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At least 199 records · Page 11

Status memorandum on ORNL support of vendor irradiation capsule design and ASME irradiation code development and new ASTM test standard development activities

This report is in submission of completion of the Level 4 milestone number M4TG-24OR0501111 within the larger Advanced Reactor Technologies Gas Cooled Reactor program at Oak Ridge National Laboratory (ORNL). The focus of this year’s efforts is to continue support of industry needs related to the development of future industry-funded irradiation programs. At ORNL these efforts included the development of a generalized three-dimensional CAD model of an irradiation creep capsules for graphite, cost estimates of the expansion of the Materials Irradiation Facility (MIF), involvement with ASTM D02.F0 “Manufactured Carbon and Graphite Products” and the ASME Boiler and Pressure Vessel Code, and publication of papers supporting these efforts. This report will document the status of these activities.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Thermal energy grid storage: Liquid containment and pumping above 2000 °C

As the cost of renewable energy falls below fossil fuels, the key barrier to widespread sustainable electricity has become availability on demand. Energy storage can enable dispatchable renewables, but only with drastic cost reductions compared to current battery technologies. One electricity storage concept that could enable these cost reductions stores electricity as sensible heat in an extremely hot liquid (>2000°C) and uses multi-junction photovoltaics (MPV) as a heat engine to convert it back to electricity on demand hours, or days, later. Furthermore, this paper reports the first containment of silicon in a multipart graphite tank above 2000°C, using material grades that are affordable for energy storage at GWh scales. Low cost molded graphite with particle sizes as large as 10 μm successfully contained metallurgical grade silicon, even with as much as twothirds iron by mass for up to 10 hours and temperatures as high as 2300°C, in tanks as large as two gallons.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Microwave-Assisted Reactive CO 2 Capture with the SrCO 3 -Graphite System

This study details the initial development of a microwave heat-driven reactive CO 2 capture (RCC) process using the SrO/SrCO 3 cycle and graphitic carbon to absorb ppm-levels of CO 2 from humidified room temperature air and selectively convert it into CO. By combining first-principles density functional theory (DFT) simulations with thermogravimetric analysis (TGA) and X-ray diffraction (XRD) verification, it is demonstrated that SrO spontaneously absorbs moisture to generate Sr(OH) 2 followed by Sr(OH) 2 *1H 2 O, which then can spontaneously react with atmospheric levels of CO 2 to form SrCO 3 . The resulting SrCO 3 can then react with solid carbon at elevated temperatures to selectively produce CO and regenerate SrO. Graphitic carbon is an excellent microwave absorber that can quickly generate temperatures approaching 1000 °C and then cool to room temperature within minutes, potentially allowing for integration with intermittent electricity. It is shown that using microwaves to selectively heat a mixture of graphitic carbon and SrCO 3 produced CO with 85 ± 3% selectivity and stable performance over ten cycles. The rapid heating for release and room temperature CO 2 uptake processes appeared to prevent performance loss from particle sintering typically observed with traditional thermal systems. In conclusion, these results demonstrate a new RCC approach that adds to the growing number of potential technologies available for converting CO 2 to useful chemicals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Remote isotope detection and quantification using femtosecond filament-laser ablation molecular isotopic spectrometry

We demonstrate the detection and quantification of isotopes from solid samples remotely at a distance of 36 m. This was accomplished through the combination of femtosecond filaments and laser ablation molecular isotopic spectrometry (F 2 -LAMIS). Isotopically enriched graphite samples with varying 13 C concentration were used and the F 2 -LAMIS emission was measured remotely using a portable spectrometer system. A standardless quantification approach was used to determine the corresponding isotopic ratios. The use of F 2 -LAMIS for the detection and quantification of isotopes at atmospheric pressure without the use of calibration standards opens the possibility to implement this technology for remote sensing of isotopes in field applications

07 ISOTOPE AND RADIATION SOURCES↗

The Evolution of LiNi 0.5 Mn 0.3 Co 0.2 O 2 Particle Damage from Fast Charging in Optimized, Full Li-Ion Cells

Fast charging batteries are critical to the widespread adoption of electric vehicles to compete with refueling times of combustion-based vehicles. In the near term, adapting current commercial battery technologies to perform better under fast charging conditions through engineering optimizations will greatly expedite the process while exploratory fast-charging electrode materials are being pursued. To do so, the degradation modes in optimized Li-ion batteries need to be completely explored to understand fast charging limits while maintaining a high energy density and a long cycle life. While lithium plating on graphite still remains a challenge, cathode degradation also plays a key role in battery performance. In this work, we used nano- and micro-X-ray computed tomography to characterize the mechanical degradation of LiNi 0.5 Mn 0.3 Co 0.2 O 2 (NMC532) in optimized Li-ion batteries cycled at three rates, 1C, 6C, and 9C, and at different stages of cycle life, 225 and 600 cycles. We report despite using a conservative upper voltage cutoff limit aimed to minimize extensive cathode degradation, higher charging rates and increased cycling caused the polycrystalline NMC532 particles to fracture and pulverize, which likely drives cathode capacity fade and contributes to the decrease in overall cell performance.

25 ENERGY STORAGE↗

An overview of bipolar plates in proton exchange membrane fuel cells

Bipolar plates are a crucial component of proton exchange membrane fuel cells. They are responsible for transporting reactant gases, carrying the current from the membrane electrode assembly to the end plates, providing heat and water management, and separating the individual cells. However, these plates also contribute to 80% of the fuel cell’s weight, 50% of its volume, and 40% of its cost, posing a barrier to the commercialization of fuel cells. This paper provides a comprehensive review of the materials and manufacturing processes used in the fabrication of bipolar plates as well as recent research conducted on the improvement of bipolar plate weight, volume, and cost through material selection and manufacturing methods. Additive manufacturing is highlighted in this work as an innovative manufacturing method to produce bipolar plates. Novel contributions in this paper include a detailed explanation of traditional manufacturing processes for metallic and graphitic-polymer bipolar plates as well as a cost comparison between additive and traditional manufacturing processes.

08 HYDROGEN↗

Covalent Surface Modification Effects on Single‐Walled Carbon Nanotubes for Targeted Sensing and Optical Imaging

Abstract Optical nanoscale technologies often implement covalent or noncovalent strategies for the modification of nanoparticles, whereby both functionalizations are leveraged for multimodal applications but can affect the intrinsic fluorescence of nanoparticles. Specifically, single‐walled carbon nanotubes (SWCNTs) can enable real‐time imaging and cellular delivery; however, the introduction of covalent SWCNT sidewall functionalizations often attenuates SWCNT fluorescence. Recent advances in SWCNT covalent functionalization chemistries preserve the SWCNT's pristine graphitic lattice and intrinsic fluorescence, and here, such covalently functionalized SWCNTs maintain intrinsic fluorescence‐based molecular recognition of neurotransmitter and protein analytes. The covalently modified SWCNT nanosensor preserves its fluorescence response towards its analyte for certain nanosensors, presumably dependent on the intermolecular interactions between SWCNTs or the steric hindrance introduced by the covalent functionalization that hinders noncovalent interactions with the SWCNT surface. These SWCNT nanosensors are further functionalized via their covalent handles with a targeting ligand, biotin, to self‐assemble on passivated microscopy slides, and these dual‐functionalized SWCNT materials are explored for future use in multiplexed sensing and imaging applications.

Chio, Linda↗

Magnetite nanoparticle anchored graphene cathode enhances microbial electrosynthesis of polyhydroxybutyrate by Rhodopseudomonas palustris TIE-1

Microbial electrosynthesis (MES) is an emerging technology that can convert carbon dioxide (CO 2 ) into value-added organic carbon compounds using electrons supplied from a cathode. However, MES is affected by low product formation due to limited extracellular electron uptake by microbes. Herein, a novel cathode was developed from chemically synthesized magnetite nanoparticles and reduced graphene oxide nanocomposite (rGO-MNPs). This nanocomposite was electrochemically deposited on carbon felt (CF/rGO-MNPs), and the modified material was used as a cathode for MES production. The bioplastic, polyhydroxybutyrate (PHB) produced by Rhodopseudomonas palustris TIE-1 (TIE-1), was measured from reactors with modified and unmodified cathodes. Results demonstrate that the magnetite nanoparticle anchored graphene cathode (CF/rGO-MNPs) exhibited higher PHB production (91.31 ± 0.9 mg l -1 ). This is ~4.2 times higher than unmodified carbon felt (CF), and 20 times higher than previously reported using graphite. This modified cathode enhanced electron uptake to -11.7 ± 0.1 μ A cm -2 , ~5 times higher than CF cathode (-2.3 ± 0.08 μ A cm -2 ). The faradaic efficiency of the modified cathode was ~2 times higher than the unmodified cathode. Electrochemical analysis and scanning electron microscopy suggest that rGO-MNPs facilitated electron uptake and improved PHB production by TIE-1. Overall, the nanocomposite (rGO-MNPs) cathode modification enhances MES efficiency.

Materials Science↗

Control of the Plasma-Material Interface for Long Pulse Optimization in the Experimental Advanced Superconducting Tokamak (EAST) (Final Report)

This project involved a collaborative effort, led by Dr. Rajesh Maingi of Princeton Plasma Physics Laboratory, to understand and control the plasma-material interface to improve long pulse discharge control and performance in the EAST devices. The focus is on long pulse recycling control and optimization, which can be challenging because of their broad range of materials used for plasma-facing components (PFC) and wall conditioning techniques. The purpose of the EAST device is to demonstrate long-pulse, stable, high performance plasma operation, providing a test-bed for key physics and technology issues for next step devices. As part of these tests, EAST has deployed carbon for the lower divertor PFC, tungsten for the upper divertor, and molybdenum for the main wall. In addition wall coatings are deployed for long pulse recycling control: lithium (Li) via several delivery tools, boronization, and recently also siliconization; for example, in 2013, a layer of SiC was deposited on all of the graphite tiles. Oxygen is also present at trace levels, making for a complex mix of materials and plasma-materials interactions (PMI). This mix of materials and the limited durability of wall coatings, coupled to partially optimized cryo-pumping, lead to evolution of the recycling off the PFCs, which restricts the duration of stationary, high performance, long pulse discharges. Comparing the wall conditioning techniques, Li enables the highest energy confinement and lowest recycling for the longest duration, while also suppressing ELMs in certain discharges. More specifically, research activities at the University of Tennessee focused on heat flux profile measurements in EAST, modeling the surface response, including the bonding energetics and chemical interactions between Li with carbon, tungsten, hydrogen and impurities, in addition to post situ experimental characterization and analysis of the divertor plasma facing components in EAST. This final report describes the overall progress within each of these tasks at the University of Tennessee within the project.

36 MATERIALS SCIENCE↗

Transforming CO 2 to Porous Carbon as a High-Performing Sodium-Ion Battery Anode via Electrochemical Reduction in Molten Carbonates

The prevalence of sodium over lithium prompts exploration of sodium-ion batteries (SIBs) as a viable alternative to lithium-ion batteries (LIBs). Hard carbon has emerged as a promising anode material for SIBs, yet its synthesis poses sustainability challenges and emits pollutants. Here, in this study, we introduce CO 2 -derived porous carbon (graphitic and amorphous) as an anode for SIBs via electrochemical reduction of CO 2 in a molten eutectic carbonate salt at a lower temperature that yields materials with controlled microstructure, morphology, and porosity conducive to energy storage. Our CO 2 -derived carbon demonstrates remarkable specific capacity, superior rate capability, and stable cycling performance as a SIB anode. This innovative strategy harnesses waste CO 2 toward advancing SIB energy technology.

CO2-derived carbon↗

Metal-free carbocatalyst for room temperature acceptorless dehydrogenation of N-heterocycles

Catalytic dehydrogenation enables reversible hydrogen storage in liquid organics as a critical technology to achieve carbon neutrality. However, oxidant or base-free catalytic dehydrogenation at mild temperatures remains a challenge. Here, we demonstrate a metal-free carbocatalyst, nitrogen-assembly carbons (NCs), for acceptorless dehydrogenation of N-heterocycles even at ambient temperature, showing greater activity than transition metal–based catalysts. Mechanistic studies indicate that the observed catalytic activity of NCs is because of the unique closely placed graphitic nitrogens (CGNs), formed by the assembly of precursors during the carbonization process. The CGN site catalyzes the activation of C–H bonds in N-heterocycles to form labile C–H bonds on catalyst surface. The subsequent facile recombination of this surface hydrogen to desorb H 2 allows the NCs to work without any H-acceptor. With reverse transfer hydrogenation of various N-heterocycles demonstrated in this work, these NC catalysts, without precious metals, exhibit great potential for completing the cycle of hydrogen storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of free chlorine levels in water using potentiometric responses of biofilms and applications for monitoring and managing the quality of potable water

We report residual free chlorine is not monitored continuously at scale in drinking water distribution systems because existing real-time sensor technologies require frequent maintenance, cleaning, and calibration, which makes these products too costly to be used throughout a distribution system. As a result, current measurement approaches require manual sampling, which is not feasible for the consistent monitoring of free chlorine because chlorine concentrations vary significantly throughout pipeline distribution and over time and space. This research presents an alternative and cost-effective method of predicting free chlorine levels in drinking water using graphite electrodes coated with naturally grown microbial biofilms. This Microbial Potentiometric Sensor (MPS) array was installed in a Continuously Mixed Batch Reactor (CMBR), and drinking water containing variable free chlorine concentrations. The chlorine concentrations were introduced in a controlled manner, and the MPS signals were monitored over time. MPS signals were measured from the change in Open Circuit Potential (OCP) across the MPS array in real-time. An empirically derived relationship between the normalized change in OCP and free chlorine was established by fitting individual and average MPS data to a decaying exponential growth function in order to predict free chlorine levels. The results show that free chlorine can be predicted with reasonable accuracy, with model validation showing an average absolute error of ±0.09 ppm below 1.1 ppm and ±0.30 ppm between 1.1 and 2.7 ppm. However, the accuracy of predictions was reduced at higher free chlorine levels. The researchers conclude that MPS systems may benefit drinking water distribution systems by measuring free chlorine. These advantages of the MPS are especially pronounced in the developing world because this system is inexpensive and does not require routine maintenance or cleaning. The system relies on a naturally forming and regenerating biofilm and an inexpensive potentiometric meter to produce stable measurements.

54 ENVIRONMENTAL SCIENCES↗

Nuclear Data Management and Analysis System Plan

The United States Department of Energy Advanced Reactor Technologies Program was formed in Fiscal Year 2015 and encompasses the Next Generation Nuclear Plant Project and Very High Temperature Reactor (VHTR) Program as they were known previously. The VHTR Program was created to support design and licensing of the first VHTR nuclear plant. Data created for and used by the program must be qualified for use, stored in a readily accessible electronic form, categorized to assure the correct data are used, and controlled to prevent data corruption or inadvertent changes. The Nuclear Data Management and Analysis System was designed to support the data needs of the VHTR Program, at the time and now the Advanced Reactor Technologies Program. Since its inception, use of the Nuclear Data Management and Analysis System has expanded to support additional projects and programs with similar requirements for control, analysis, and availability of large data sets.

99 GENERAL AND MISCELLANEOUS↗

Using the Principals of Electrochemistry to Understand and Overcome the Complicated Degradation Mechanisms of Silicon Anodes in Lithium-Ion Batteries [Slides]

Battery technology is the most significant problem facing widespread market adoption of battery electric vehicles (BEVs). The low energy density of state-of-the-art lithium-ion electrode materials leaves BEV owners and prospective buyers with lower ranges than a comparable internal combustion engine (ICE) vehicle, and vulnerable to a nascent fast charging network. Silicon has the potential to increase the anode energy density by nearly ten times compared to the incumbent material (graphite) and make BEVs a more competitive transportation option. However, lithiated silicon is extremely reactive towards components of the electrolyte and forms a heterogeneous, complicated, and dynamic solid at its surface known as the solid electrolyte interphase (SEI). Ideally, the SEI would passivate the silicon surface, but continuous chemical degradation persists even when the battery is not operating. This reactivity reduces silicon anode lifetimes well below the necessary standards for BEVs. The NREL-led Silicon Consortium Project is dedicated to understanding and solving these mechanisms of degradation. Here, I will discuss an electrochemical method that provides deep insights into the silicon interface during battery operation. I will link these observations to fundamental electrochemical principals and how they translate into actionable strategies that extend the lifetime of silicon anodes.

25 ENERGY STORAGE↗

Visualizing Energy Transfer at Buried Interfaces in Layered Materials Using Picosecond X-Rays

Understanding the fundamentals of nanoscale heat propagation is crucial for next-generation electronics. For instance, weak van der Waals bonds of layered materials are known to limit their thermal boundary conductance (TBC), presenting a heat dissipation bottleneck. In this paper we present a new non-destructive method to probe heat transport in nanoscale crystalline materials using time-resolved x-ray measurements of photo-induced thermal strain. This technique directly monitors time-dependent temperature changes in the crystal and the subsequent relaxation across buried interfaces by measuring changes in the c-axis lattice spacing after optical excitation. We investigate films of five different layered transition metal dichalcogenides MoX 2 [X= S, Se, Te] and WX 2 [X= S, Se] as well as graphite and a W-doped alloy of MoTe 2 , on c-plane sapphire substrates, finding TBC values in the range 10-30 MWm -2 K -1 at room temperature. In conjunction with molecular dynamics simulations, we show that the high thermal resistances are a consequence of weak interfacial van der Waals bonding and low phonon irradiance. This work paves the way for an improved understanding of thermal bottlenecks in emerging three-dimensional heterogeneously integrated technologies.

36 MATERIALS SCIENCE↗

Electrochemical behavior and separation of iodide in molten LiF-NaF-KF melt

This work studied the electrochemical behavior of iodide in molten LiF-NaF-KF mixture and the separation of iodide from the molten salt at 973 K using a graphite working electrode. The cyclic voltammetry (CV) and chronoamperometry (CA) measurements indicated an anodic passivation layer was formed on the graphite electrode in this melt and the layer blocked the charge transfer across the electrolyte/electrode interface. However, the added I- ions could pass through the passivation layer and were oxidized at the graphite electrode. The characterization of the obtained products proved that iodide ions was efficiently oxidized to I2 gas during electrolysis. Furthermore, the graphite anode showed excellent stability without any obvious change in dimensions after electrolysis, which showed the high current efficiency of I2 evolution reaction. Thus, the graphite electrode was possible to be served as an excellent anode to separate other anions (such as Br) from molten fluoride salts.

36 MATERIALS SCIENCE↗