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At least 775 records · Page 43
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Proton irradiation effects in Molybdenum-Carbide-Graphite composites

The High Luminosity upgrade of the Large Hadron Collider (HL-LHC) has prompted the investigation of novel materials for beam-intercepting devices, and in particular for the collimators responsible for protecting the machine from beam losses. The HL-LHC collimation system will inevitably experience increased levels of radiation damage and undergo changes in their crucial physio-mechanical properties. Graphite-matrix composite materials containing molybdenum carbide particles, along with small amounts of titanium carbide, were developed with the objective of enhanced in-beam performance and tested under proton irradiation. The physical degradation observed in early grades of molybdenum carbide compounds, even after modest proton fluences, has prompted the development of advanced compounds. In this work, we examine the effects of proton irradiation on the microstructural and thermophysical properties of new grades of Molybdenum-carbide-graphite compounds up to fluences of ~2 × 10 20 p/cm 2 . Here, we employ a combination of precision dilatometry and high-energy X-ray diffraction to quantify the dimensional stability and crystallographic phase evolution both pre- and post-irradiation. Our results reveal that these new compounds exhibit superior resilience to radiation damage than their predecessors.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Understanding the effect of specimen size on the properties of fine-grain isotropic nuclear graphite for irradiation studies: Physical, electrical, thermal properties

Programs at Oak Ridge National Laboratory are investigating the effects of neutron irradiation in the High Flux Isotope Reactor (HFIR) on properties of fine-grain nuclear graphites. Specimens were irradiated in the HFIR flux trap, which required using specimens that are smaller than the sizes recommended by ASTM standards. Here, this work has investigated whether subsized specimens can be used to reliably determine the measured physical (density, elastic moduli, and electrical resistivity) and thermal properties (coefficient of thermal conductivity and thermal conductivity). The results show the specimen sizes in this investigation had a minimal influence on any of the measured properties. Even for the properties where size influenced the measured value (density and thermal conductivity), an explanation is provided, and the consequences can be accounted for in post-irradiation results. This work demonstrated that using subsized specimens for physical and thermal property measurements is suitable when necessary for fine-grain isotropic graphite.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Insights from incorporating reference electrodes in symmetric lithium-ion cells with layered oxide or graphite electrodes

Symmetric cells provide complementary means to probe electrochemical processes in lithium-ion batteries. Here, positive and negative electrodes harvested from conventional oxide/graphite cells are cross-paired, and the assembled reference-electrode-bearing symmetric cells are cycled/aged. For graphite symmetric cells, the electrode potentials and impedances remain nearly constant during calendar aging and the parasitic currents are typically small. However, at higher cell voltages when the “positive” graphite potential exceeds 1.0 V vs. Li/Li + , the capacity loss is higher, indicating that even a mild (but prolonged) overdischarge can damage the SEI. For the layered-oxide symmetric cells there are strong parasitic currents and a persistent slide of the electrode potential over time during calendar aging. Significant cell impedance rise, especially at higher hold voltages, is also observed. Curiously, the impedance rise in the “negative” oxide electrode, which experiences potentials below 4.0 V vs. Li/Li + , is greater than in the “positive” oxide electrode that experiences much higher potentials. We postulate that electrolyte oxidation is responsible for the behavior of these oxide symmetric cells, as it supplies electrons (that bind more Li + into the cathode, causing the potential slide) and protons (that contribute to impedance rise). Furthermore, these insights can guide the development of future lithium-ion cell chemistries.

25 ENERGY STORAGE↗
DOE OSTI2020

Failure investigation of nuclear grade POCO graphite target in high energy neutrino physics through numerical simulation

In many high energy physics neutrino beamlines, targets are made up of isotropic POCO graphite grade for production of neutrinos for high energy particle physics research and are bombarded with highly energetic pulsed proton beam. The pulsed proton beam with a small beam size creates thermal stress waves as well as radiation damage such as displacement damage, void formation, swelling, and gas formation amongst others. As a result, after a few years of operation one of the longest operated targets appears to have undergone bulk swelling and fractured along the beam centerline. A complex interaction of dynamic loading due to beam, material degradation due to irradiation are thought to have caused such a failure. Here, we present a numerical simulation to capture the combined effects of swelling and the dynamic effect of thermal stress waves due to beam heating, to explain the failure of target. An empirical formula has been developed to take into account swelling as a function of temperature and proton fluence and has been implemented in a commercial finite element code. Extensive X-ray diffraction (XRD) were performed on graphite samples from the failed target to understand the lattice parameter changes due to irradiation and build a valid empirical model. Simulation results show that swelling plays a major role in elevating the stress state in the material exceeding the failure strength while the pulsed beam heating also introduces fatigue loading that would explain brittle fracture emanating from inside of the material and propagating outward. Such empirical formulations will help in identifying the threshold values of critical parameters to extend the service life of future multi-megawatt neutrino targets and targets in other accelerator environments.

43 PARTICLE ACCELERATORS↗
DOE OSTI2025

Thermal oxidation of nuclear graphite and pyrolytic carbon coatings

The oxidation of pyrolytic carbon (PyC) deposited via fluidized bed chemical vapor deposition was characterized and compared with that of standard nuclear-grade graphite. The materials were heated at 700 to 1000 °C in a thermogravimetric analysis system under 20% v/v O 2 flow, allowing for direct comparison of dynamic oxidative mass change in each material. Further, three different PyC samples fabricated under different conditions exhibited variation in total mass loss and mass loss rate, varying by as much as 709 mg/cm 2 in total mass loss and 14.2 (mg/cm 2 )/min in mass loss rate at a single temperature. These variations highlight the correlation between PyC microstructure/defect density and oxidation susceptibility. Additionally, changes in the microstructure and composition between PyC and graphite were characterized via scanning electron microscopy and correlated to the mass loss results. The results of this work have implications toward the safety of tristructural isotropic (TRISO) and other coated particle fuels, especially under off-normal conditions, given the limited information that exists about the oxidation behavior of PyC.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Simultaneous neutron and X-ray tomography for visualization of graphite electrode degradation in fast-charged lithium-ion batteries

Advanced battery characterization using neutron and X-ray-based imaging modalities is crucial to reveal fundamental degradation modes of lithium-ion batteries (LIBs). Taking advantage of the sensitivity of neutrons to some low-Z (Li) and X-rays to high-Z materials (Cu), here we demonstrate the viability of simultaneous neutron and X-ray tomography (NeXT) as a non-destructive imaging platform for ex-situ 3D visualization of graphite electrode degradation following extreme fast charging (XFC). In addition, we underscore the benefits of the simultaneous of NeXT by combining the neutron and X-ray tomography data from the same sample location for material identification and segmentation of one pristine and two XFC-cycled graphite electrodes (9C charge for 450 cycles). Our ex-situ results and methodology development pave the way for the design of NeXT-friendly LIB geometries that will allow operando and/or in-situ 3D visualization of electrode degradation during XFC.

25 ENERGY STORAGE↗
DOE OSTI2024

Monitoring SEIRAS on a Graphitic Electrode for Surface-Sensitive Electrochemistry: Real-Time Electrografting

The ubiquity of graphitic materials in electrochemistry makes it highly desirable to probe their interfacial behavior under electrochemical control. Probing the dynamics of molecules at the electrode/electrolyte interface is possible through spectroelectrochemical approaches involving surface-enhanced infrared absorption spectroscopy (SEIRAS). Usually, this technique can only be done on plasmonic metals such as gold or carbon nanoribbons, but a more convenient substrate for carbon electrochemical studies is needed. Here, we expanded the scope of SEIRAS by introducing a robust hybrid graphene-on-gold substrate, where we monitored electrografting processes occurring at the graphene/electrolyte interface. These electrodes consist of graphene deposited onto a roughened gold-sputtered internal reflection element (IRE) for attenuated total reflectance (ATR) SEIRAS. The capabilities of the graphene-gold IRE were demonstrated by successfully monitoring the electrografting of 4-amino-2,2,6,6-tetramethyl-1-piperidine N -oxyl (4-amino-TEMPO) and 4-nitrobenzene diazonium (4-NBD) in real time. These grafts were characterized using cyclic voltammetry and ATR-SEIRAS, clearly showing the 1520 and 1350 cm –1 NO 2 stretches for 4-NBD and the 1240 cm –1 C–C, C–C–H, and N–Ȯ stretch for 4-amino-TEMPO. Successful grafts on graphene did not show the SEIRAS effect, while grafting on gold was not stable for TEMPO and had poorer resolution than on graphene-gold for 4-NBD, highlighting the uniqueness of our approach. The graphene-gold IRE is proficient at resolving the spectral responses of redox transformations, unambiguously demonstrating the real-time detection of surface processes on a graphitic electrode. This work provides ample future directions for real-time spectroelectrochemical investigations of carbon electrodes used for sensing, energy storage, electrocatalysis, and environmental applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Local Thermochemical Mechanisms in Direct Solar Graphite Synthesis from Methane

Methane pyrolysis is known to produce hydrogen and solid carbon in a variety of thermal processes. However, the generated carbon product typically belongs to a low-value amorphous type. Here, we elucidate the thermochemical mechanisms of a reaction that produces high-quality graphite via direct solar methane pyrolysis on a porous substrate. By comparing graphite deposition rates and local reaction zone temperatures of exposed and shadowed regions from the same experiment, we clarify the effects of thermolysis and photolysis in this emission-free process that both decarbonizes a fuel and produces a critical material for the sustainable energy transition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Graphitized Biocarbon Derived from Hydrothermally Liquefied Low-Ash Corn Stover

Graphitized biocarbon can be utilized for energy storage applications such as supercapacitors. The scientific community have geared their attention to obtain such value-added product from abundantly available and low-cost biomass feedstock agricultural residues such as corn stover. Lignocellulosic components embedded within the cell wall of biomass substrates can provide a fine template for enhanced ion storage, transport, and rate capabilities, desirable for electrochemical storage. Presented is the utilization of homogenized low ash content corn stover milled and sieved to desired specifications, which underwent hydrothermal liquefaction in the presence of Ni-based catalytic salts at 275 o C. The hydrochar obtained by solid residue extracted from the reaction slurry was washed to acid neutral and subjected to catalytic activation using ZnCl 2 , followed by thermal annealing at 400 o C for morphological and pore size enhancement of the resulting biochar. Carbonization was performed on acid neutralized hydrochar at 850 °C to further enhance pore structures and increase graphitization for improved conductivity. Catalytic materials exhibited a specific capacitance of 316 F g -1 and held a 100% retention beyond 10,000 cycles. BET, Raman, XRD, cyclic voltammetry, chronopotentiometry, and EIS are discussed herein.

Biomass↗
DOE OSTI2016

Li Intercalation into Graphite: Direct Optical Imaging and Cahn–Hilliard Reaction Dynamics

Lithium intercalation into graphite is a critical process in energy storage technology. Studies of Li intercalation kinetics have proved challenging due to structural and phase complexity, and sample heterogeneity. Here we report direct time- and space-resolved, all-optical measurement of Li intercalation. We use a single crystal graphite electrode with lithographically defined disc geometry. All-optical, Raman and reflectance measurements distinguish the intrinsic intercalation process from side reactions, and provide new insight into the microscopic intercalation process. The recently proposed Cahn–Hilliard reaction (CHR) theory quantitatively captures the observed phase front spatial patterns and dynamics, using a two-layer free-energy model with novel, generalized Butler–Volmer kinetics. This approach unites Cahn–Hilliard and electrochemical kinetics, using a thermodynamically consistent description of the Li injection reaction at the crystal edge that involves a cooperative opening of graphene planes. Here, the excellent agreement between experiment and theory presented here, with single-crystal resolution, provides strong support for the CHR theory of solid-state reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electrically Conductive Amine Functionalized Reduced Graphite Oxide Foam for CO 2 Removal from the Air

Rapid regeneration of CO 2 adsorbents is critical to improving the productivity of direct air capture (DAC) systems. In this study, we codesigned a material to have appropriate electrical conductivity and CO 2 adsorption properties to enable efficient CO 2 capture from air. Specifically, we present a poly(ethylenimine) (PEI)-impregnated thermally annealed graphite oxide (TAGO900) foam adsorbent tailored for vacuum-assisted electrically driven thermal swing adsorption (V-ETSA). This structured adsorbent leverages the high electrical conductivity of the reduced graphite oxide framework to enable fast and direct heating of the adsorbent material by electrical resistance heating (Joule heating). An optimal sample, 40 wt % PEI (molecular weight 25k) impregnated TAGO900, shows the best balance between adsorption capacity (1.54 mmol g –1 ) and adsorption rates (0.016 mmol g –1 min –1 ) using fixed bed breakthrough experiments at 25 °C and 70% RH using 50 sccm 400 ppm of CO 2 /N 2 flow. Compared to conventional temperature vacuum swing adsorption (TVSA), the V-ETSA approach achieves substantially faster CO 2 desorption, achieving average desorption rates (including cooling time) of 0.09 mmol g –1 min –1 ─approximately 2.5 times faster than TVSA under similar operating conditions. The maximum desorption rate reaches 0.23 mmol/g/min during the desorption stage. These results underscore the importance of the direct heating strategy, such as Joule heating, for fast and highly productive vacuum swing adsorption in DAC systems.

amines↗
DOE OSTI2019

Graphite-conjugation enhances porphyrin electrocatalysis

We synthesize porphyrins that are strongly electronically coupled to carbon electrodes by condensing diaminoporphyrin derivatives onto o-quinone moieties native to graphitic carbon surfaces. X-ray photoelectron and absorption spectroscopies along with electrochemical data establish the formation of a high-fidelity conjugated pyrazine linkage to the surface with preservation of the metalloporphyrin scaffold. Using the O 2 reduction reaction (ORR) as a probe, we find that conjugation dramatically promotes the rate of catalysis. A graphite-conjugated Co porphyrin, GCC-CoTPP, displays an onset current of 10 μA/cm 2 at 0.72 V versus the reversible hydrogen electrode, whereas a non-conjugated amide-linked Co-porphyrin onsets at 0.66 V. This corresponds to an order of magnitude enhancement in the activation-controlled turnover frequencies for ORR upon conjugation. Conclusively, this work establishes a versatile platform for examining the emergent reactivity of porphyrins strongly coupled to metallic electrodes.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2017

Hierarchically Porous Graphitic Carbon with Simultaneously High Surface Area and Colossal Pore Volume Engineered via Ice Templating

Developing hierarchical porous carbon (HPC) materials with competing textural characteristics such as surface area and pore volume in one material is difficult to accomplish—particulalry for an atomically ordered (graphitic) carbon. Herein we describe a synthesis strategy to engineer tunable hierarchically porous carbon (HPC) materials across micro- meso- and macroporous length scales, allowing the fabrication of a graphitic HPC with both very high surface area (> 2500 m2/g) and pore volume (>10 cm3/g), the combination of which has not been seen previously. The mesopore volume alone for these materials is up to 7.91 cm3/g, the highest ever reported. The unique material was explored for use as a supercapaictor electrode and for oil adsorption; two applications that require textural properties that are typicaly exclusive to one another. This design scheme for HPCs can be utilized in broad applications, including electrochemical systems such as batteries and supercapacitors, sorbents, and catalyst supports.

Estevez, Luis↗
DOE OSTI2018

Strong Electronic Coupling of Molecular Sites to Graphitic Electrodes via Pyrazine Conjugation

Glassy carbon electrodes were functionalized with redox-active moieties by condensation of o-phenylenediamine derivatives with o-quinone sites native to graphitic carbon surfaces. Electrochemical and spectroscopic investigations establish that these graphite-conjugated catalysts (GCCs) exhibit strong electronic coupling to the electrode, leading to electron transfer (ET) behavior that diverges fundamentally from that of solution-phase or surface-tethered analogues. We find that (1) ET is not observed between the electrode and a redox-active GCC moiety regardless of applied potential. (2) ET is observed at GCCs only if the interfacial reaction is ion-coupled. (3) Even when ET is observed, the oxidation state of a transition metal GCC site remains unchanged. From these observations, we construct a mechanistic model for GCC sites in which ET behavior is identical to that of catalytically active metal surfaces rather than to that of molecules in solution. These results suggest that GCCs provide a versatile platform for bridging molecular and heterogeneous electrocatalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Graphite Conjugation Eliminates Redox Intermediates in Molecular Electrocatalysis

The efficient interconversion of electrical and chemical energy requires the intimate coupling of electrons and small-molecule substrates at catalyst active sites. In molecular electrocatalysis, the molecule acts as a redox mediator which typically undergoes oxidation or reduction in a separate step from substrate activation. These mediated pathways introduce a high-energy intermediate, cap the driving force for substrate activation at the reduction potential of the molecule, and impede access to high rates at low overpotentials. Here we show that electronically coupling a molecular hydrogen evolution catalyst to a graphitic electrode eliminates stepwise pathways and forces concerted electron transfer and proton binding. Electrochemical and X-ray absorption spectroscopy data establish that hydrogen evolution catalysis at the graphite-conjugated Rh molecule proceeds without first reducing the metal center. These results have broad implications for the molecular-level design of energy conversion catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Effect of deuterium irradiation on graphite boronized in the NSTX-U tokamak

Boronization has been used in the National Spherical Torus-Upgrade (NSTX-U) as first wall conditioning technique. The technique decreased the oxygen impurities in the plasma and the O% on the Plasma Facing Components (PFC) as measured with an in-vacuo probe. Samples were extracted from tiles removed from the tokamak for post-mortem and controlled studies. Ex-vessel low energy and fluence D2+ and Ar+ irradiations were characterized in-situ to elucidate surface evolution of a cored graphite sample with an intrinsic concentration of boron from a tokamak environment. In addition, quadrupole mass spectrometer measurements of emitted D-containing species during irradiation, indicate potential retention of D by the boronized graphite interface and correlated back to the surface chemistry evolution. Classical Molecular Dynamics (CMD) simulations were used to investigate the chemistry of the B-C-O-D system. The results suggest that boron coatings retain oxygen by forming oxidized boron states in the presence of deuterium plasmas and corroborate empirical findings. A four times increase in the O% of the boron coatings was observed following in-situ deuterium exposures, in contrast with a reduction of equal magnitude observed after Ar irradiations. These results illustrate the complex chemistry driven by energetic ions at the edge of tokamaks plasmas on the PFCs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Heptagraphene: Tunable dirac cones in a graphitic structure

Here, we predict the existence and dynamical stability of heptagraphene, a new graphitic structure formed of rings of 10 carbon atoms bridged by carbene groups yielding seven-membered rings. Despite the rectangular unit cell, the band structure is topologically equivalent to that of strongly distorted graphene. Density-functional-theory calculations demonstrate that heptagraphene has Dirac cones on symmetry lines that are robust against biaxial strain but which open a gap under shear. At high deformation values bond reconstructions lead to different electronic band arrangements in dynamically stable configurations. Within a tight-binding framework this richness of the electronic behavior is identified as a direct consequence of the symmetry breaking within the cell which, unlike other graphitic structures, leads to band gap opening. A combined approach of chemical and physical modification of graphene unit cell unfurls the opportunity to design carbon-based systems in which one aims to tune an electronic band gap.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Optimizing dicyandiamide pretreatment conditions for enhanced structure and electronic properties of polymeric graphitic carbon nitride

Graphitic carbon nitride, a polymeric semiconductor, possesses a distinctive electronic band structure and exceptional chemical stability, making it a highly promising material for various catalytic applications such as electrocatalysis, photocatalysis, and photo-electrocatalysis. However, its practical applications remain limited due to its low active site density and poor electrical conductivity. In this study, to overcome such limitations, we have conducted a thorough investigation to explore the impact of dicyandiamide (DCDA) precursor pretreatment prior to thermal polymerization to graphitic carbon nitride. The DCDA precursor was subjected to various pretreatment methods including grinding using mortar and pestle, recrystallization through stirring or probe sonication after dissolving in deionized water, and freeze drying, prior to thermal polymerization at 550 °C for 2 hours. The structural and morphological properties of the catalysts prepared were compared and characterized by X-ray diffraction (XRD), attenuated total reflectance–Fourier transform infrared (ATR-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis while the electronic band gap properties were determined based on density functional theory (DFT) calculations for a set of crystalline systems having C/N ratios similar to those identified experimentally. In comparison to direct thermal polymerization, pretreated samples rendered the same product yield, diverse morphologies with flat or wrinkle structures, and reduced electrochemical resistance, making them suitable for use in various catalytic processes.

36 MATERIALS SCIENCE↗