Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Graphite Oxidation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 685 records · Page 38
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Property evaluation and microstructure characterization of the A3-3 matrix graphite - 18440

Spherical fuel elements with TRISO fuel will be used in the pebble-bed high temperature gas-cooled nuclear reactor. The fuel will be located within the center region of the elements, and will be suspended in, and surrounded by a shell of matrix graphite. The matrix graphite provides structural support to the fuel, prevents fuel damage, and allows for heat transfer from the fuel to the coolant. The raw materials for the matrix graphite, type A3-3, includes 64 wt% natural flake graphite, 16 wt% artificial graphite and 20 wt% phenol resin binder. After the final heat treatment, the resulting A3-3 matrix is composed of 71 wt% natural graphite, 18 wt% artificial graphite, and 11 wt% phenol resin-derived coke carbon. The microstructure of A3-3 matrix graphite has direct influences on the material properties, which are crucial to maintaining the integrity and safety of the fuel elements. This presentation will discuss microstructure features, such as lattice, and crystal parameters, porosity, pore size and distribution, and anisotropy. The multiple physical, mechanical and thermal properties of this material, including: elastic modulus, mechanical strength, and oxidation property will also be presented. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Production of graphene-derivatives using organic molecules for supercapacitors and beyond

Graphene is rapidly expanding for applications ranging from nanoelectronics to space exploration. A material with such enormous potential requires a variety of synthesis methods. Here, we report a library of relatively sustainable redox-active organic molecules for the reduction of graphene oxide (GO) namely N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), 7,7,8,8-tetracyanoquinodimethane (TCNQ), ferrocene (Ferro), and decamethylferrocene (DFerro). Among them, the reduction of GO using TMPD starts even with simple hand-shaking for just a few minutes. By controlling the sonication time under ambient conditions, one can control the electronic properties of the reduced graphene oxide (rGO). The resulting free-standing films delivered a capacitance of 185 F/g when tested them as supercapacitor electrodes. We also demonstrated that TMPD can exfoliate graphite into few-layer graphene sheets with simple sonication. Here, we further show that under mild heating, these molecules can serve as dopants during the reduction process to produce nitrogen-doped graphene. Our results may guide researchers to explore sustainable organic molecules for the large-scale production of graphene-based materials for diverse applications.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Perfluoro Aryl Boronic Esters as Chemical Shuttle Additives in Lithium Ion Batteries

Redox shuttles could provide an added measure of control for lithium ion batteries beyond that which is provided by the battery management system. Redox shuttles, which are electrolyte additives, provide electrochemical overcharge protection. Since they possess a reduction-oxidation potential that is slightly above the maximum cathode potential during normal use, they should cause no degradation in cell performance during normal operation, but should shuttle excess electrons during overcharge conditions, effectively limiting the full cell voltage. The goals of the Chemical Shuttle Additives program were to discover and implement a redox shuttle that is compatible with large format lithium ion cells utilizing LiNi 1/3 Mn 1/3 Co 1/3 O 2 (NMC) cathode material and to understand the mechanism of redox shuttle action. Many redox shuttles, both commercially available and experimental, were tested and much fundamental information regarding the mechanism of redox shuttle action was discovered. In particular, studies surrounding the mechanism of the reduction of the oxidized redox shuttle at the carbon anode surface were particularly revealing. Shuttles that were evaluated in various lithium ion cell chemistries include: • 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (BDB) supplied by Argonne National Laboratory (ANL), Lemont, Illinois; • 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB) supplied by 3M, St. Paul, Minnesota; • Li 2 B 12 F 12 supplied by Air Products, Allentown, Pennsylvania (pure compound) and Showa Denko, Japan (in electrolyte); • 1,4-bis(2-methoxyethoxy)-2,5-di-tert-butyl-benzene (ANL-RS2) supplied by Argonne National Laboratory (ANL), Lemont, Illinois; and • A 4.5V class redox shuttle supplied by Argonne National Laboratory (ANL), Lemont, Illinois Although redox shuttles with an appropriate redox potential and sufficient chemical and electrochemical stability for cells utilizing cathodes with potentials higher and lower than that of NMC, a redox shuttle that is viable for use in large format lithium ion cells with NMC cathodes was not found. The effect of the anode on the capacity loss of lithium ion cells with redox shuttles in cells utilizing lithium, lithium titanate, or graphite cells was studied. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.

25 ENERGY STORAGE↗
DOE OSTI2019

Kinetics of SiC Formation on Graphite Using N{sub 2}-CO-SiO and N{sub 2}-CO-H{sub 2}-SiO Gas Mixtures

The formation of SiC on a graphite surface through the reaction between SiO gas and C was investigated. Experiments were conducted at 1843 K, 1873 K, and 1903 K (1570 °C, 1600 °C, and 1630 °C) under N{sub 2}-CO-SiO or N{sub 2}-CO-H{sub 2}-SiO gas mixture atmospheres. The formation rate of SiC on the graphite increased with the increasing temperature and with the decreasing partial pressure of CO gas. The forward (k{sub f}) and backward (k{sub b}) reaction rate constants of SiC formation with SiO gas were obtained as follows: lnk{sub f}(mol/cm{sup 2}⋅s⋅atm)=29.175−76,083/Tlnk{sub b}(mol/cm{sup 2}⋅s⋅atm)=53.518−129,072/TUnder the N{sub 2}-CO-H{sub 2}-SiO gas mixture atmosphere, the formation rate of SiC on the graphite increased. It was observed that the formation of SiC whiskers was enhanced by the catalytic reaction in liquid Fe-based nanodroplets.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Microwave-assisted catalytic gasification of mixed plastics and corn stover for low tar, hydrogen-rich syngas production

The challenge for efficient management of post-consumer plastic and biomass waste has grown over the past few decades due to their dramatic increases. In comparison to conventional gasification, microwave-assisted co-gasification of plastics and corn stover offers many benefits, including increased H 2 yield and gas components compared to unfavorable char/tar. Nonetheless, for future commercialization of the process and ease of product separation, further reduction of the undesirable tar is necessary, which can be achieved over the catalytic route. Here, in this work, we studied the catalytic effect of magnetite for microwave-assisted co-gasification of corn stover and plastic to make syngas with higher H 2 and lower tar selectivity over non-catalytic conditions. A 1:1:1 ratio of plastic-corn stover-magnetite was used to evaluate the reaction parameters such as temperature, space velocity, heating media, and catalytic cycles under gasification conditions. In comparison with the microwave non-catalytic route, a 100% increase in the total H 2 yield with 76% higher H 2 production efficiency (mmol/kWh) was achieved in the presence of the magnetite catalyst, while reducing the overall tar formation from 9% to 2%. When magnetite was reduced in situ during the reaction, it coupled with microwave and delivered oxygen radicals that cracked down plastic and corn stover intermediates generated from the synergistic effect under microwave heating. Soon after the oxygen transfer process initiated, magnetite reached its final oxidation state consisting of microwave-active Fe and Fe 3 C phases that continued coupling with microwaves along with the generated graphitic carbon to maintain the heat necessary to further reduce the generated tar and make additional gaseous products, as confirmed by XRD, Raman, and TGA analyses.

08 HYDROGEN↗
DOE OSTI2016

Nanographite-TiO{sub 2} photoanode for dye sensitized solar cells

Nanographite-TiO{sub 2} (NG-TiO{sub 2}) composite was successfully synthesized by the hydrothermal method and its performance as the photoanode for dye-sensitized solar cells (DSSCs) was investigated. Environmental Scanning electron microscope (E-SEM) micrographs show the uniform distribution of TiO{sub 2} nanoflowers deposited over nanographite sheets. The average performance characteristics of the assembled cell in terms of short-ciruit current density (J{sub SC}), open circuit voltage (V{sub OC}), fill factor (FF) and photoelectric conversion efficiency (η) were measured.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
NASA NTRS1991

Pretreatment of lubricated surfaces with sputtered cadmium oxide

Cadmium oxide is used with a dry solid lubricant on a surface to improve wear resistance. The surface topography is first altered by photochemical etching to a predetermined pattern. The cadmium oxide is then sputtered onto the altered surface to form an intermediate layer to more tightly hold the dry lubricant, such as graphite.

Fusaro, Robert L.↗
DOE OSTI2023

NanoMechanics: Elasticity and Friction in Nano‐Objects

A large scientific and technological effort is underway to investigate the properties of two‐dimensional (2D) materials to become building blocks in integrated nano‐electronic and photonic circuits, composites, coatings, energy harvesting nano‐ systems, nano‐sensors, and nano‐electro‐mechanical systems (NEMS).While several experiments and calculations have revealed exciting novel phenomena in these nanostructures, many scientific and technological questions remain open. In particular, understanding and controlling the structure and mechanical properties of 2D materials at the interface with a solid surface is of key importance to enable the aforementioned nanotechnologies, as well as to fulfill the potential of strain engineering to tailor their properties. The vision of this DoE research program was to investigate novel mechanical properties and phenomena in 1D and 2D materials with the overarching goal of defining a new basic understanding of mechanical behavior in nano and quantum systems. The group of the PI has developed in the last years several studies on the mechanical properties of Carbon nanotubes and oxide nanobelts, more recently the PI has focused her attention on the properties of two‐dimensional materials, such as graphene and MoS 2 , which are a few‐atomic‐layer thick films and hold a great potential for technological and energy applications. The most studied 2D material is graphene, existing as a single layer of graphite or a few‐layer thick epitaxial graphene film. Graphene possesses a large in‐plane Young’s modulus as well as high intrinsic carrier mobility, and high in‐plane thermal conductivity. Besides graphene, also 2D films of graphene oxide (GO), hexagonal Boron Nitride (h‐BN), and transition metal dichalcogenides such as MoS 2 exhibit unique and excellent properties and hold great promise for nanotechnology applications. This research program was aimed at developing a new basic understanding of the mechanical properties of 1D and 2D materials at the interface with solid substrates, with a focus on the role of defects, materials structure, and substrate interaction. Ultimately, we aimed at developing the basic knowledge and experimental tools for manipulating 1D and 2D materials’ structure, stacking, substrate interaction, defects, and number of layers to realize an entirely new class of ultra‐hard, ultra‐thin, and ultra‐light active materials with ad‐ hoc mechanical properties for a variety of applications.

2D Materials↗
DOE OSTI2022

Graphene coating on silicon anodes enabled by thermal surface modification for high-energy lithium-ion batteries

Silicon is a high-energy density anode material for lithium-ion batteries, but it possesses shortcomings such as poor electronic conductivity, interfacial instability and mechanical fracturing that hinder its battery cycling. Carbon coating has been an important strategy for stabilizing silicon anodes, but the effects of the silicon surface properties on carbon coating morphology and the consequent silicon cycling stability have not been clearly elucidated. Herein, we find that thermal oxidation of the silicon anodes followed by chemical vapor deposition of carbonaceous precursors leads to a well-ordered graphene coating, whereas disordered graphite coating is formed on the native silicon surface. Graphene-coated silicon exhibits superior cycling performance, retaining a discharge capacity of ~1300 mAh g -1 after 300 cycles, whereas the disordered graphite-coated silicon suffers continuous degradation, retaining only~600 mAh g -1 after 300 cycles. Cryogenic electron microscopy reveals the mechanism behind the difference in cycling stabilities; graphene coated silicon is able to withstand the large mechanical strains induced during extended cycling, whereas disordered graphite coating is ruptured, exposing silicon surfaces to the electrolyte, leading to extensive buildup of SEI and poor cycling performance. Characterization of the silicon surface reveals that thermal treatment yields an oxygen-rich surface layer, which is hypothesized to play a decisive role in dictating the carbon coating. This work highlights the effect of silicon surface properties on carbon coating microstructure, and presents thermal treatment as a facile avenue to attain graphene coating on silicon anodes.

25 ENERGY STORAGE↗
NASA NTRS1992

Structure-to-property relationships in addition cured polymers. 4: Correlations between thermo-oxidative weight losses of norbornenyl cured polyimide resins and their composites

Relationships are identified between the thermo-oxidative stability (TOS) at 316 C of a wide variety of PMR (polymerization of monomeric reactants) addition cured polyimide resins and their corresponding graphite fiber composites. Weight loss results at 316 C confirmed the expected relationship of increasing aliphatic endcap content with decreasing TOS. Moreover, the resin TOS study also showed an unexpected linear correlation of decreasing weight loss to increasing ratio of benzylic diamine to aliphatic endcap in the range of the stoichiometries studied. Only after long term 316 C aging does the dianhydride used with the benzylic diamines become an additional factor in influencing the amount of PMR resin and composite weight losses. Also, the benzylic systems consistently showed much lower resin and composite weight losses at 316 C than the corresponding nonbenzylic norbornenyl resins and composites, except when the nonbenzylic diamine monomer does not contain a connecting group. Instead, this diamine resulted in a 316 C resin and composite weight loss that was only competitive with benzylic type diamines. Results show excellent correlation between TOS of all graphite fiber PMR composites and resins.

Alston, William B.↗
DOE OSTI2018

Mn versus Al in Layered Oxide Cathodes in Lithium-Ion Batteries: A Comprehensive Evaluation on Long-Term Cyclability

Nickel-rich layered oxide cathodes with the composition LiNi 1-x-y Co x Mn y O 2 (NCM, (1-x-y) ≥ 0.6) are under intense scrutiny recently to contend with commercial LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA) for high-energy-density batteries for electric vehicles. However, a comprehensive assessment of their electrochemical durability is currently lacking. Herein, two in-house cathodes, LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 0.7 Co 0.15 Mn 0.15 O 2 , are investigated in a high-voltage graphite full cell over 1500 charge-discharge cycles (≈5–10 year service life in vehicles). Despite a lower nickel content, NCM shows more performance deterioration than NCA. Critical underlying degradation processes, including chemical, structural, and mechanical aspects, are analyzed via an arsenal of characterization techniques. Overall, Mn substitution appears far less effective than Al in suppressing active mass dissolution and irreversible phase transitions of the layered oxide cathodes. The active mass dissolution (and crossover) accelerates capacity decline with sustained parasitic reactions on the graphite anode, while the phase transitions are primarily responsible for cell resistance increase and voltage fade. With Al doping, on the other hand, secondary particle pulverization is the more limiting factor for long-term cyclability compared to Mn. Finally, these results establish a fundamental guideline for designing high-performing Ni-rich NCM cathodes as a compelling alternative to NCA and other compositions for electric vehicle applications.

25 ENERGY STORAGE↗
NASA NTRS1975

The effect of C/O ratio on the condensation of planetary material

The condensation temperatures of refractory silicates and oxides in a gas of cosmic composition are strongly dependent on the C/O ratio. As the ratio increases from 0.4 to 0.9, condensation temperatures of compounds such as Al2O3, Ca2Al2SiO7, MgAl2O4, Mg2SiO4, and MgSiO3 decrease by 50-100 degrees. As C/O increases from 0.9 to 1.0, these temperatures drop an additional 300-400 degrees. Other chemical differences result when C/O approximately equals or exceeds 0.9. A new suite of high-temperature minerals appears (graphite, CaS, Fe3C, SiC and TiN); the reaction CO + 3H2 yields CH4 + H2O proceeds to the right at higher temperatures; and iron, whose condensation temperature is unaffected, condenses at higher temperatures than any silicate or oxide.

Larimer, J. W.↗
DOE OSTI2018

A look into the voltage plateau signal for detection and quantification of lithium plating in lithium-ion cells

Voltage plateau during relaxation or discharge after charging is a distinct signal associated with stripping of deposited Li metal and hence a feasible tool for online detection of Li plating in Li-ion batteries. In this report we present a physics-based model with incorporation of Li plating and stripping to gain a fundamental understanding of the voltage plateau behavior. Specifically, we focus on the internal cell characteristics when voltage plateau occurs and on key factors affecting the shape and duration of voltage plateau. Furthermore, the validity of using the duration of voltage plateau for estimating Li plating amount is assessed. It is found that the duration of voltage plateau depends on the rate of Li stripping, while the stripping rate is restricted by the capability of Li+ intercalation into graphite. Parameters like intercalation kinetics, solid-state diffusivity of graphite and cell temperature can substantially influence the voltage curves even with the same amount of Li plating. Further, we report an interesting phenomenon that during Li stripping one part of anode near the separator has net oxidation current (local stripping rate > intercalation rate), providing Li+ ions and electrons to the other part of anode near the foil which has net reduction current.

25 ENERGY STORAGE↗
DOE OSTI2019

Investigation of Vipera Anatolica Venom Disintegrin via Intracellular Uptake with Radiolabeling Study and Cell-Based Electrochemical Biosensing Assay

Snake venoms are a natural biological source that has potential therapeutic value with various protein compounds. Disintegrins originally were discovered as a family of proteins from snake venoms composed of cysteine rich low molecular weight polypeptides. Disintegrins exhibit specific binding and higher affinity toward integrin with potential inhibition of function. Trans-membrane receptors of the integrin family may involve in many pathological conditions such as inflammation and tumor progression with important processes related to invasion and migration. Since disintegrins have the ability to bind to integrins, they could be used for cancer detection and treatment, and in monitoring of therapy in select cancer types. The main purpose of the study is to investigate disintegrin containing Vipera anatolica (VAT) crude venom potential for radiolabeling and intracellular uptake as well as electrochemical biosensing assay against U87MG human brain glioblastoma cells. For this purpose, VAT crude venom containing U87MG cell-specific disintegrin was investigated in terms of radiolabeling and intracellular uptake as well as electrochemical biosensing assay in comparison with echistatin (ECT) disintegrin in cells. The interaction between VAT crude venom and ECT with HEK293 human non-tumorigenic embryonic kidney cells and glioblastoma U87MG cells was electrochemically investigated using pencil graphite electrodes (PGEs). The interaction of the VAT crude venom and ECT with HEK293 and U87MG cells was detected according to the changes in oxidation signals. Then, VAT crude venom and echistatin were labeled with {sup 131}I via iodogen method. Intracellular uptakes of radiolabeled molecules were investigated in U87MG cell line. {sup 131}I-VAT can be an agent for imaging of glioblastoma cancer. Further work will focus on the production of large quantities of pure VAT disintegrin with a biotechnological approach to improving imaging agent.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2015

Catalytic propane dehydrogenation over In₂O₃–Ga₂O₃ mixed oxides

We have investigated the catalytic performance of novel In₂O₃–Ga₂O₃ mixed oxides synthesized by the alcoholic-coprecipitation method for propane dehydrogenation (PDH). Reactivity measurements reveal that the activities of In₂O₃–Ga₂O₃ catalysts are 1–3-fold (on an active metal basis) and 12–28-fold (on a surface area basis) higher than an In₂O₃–Al₂O₃ catalyst in terms of C₃H₈ conversion. The structure, composition, and surface properties of the In₂O₃–Ga₂O₃ catalysts are thoroughly characterized. NH₃-TPD shows that the binary oxide system generates more acid sites than the corresponding single-component catalysts. Raman spectroscopy suggests that catalysts that produce coke of a more graphitic nature suppress cracking reactions, leading to higher C₃H₆ selectivity. Lower reaction temperature also leads to higher C₃H₆ selectivity by slowing down the rate of side reactions. XRD, XPS, and XANES measurements, strongly suggest that metallic indium and In₂O₃ clusters are formed on the catalyst surface during the reaction. The agglomeration of In₂O₃ domains and formation of a metallic indium phase are found to be irreversible under O₂ or H₂ treatment conditions used here, and may be responsible for loss of activity with increasing time on stream.

Tan, Shuai↗
DOE OSTI2016

The optical properties and photocatalytic activity of CdS-ZnS-TiO{sub 2}/Graphite for isopropanol degradation under visible light irradiation

This research prepared a photocatalyst tablet of CdS-ZnS-TiO{sub 2} on a graphite substrate. The synthesis was conducted through chemical bath deposition method. The graphite substrate used was a waste graphite rod from primary batteries. The aims of this research are studying the crystal structure, the optical properties and the photocatalytic activity of the prepared material. The photocatalytic activity was determined through isopropanol degradation. The result shows that the TiO{sub 2}/Graphite provide direct transition gap energy at 2.91 eV and an indirect transition gap energy at 3.21 eV. Deposition of CdS-ZnS changed the direct transition gap energy to 3.01 eV and the indirect transition gap energy to 3.22 eV. Isopropanol degradation with the prepared catalyst produced new peaks at 223-224 nm and 265-266 nm confirming the production of acetone. The degradation follows first order with rate constant of 2.4 × 10{sup −2} min{sup −1}.

36 MATERIALS SCIENCE↗