing precursor solubility. Further this study confirms the ferroelectric nature of these nanoplatelets using second harmonic generation, electrical characterizations, and piezoresponse force microscopy. This work paves the way for utilizing ferroelectric CsPbBr 3 in novel optoelectronic devices, significantly expanding the potential of this material and opening doors for further exploration in this exciting field.

25 ENERGY STORAGE↗

Godiva IV Simulated Radiation Field Characterization and Variance Reduction

Godiva IV is a system comprised of highly enriched uranium alloyed with molybdenum in the form of fuel plate rings. The reactor, along with its predecessors, was designed with the unique ability to satisfy interests in the super-prompt-critical reactor operation space. Originally, the reactor was part of the Los Alamos Critical Experiments Facility (LACEF) at Technical Area-18 (TA-18). The radiation field around Godiva at this facility was well characterized and understood. As a fast neutron system, the neutron spectrum in and around Godiva was close to a Watt Fission spectrum. The Kiva where Godiva IV was located at LACEF was made of thin, sheet metal walls which did not contribute significantly to the neutron spectrum. Following the transition of LACEF to the National Critical Experiments and Research Center (NCERC) in Nevada, Godiva-IV was moved from TA-18 to the Device Assembly Facility (DAF) at the Nevada National Security Site (NNSS). Part of this move brought renewed interest in radiation field characterization. The new facility introduced significant changes to the environment surrounding Godiva, and preliminary foil irradiation results suggested that the room contribution to the neutron spectrum was significant. Unlike at TA-18, a large thermal neutron signature was added to the fast spectrum from Godiva due to significant room return. A primary goal due to the additional complexity that the room return adds to the Godiva IV radiation emission spectrum was the development of an efficient Monte Carlo N-Particle (MCNP) calculation capable of characterizing the neutron spectrum anywhere in the room around Godiva. A campaign of activation foil irradiations and analysis were completed to support the validation of the MCNP model. The modeling of these foils in MCNP can be easily done with a standard volumetric neutron flux tally. However, given the multitude of locations and reaction rates to be modeled, further steps must be taken to increase the efficiency of these calculations in MCNP. During this study, a benchmark model currently under development for Godiva IV was used. A qualitative assessment of the thermal neutron contributors was performed using spatial neutron distribution plots. Additional detail was added to the model based on the qualitative results showing the thermal spectrum’s large sensitivity to hydrogenous material. Neutron energy spectra was evaluated at discrete locations in the room around Godiva to quantify the relative contribution of various components. It was discovered that the concrete walls are the largest contributor to the thermal signature, with minor contributions from plastic components surrounding Godiva. Following these results, two different variance reduction techniques were implemented to improve the problem efficiency in these calculations. In the first approach, an F5 point detector tally was implemented in the standard Godiva IV criticality problem. The second approach involved a weight-window generator implementation with an F5 point detector tally in a fixed source problem. The weight window implementation reduced the runtime from 42739.55 minutes to 1803.34 minutes (computer time), compared to the F5 KCODE implementation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Alternate Methods for Cleaning Zirconium Plate

The United States High Performance Research Reactor Conversion Program identified the need to transition from highly enriched uranium fuel to lowly enriched uranium fuel for high power research and civil reactors. One of the fuel configurations selected for these reactors was a uranium (U) foil alloyed with 10% molybdenum (Mo). The U-10Mo fuel foil was then covered with a zirconium (Zr) interlayer and pressed into an aluminum cladding. Idaho National Laboratory prescribed a need to remove surface oxidation on the Zr prior to bonding it with U-10Mo fuel foil. To determine the best method of oxidation removal, a variety of polishing methods, including hand polishing with a diamond paste or Scotch-Brite™ pads, mechanically wet-polishing with abrasive belts, and chemical etching with hydrofluoric/nitric acid mixtures, were investigated on pre-polished Zircaloy 702 sheets purchased directly from the manufacturer. No change in surface roughness was detected using any of these methods relative to the as-received material. In fact, scanning electron microscopy detected grit from hand polishing with Amplex Grade 30 waste soluble diamond paste and Scotch-Brite™ pads. Visible staining was found, and fluorine detected via X-ray photoelectron spectroscopy on the flash etching samples. These contaminants were not seen on the as-received material. In addition to the need to remove the oxide layer on the Zr prior to co-rolling, there are concerns that the Neolube debonding agent on the co-rolling can may contaminate the Zr surface after co-rolling. The experimental results found that zirconium in contact with Neolube coated steel plates was easily cleaning with ethanol wiping after heat treated and no carbide inclusions remained on the surface. Overall, all cleaning methods tested did not significantly change the surface roughness of the plates or reduce the oxide layer present on the zirconium. Carbon was found on all the samples, before and after cleaning, except for the flash etch samples which detected fluorine instead. The insignificant changes seen in the cleaned plates relative to the as received plates question the need for cleaning prior to rolling. Further investigation in the requirements for cleaning at this step is recommended. Current methods for cleaning the surface after hot rolling with alcohol appear sufficient. After hot rolling, if Neolube does peel off the can and onto the zirconium coated foil surface, a dry abrasive or diamond paste polish is not recommended due to the chance of abrasive being embedded into the surface. However, the ability of an etchant to lift the lubricant off the zirconium surface indicates that a spot etch method could work to clean specific spots where Neolube is present, if the need arises.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Correlation‐Driven Magnetic Frustration and Insulating Behavior of TiF 3

The halide perovskite TiF 3 , renowned for its intricate interplay between structure, electronic correlations, magnetism, and thermal expansion, is investigated. Despite its simple structure, understanding its low‐temperature magnetic behavior has been a challenge. Previous theories propose antiferromagnetic ordering. In contrast, experimental signatures for an ordered magnetic state are absent down to 10 K. The current study has successfully reevaluated the theoretical modeling of TiF 3 , unveiling the significance of strong electronic correlations as the key driver for its insulating behavior and magnetic frustration. In addition, frequency‐dependent optical reflectivity measurements exhibit clear signs of an insulating state. The analysis of the calculated magnetic data gives an antiferromagnetic exchange coupling with a net Weiss temperature of order 25 K as well as a magnetic response consistent with aS = 1/2 local moment per Ti 3+ . Yet, the system shows no susceptibility peak at this temperature scale and appears free of long‐range antiferromagnetic order down to 1 K. Extending ab initio modeling of the material to larger unit cells shows a tendency for relaxing into a noncollinear magnetic ordering, with a shallow energy landscape between several magnetic ground states, promoting the status of this simple, nearly cubic perovskite structured material as a candidate spin liquid.

Materials Science↗

Early Holocene cold snaps and their expression in the moraine record of the eastern European Alps

Glaciers preserve climate variations in their geological and geomorphological records, which makes them prime candidates for climate reconstructions. Investigating the glacier–climate system over the past millennia is particularly relevant first because the amplitude and frequency of natural climate variability during the Holocene provides the climatic context against which modern, human-induced climate change must be assessed. Second, the transition from the last glacial to the current interglacial promises important insights into the climate system during warming, which is of particular interest with respect to ongoing climate change. Evidence of stable ice margin positions that record cooling during the past 12 kyr are preserved in two glaciated valleys of the Silvretta Massif in the eastern European Alps, the Jamtal (JAM) and the Laraintal (LAR). We mapped and dated moraines in these catchments including historical ridges using beryllium-10 surface exposure dating (10Be SED) techniques and correlate resulting moraine formation intervals with climate proxy records to evaluate the spatial and temporal scale of these cold phases. The new geochronologies indicate the formation of moraines during the early Holocene (EH), ca. 11.0 ± 0.7 ka (n = 19). Boulder ages along historical moraines (n = 6) suggest at least two glacier advances during the Little Ice Age (LIA; ca. 1250–1850 CE) around 1300 CE and in the second half of the 18th century. An earlier advance to the same position may have occurred around 500 CE. The Jamtal and Laraintal moraine chronologies provide evidence that millennial-scale EH warming was superimposed by centennial-scale cooling. The timing of EH moraine formation coincides with brief temperature drops identified in local and regional paleoproxy records, most prominently with the Preboreal Oscillation (PBO) and is consistent with moraine deposition in other catchments in the European Alps and in the Arctic region. This consistency points to cooling beyond the local scale and therefore a regional or even hemispheric climate driver. Freshwater input sourced from the Laurentide Ice Sheet (LIS), which changed circulation patterns in the North Atlantic, is a plausible explanation for EH cooling and moraine formation in the Nordic region and in Europe.

54 ENVIRONMENTAL SCIENCES↗

Data from: "Moisture rivals temperature in limiting photosynthesis by trees establishing beyond their cold-edge range limit under ambient and warmed conditions"

This archive contains data files that were used to draw conclusions in “Moisture rivals temperature in limiting photosynthesis by trees establishing beyond their cold-edge range limit under ambient and warmed conditions”, by Moyes et al., 2015. All field research was completed in common garden plots set up as part of the Alpine Treeline Warming Experiment (ATWE) on Niwot Ridge, Colorado, USA.There are two main data file formats in this archive: comma-separated values (.csv), and Microsoft Excel (.xls and .xlsx). .xlsx files can be read using Microsoft Excel and Google Sheets, and .csv files can be read using any simple text editor program, such as TextEdit (Mac) and Notepad (Windows). This .pdf data user’s guide can be read using Adobe Acrobat Reader, or any other compatible software. Seedling photographs and their corresponding leaf area-processed images are available in .jpg/.JPG image format, and can be opened using Preview (Mac) and Photos (Windows). To provide additional spatial context, two types of geospatial files are also published in this data package: ESRI shapefiles (.shp) and .kml files. Shapefiles are compatible with any GIS software able to read the file type (such as QGIS or ESRI’s ArcGIS suite), and .kml files can be opened with Google Earth or Google Maps. Figures 3 and 4 in the publication contain data from Moyes et al. 2013. This publication is cited in the References section in this archive, and data files can be accessed via the Alpine Treeline Warming Experiment project portal on ESS-DIVE. ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Climate change is altering plant species distributions globally, and warming is expected to promote uphill shifts in mountain trees. However, at many cold-edge range limits, such as alpine treelines in the western United States, tree establishment may be colimited by low temperature and low moisture, making recruitment patterns with warming difficult to predict.- We measured response functions linking carbon (C) assimilation and temperature- and moisture-related microclimatic factors for limber pine (Pinus flexilis) seedlings growing in a heating × watering experiment within and above the alpine treeline. We then extrapolated these response functions using observed microclimate conditions to estimate the net effects of warming and associated soil drying on C assimilation across an entire growing season.- Moisture and temperature limitations were each estimated to reduce potential growing season C gain from a theoretical upper limit by 15–30% (c. 50% combined). Warming above current treeline conditions provided relatively little benefit to modeled net assimilation, whereas assimilation was sensitive to either wetter or drier conditions.- Summer precipitation may be at least as important as temperature in constraining C gain by establishing subalpine trees at and above current alpine treelines as seasonally dry subalpine and alpine ecosystems continue to warm.

54 ENVIRONMENTAL SCIENCES↗

Mining Air for Fuels and Fine Chemicals

The Intergovernmental Panel on Climate Change’s 2021 report underscores that Direct Air Capture (DAC) is an essential component to limiting global warming to 2 °C, yet separating CO 2 from air and its subsequent concentration for conversion into carbon neutral fuels/chemicals or permanent storage remains energy intensive and costly. Further, most DAC technologies rely on repetitive capture and release cycles that reduces the amount of time the DAC materials are able to collect CO 2 and increases wear and tear. Moisture swing (MS) sorption within anion exchange materials utilizes differences in relative humidity to capture and concentrate CO 2 up to 500-fold with negligible energy inputs and low-cost sorbents. Molecular modeling predicts that membranes with a dry and wet side would actively transport CO 2 from its dry side to its wet side against a counter flow of H 2 O evaporating on the dry side, however, existing MS materials are too brittle to be processed into membranes to test this hypothesis. This project brought together experts in DAC materials and design, techno-economic analysis and project management at Arizona State University (ASU), polymer processing at University of Texas at Austin (UTA) and modeling gas transport and exchange at Norther Arizona University (NAU) to develop hollow fiber membranes that use energy from water evaporation to continuously pump CO 2 from air against a concentration gradient to the membranes interior and requiring significantly less energy than current DAC technologies. While this project did not meet its ultimate objectives of demonstrating an active CO 2 pumping membrane, a number of key accomplishments were made in developing low-cost, flexible anion exchange membranes (AEM) at 3.5 m 2 scale, characterizing the ionic and molecular transport within MS materials, and developing several analytical and mathematical models of the MS and pumping process leading to new fundamental knowledge about key rate limiting steps of CO 2 flux in anion exchange membranes at low water activity. Technoeconomic models show that if CO 2 fluxes ≥ 25 µmol CO 2 m -2 s -1 (membrane surface area) are achieved that cost ≤ $\$$100/tonne CO 2 captured, purified and compressed to pipeline quality is possible. The knowledge gained in this research will guide future research in developing new materials toward overcoming these rate limiting steps that in turn could enable transformative and disruptive DAC technologies needed for capturing gigatons of CO 2 per year needed to limiting global warming to 2 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantifying Properties for a Mechanistic, Predictive Understanding of Aqueous Impact on Aging of Medium and Low Voltage AC and DC Cabling in Nuclear Power Plants

To address the gap in knowledge in understanding degradation in relevant service conditions, this project aimed to develop a mechanistic, predictive model of medium and low voltage cable failure based on the primary environmental degradation parameters of aqueous immersion time, temperature, and the oxidation extent. To do so, we took a two-fold approach toward evaluating degradation as related to the aqueous condition. First, we evaluated the chemical, mechanical, and electrical properties of polymers that comprise the cabling insulation under varied aqueous conditions at different temperatures. Secondly, we evaluated the performance of insulation materials under similar accelerated aging conditions in addition to the dielectric breakdown of the cabling under submersion conditions. Thermal oxidation and immersion of LDPE thin films were done using a Parr vessel and the extent of oxidation was monitored using the carbonyl index from ATR-FTIR spectrum, a ratio quantifying the carbonyl functionality produced on the LDPE film surface. Increasing the temperature, oxidation time, and oxygen pressure increased the water-vapor permeability and the carbonyl content. Thermogravimetric analysis of the films confirmed that there is indeed an initial weight loss of the smaller molecular weight molecules and volatiles. At higher temperatures, there is a secondary mass loss. Up to 70°C, the mass loss curves were similar until 80°C, when the aged films decreased at a much greater rate with respect to increasing temperature. This was seen in the 10, 50, 90% weight loss temperatures. The mechanical properties of sheet PP and HDPE as well as injection molded LDPE, HDPE, HDPP dog bones were plotted with respect to the time spent in the Parr vessel during thermal oxidation. For the sheet PP and HDPE, the UTS and the modulus of elasticity decreased while the elongation increased. The injection-molded LDPE, HDPE, and HDPP dog bones experienced a similar trend where the changes in the properties were within experimental uncertainty. This analysis of LDPE in dry and immersive oxygen-rich environments is an important baseline for future experiments looking at other degradation mechanisms. A predictive aging model for low-density polyethylene insulative cable housings was developed. This model revealed a combination of physical and chemical processes which lead to an increase in permeability and a decrease in strength of the insulator. In creating this predictive model, a gap of knowledge in the literature was revealed in two areas: understanding how the crystallinity of a polymer changes with time and visualizing the predicted pores formed through the insulator which leads to failure. Developing and using an adapted ATR-FTIR method, crystallinity was monitored and compared to bulk crystallinity found via DSC. Inhomogeneity in crystallinity changes were observed but the FTIR method but was found to be less reliable. Pore visualization was found utilizing electrical impedance spectroscopy saturated aged polyethylene films with synthesized citrate-capped gold nanoparticles, and chloroauric acid precursor. results indicate a decreasing impedance of the polyethylene films caused by the transport of ions through the film. SEM imaging was then performed for elemental analysis of the films and counter electrodes for the presence of ions. Chloride and gold ions were detected; however, no nanoparticles were found. This gives an estimated pore size of at least 0.3 nm through the aged film. Cyclic submergence of polyethylene and polypropylene in aqueous solutions of copper sulfate and Harrison’s solution were examined. It was discovered that aging in these mixed conditions and at 90°C did cause a small, yet significant increase to tensile strength for both unaged polyethylene and polypropylene. The PE and PP in cycled and submerged conditions did not have tensile strengths significantly different from dry-aged after 16 weeks. For both solutions, it was determined that capacitance increases with both water tree depth and cable temperature and is relatively independent of changing water tree AR. As for resistance, there is no apparent change between depth percentages of 10 and 80 for both solutions. This is because the water tree has not yet entered the conductor and thus there is no shorting current flowing through the tree yet. Between 80 and 100% water tree depth, it is observed that for both solutions there is a rapid decrease in resistance because the tree is now impacting the conductor shield and allowing shorting current to flow through it. The relationship between resistance and temperature was found to be inversed. As temperature increases, resistance decreases for both water tree solutions with distilled water having the most apparent difference across the range of temperatures simulated. With regards to water tree AR, resistance was found to be relatively independent at depth percentages of 10, 50, and 70, but there was some relationship at 100% depth for both solutions. At this depth, as water tree AR increased, resistance was found to also increase. Through the examination of voltage and electric field distribution plots, it was confirmed for EPR cables that increasing water tree depth leads to increasing distortion. The increase in shorting current at 100% depth for aqueous copper sulfate compared to distilled water was also visualized. Lastly, the relationship between shorting current and temperature for narrow water trees was visualized and validated using the distribution plots. This study has led to a better understanding of the effect of cable temperature, water tree solution, and geometry of the tree region on cable degradation. Furthermore, this study has documented simulation results of water tree degradation in EPR MV cables, which had been previously lacking in information. Future work in this area will add frequency into the mix and examine what effect it has on the rate of cable degradation as a result of water treeing. To compliment the work being carried by UMD on different polymer chemistries, harvested medium voltage (MV) cables were selected for accelerated aging study at ORNL. These medium voltage cables are representative of the vintages and materials that are currently in use at existing nuclear power plants (NPPs). These cables were immersed in water at 90°C and energized for a period of two years at elevated voltage. Partial discharge was measured during this period of time to track potential degradation. Unfortunately, due to the absence of failure, the extent of integration between the UMD techniques and the harvested MV insulation was limited. However, based on the findings and from the UMD research in the previous sections on polyethylene and polypropylene, follow-on characterization for harvested MV cable insulation should focus on sample preparation to take advantage of the UMD techniques to better understand mechanistic degradation in MV cable insulations. This would include: 1.) Utilization of solutions and impedance measurement insulation to track permeability in harvested and accelerated aging insulation samples, 2.) Adaptation of gold nanoparticle synthesis for electrical impedance spectroscopy with supporting SEM characterization to study pore formation in harvested and accelerated aged insulation samples, & 3.) ATR-FTIR crystallinity with multiple temperature dependent harvested MV cable insulation under different air and submerged accelerated aging. In addition, low voltage dielectric spectroscopy and high voltage dissipation factor, tan δ, could be implemented as a condition monitoring tool for harvested MV cable insulation in submerged environments.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Hybrid Solar System (Final Scientific/Technical Report)

GTI Energy (GTI) teamed with the University of California at Merced (UCM) to scaleup the hybrid solar system (HSS) technology for demonstrating its performance at the US Gypsum (USG) plant in Plaster City, California. The technology integrates two-stage concentrating solar collector with matching particle thermal transport and storage (TSS) system to deliver cost-effective, and on-demand distributed high temperature industrial process heat up to 600°C with solar thermal, in this case to a gypsum kettle, to reduce its fuel use and carbon footprint. Current solar technologies, which reach these temperatures, are not distributable (towers) or cost-effective (dish). The research team developed a conceptual system design for host site retrofit, including preliminary heat balance, process flow diagram, particle to process heat exchanger and equipment placements at the site. Subsequently, parallel efforts were carried out at UCM to design, build and test a 12 m long commercial scale prototype concentrating thermal-only collector system and at GTI to design, build and test a matching 650°C capable particle TTS system. The nominal 50 kWth collector consists of a parabolic trough and three 4 m long two-stage receivers in series. Prior to on-sun testing, a 4 m long receiver was fabricated and successfully tested at 650 °C in a laboratory setting for 100 hrs of continuous operation showing less than 15% radiation loss. A 7 m wide x 17 m long parabolic trough was then installed at UCM for on-sun testing of the 12 m long receiver, and concurrently several 4 m long receivers were built. The optics of the parabolic trough were calibrated, and on-sun test were carried out on 12 m long receivers. During tests, the intense solar radiation (53x) caused the absorber tubes in the receivers to bend, reducing the overall optical efficiency. To address the bending issue, a self-consistent algorithm that includes ray tracing, thermal and deformation models was developed to perform thermal stress analysis on absorbers for parabolic solar collectors. Results obtained with this algorithm showed a dramatic rise in deformation as absorber tube length increases. A combined efficiency parameter that includes the occluded area for the mounts was developed to obtain an optimized tube length obtained. Based on the results, a length of 2.7 m for the absorber + 0.2 m for the coupler was chosen to minimize any bending and optimize optical efficiency while maintaining ease of mounting. The associated particle TTS system was designed, built and successfully tested at GTI. It includes storage, receiving and lock hoppers and piping that simulates the transfer of captured solar energy to an actual industrial furnace. Tests over 77 charge-discharge cycles demonstrated <2% particle degradation, with no problematic particle accumulations and no flow interruptions. The piping pressure drop was about 5 psi. The team also worked with Stanley Consultants (Stanley) to prepare conceptual and preliminary engineering packages to facilitate follow-on development and commercialization efforts. These include process and instrumentation diagram’s (P&ID’s), general arrangements, electrical one-line, project definitions document, equipment data sheets, schedule, and construction cost estimate for 2 MWth system. Updated HSS technology commercialization and customer engagement plans and detailed costs and evaluated market trade-offs and manufacturing.

03 NATURAL GAS↗

Historical and Future Learning for the New Era of Multi-Terawatt Photovoltaics

Solar photovoltaics (PV) is entering a new era of multi-terawatt deployment, with 2 TW already in service and more than 75 TW predicted in many scenarios by 2050. This next era has been enabled by over five decades of cumulative advances in PV module cost reduction, performance and reliability. The current scale of deployment also introduces new needs, opportunities and challenges. In this Perspective we frame a path forwards based on learning, broadly defined as a combination of expansion of knowledge and advances through research and development, experience and collaboration. We discuss historical topics where learning has driven PV deployment until now, and emerging areas that are required to sustain high levels of future deployment. We expect progress to continue in terms of module price, performance and reliability, driven by advances in PV cell and module design, the emergence of tandem devices and increased focus on extending module lifetimes. Large-scale deployment also means large-scale sustainability and responsibility. We therefore posit that additional metrics, such as the impact on global CO2 emissions, resource consumption and design for reuse and recycling, will become increasingly important to the PV industry and provide opportunities for further learning.

14 SOLAR ENERGY↗

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗