Search NASA⌕ Search

SEARCH · Search NASA

Results for “Graphite”

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 613 records · Page 34
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Vacancy-driven variations in the phonon density of states of fast neutron irradiated nuclear graphite

Research examining radiation damage and its effects in graphite began in the 1940’s during the development of moderated nuclear reactors. Interest in this topic is expanding because of emerging applications associated with fullerenes and carbon nanostructures as well as its long-standing use as a fission moderator. In this work, we report the measurements of the full phonon density of states of irradiated nuclear graphite using inelastic neutron scattering experiments at room temperature. The samples were previously exposed to different levels of neutron doses and irradiation temperatures. The phonon density of states of perfect and defected graphite supercells including different configurations of vacancies and interstitials were calculated using first-principles direct method. Despite high neutron irradiation doses, the scattering measurements show that the induced damage is localized, and the layered structure is preserved. In conclusion, a comparison of the measured phonon densities of states of irradiated samples with those calculated of defected supercells indicates that the main changes observed are mainly attributed to formation of vacancies.

36 MATERIALS SCIENCE↗
DOE OSTI2024

3D printed carbon fiber reinforced carbon as an energy efficient alternative to graphite for EFAS tooling

As Electric Field Assisted Sintering (EFAS) gains more industrial acceptance and use, it becomes more important to develop more efficient means to implement this technology. To this aim, 3D printed continuous carbon fiber reinforced carbon (CCC) was manufactured and fabricated into tooling for EFAS systems as an alternative to traditional graphite tooling. The impact of fiber orientation on the thermal and electrical properties of the CCC was characterized. Sample material was sintered in Tokai G535 graphite tooling, under common processing conditions and compared with CCC tooling. There was nearly 50 % energy savings compared to graphite while maintaining equivalent sample density and microstructure plus keeping ram temperatures 39 % cooler. This is due to spatial control of generated heat and thermal diffusivity within the molds, by means of fiber orientation anisotropy. Finite element modeling of the tooling design supported the experimental results as well as displays the effect of optimization of this 3D printed CCC material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Benchmarking GEANT4 and PHITS for 14.8-MeV neutron transport in polyethylene and graphite materials

The feasibility of GEANT4 and PHITS with ENDF/B-VIII.0, JEFF-3.3 and JENDL-4.0 evaluated nuclear data libraries in 14.8-MeV neutron transport simulation are verified by comparing with the MCNP calculations and the experimental data. Here the measured data are from neutron integral experiments including graphite and polyethylene samples. For 6 cm-thick polyethylene and 20 cm-thick graphite samples, the results from GEANT4 and PHITS with three evaluated nuclear data libraries agree well with the MCNP calculations. For a 2 cm-thick graphite sample, the simulated results from GEANT4 and PHITS agree with the MCNP calculations, and they all underestimate the experiment data in below 3 MeV and overestimate them in the energy range of 5–7 MeV. The difference between the simulation results and the experimental data depends on the evaluated nuclear data libraries. In overall, GEANT4 and PHITS are performing reasonable jobs for 14.8-MeV neutron transport simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Encapsulation of LiFePO{sub 4} by in-situ graphitized carbon cage towards enhanced low temperature performance as cathode materials for lithium ion batteries

The severe capacity decay of LiFePO{sub 4} at low temperatures (≤0 °C) limits its wide applications as cathode materials for energy storage batteries. Creating comprehensive carbon network between particles with improved electronic conductivity is a well known solution to this problem. Here, a novel structured LiFePO{sub 4}/C composite was prepared by a facile solid state route, in which nanosized LiFePO{sub 4} spheres were encapsulated by in-situ graphitized carbon cages. With the enhancement in electronic conductivity (2.15e−1 S cm{sup −1}), the composite presented excellent rate performance at room temperature and remarkable capacity retention at −40 °C, with charge transfer resistance much lower than commercial LiFePO{sub 4}. - Graphical abstract: A novel structured LiFePO{sub 4/}C composite was prepared by a facile solid state route, in which nanosized LiFePO{sub 4} spheres were encapsulated by in-situ graphitized carbon cages. - Highlights: • Several nano-sized LiFePO{sub 4} particles are encapsulated in carbon cage. • Carbon is in-situ graphitized with enhanced electronic conductivity. • The as prepared LiFePO{sub 4} exhibits notable capacity retention at −40 °C. • R{sub ct} is lowered by a factor of ∼10 compared with commercial LiFePO{sub 4}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Study of reaction sequences during MSR synthesis of TiC by controlled ball milling of titanium and graphite

Highlights: • Insights on oxygen-bonded features formed during reactive ball milling • Evolution of off-stoichiometric TiC before ignition • Growth sequence of the TiC manifested as stacks and multilayers • Dual morphology of the MSR reaction product - Abstract: During reactive ball milling of Ti and C, mechanically induced self-propagating reaction (MSR) synthesis of TiC is reported to occur via a process including initial formation of small amounts of TiC prior to exothermic ignition, followed by MSR and the formation of stiochiometric TiC (Dorofeev et al., 2011; Oghenevweta et al., 2016 [1, 2]). However, both the chemical evolution and mechanisms of reaction and growth of TiC both prior to, during and after ignition are not fully understood. This research focuses on fundamental understanding of the reaction sequences during MSR synthesis of TiC from elemental Ti and C (graphite). Magnetically controlled ball milling of stoichiometric (1:1) powder mixtures of titanium (Ti) and graphite (C) was performed under He gas with the exothermic ignition point by determined via in-situ temperature measurement. X-ray diffraction, Scanning Transmission Electron Microscopy (STEM) with electron energy loss spectroscopy (EELS), Raman Spectroscopy and X-ray Photoelectron Spectroscopy (XPS) were employed to interpret the reaction sequences. The reaction sequence involved the following: During milling prior to ignition, severely deformed Ti, spheriodised graphite and amorphous carbon forms, and minor amounts of off-stiochiometric nano-TiC{sub 1−x} crystals. In addition to the formation of TiC{sub 1−x}, XPS revealed the formation of oxide skins coating the surface regions of the milled powders. There is also an evolution towards stiochiometric TiC with increasing milling time. Immediately after ignition, a reacted product comprising a mixture of multi-layer stacks of thin TiC plates form, in addition to a matrix comprising large TiC particles which have been liquid phase sintered under the high local heat of reaction by thin layers of unreacted Ti. MSR occurs via a dual mechanism involving rapid growth of existing TiC, plus nucleation and growth of new TiC. High spatially resolved EELS combined with STEM revealed additional information about the inhomogeneous chemical environment of the milled powders.

36 MATERIALS SCIENCE↗
DOE OSTI2025

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↗
DOE OSTI2020

Graphite Lithiation under Fast Charging Conditions: Atomistic Modeling Insights

The charging of lithium ion batteries in a fast and safe manner is critical for promoting the mass adoption of electric vehicles. Li intercalation in graphite electrodes is known to be one of the bottlenecks during the fast charging process. The mechanism of Li diffusion in highly polarized graphite anode at high current rates remains, however, not well understood. In this work, Density Functional Theory (DFT) calculations are used to gain insights into the Li diffusion process in graphite when it is far from equilibrium under fast charging conditions. The effect of uncompensated charges on Li mobility is determined in the highly polarized regions of the anode close to the interfaces. The extra charge was found to increase the interlayer spacing in the diffusion layer and adjacent channels, increasing the diffusivity and promoting the formation of Li clusters. A concerted diffusion mechanism at the edge of high-concentration Li domains is proposed to enhance the diffusion of Li.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Consequences of 131 I Transmutation in Gas Phase Radioiodine Molecules and Adsorbed on Graphite Surface

In the case of nuclear power plant accidents, several radionuclides are being dispersed into the environment. In particular, the release of radioiodine 131 I represents a major health concern because of its absorption by the thyroid gland. To reduce the release of 131 I into the environment, capture materials, such as activated carbon, provide a mean to efficiently retain radioiodine-bound molecular species. Here, we use ab initio molecular dynamic calculations to investigate the effects of 131 I radioactive decay on the molecular stability of I 2 , acid iodine (HI, HIO, HIO 2 , and HIO 3 ), and methyl-iodine species in both gas phase and adsorbed on graphite. In gas phase, we found that I 2 is the least resistant to 131 I transmutation, followed by the HIO x family of molecules, then HI and CH 3 I which are the most resistant. However, the graphite surface is found to greatly favorize the fragmentation of adsorbed molecular species. While the identification of gas phase fragments can offer new chemical route to consider in chemical kinetics models, the formation reactive fragment products at the graphite surface can favorize their reaction with surface carbon atoms which overtime could reduce the number of adsorption sites of capture materials available, and hence, impacting their capture capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Intercalation of Lithium into Graphite: Insights from First-Principles Simulations

Understanding ion intercalation at electrode–electrolyte interfaces is key to the development of energy storage and water desalination. Here, we investigate Li + kinetics at a prototypical interface between graphite anodes and an organic electrolyte, and we elucidate key factors that determine ion transport, using first-principles methodology coupling ab initio molecular dynamics simulations with a solvation model. We show that surface chemical composition significantly influences the kinetics of ion intercalation from the liquid into graphite. We find that this is partly related to the ion desolvation process, which varies notably for different graphite surface chemical terminations. In addition, interfacial polarization is found to play an important role in determining energy barriers for ion transfer. We also discuss the impact of electrode potentials, which is often neglected in conventional first-principles calculations despite being a key factor in device configurations. Our study provides insights into the coupling of electronic and ionic effects of interfacial chemistry on ion transport at complex electrode–electrolyte interfaces.

25 ENERGY STORAGE↗
DOE OSTI2024

Strain-Induced Shifts in Defective Graphite Phonon Modes Predicted by Density Functional Theory

Carbon fiber composites have gained attention as a structural material because of their high strength-to-weight ratio, and understanding the effect of defects on reactivity and mechanical properties is important for the longevity and safety of the composite. Although it is known that strain causes the underlying graphitic vibrational modes to redshift, it is not clear how strain may alter reactivity and defect-induced vibrational changes. To investigate the strain-induced phonon changes of defective carbon fiber composites, density functional theory calculations of graphite are used, including intercalated hydrogen and fluorine defects. By comparing changes in the bond lengths, formation energies, and phonon density of states for uniaxially and biaxially strained graphite, strain was found to generally make defect formation more favorable and the specific behavior changes are dependent on the strain direction and defect identity. Specifically, intercalated fluorine phonons are more sensitive to strain than hydrogen intercalation phonons, and strain applied along the zigzag direction alters the calculated properties more than strain along the armchair direction. Finally, these results highlight the importance of understanding the microstructural effect of deviations from the ideal material because small changes in strain or defect type can significantly alter the behavior of the carbon fiber composite core.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Structure and Interaction of Ionic Liquid Monolayer on Graphite from First-Principles

The ionic-liquid/graphite interface is important in understanding the behaviors of the ionic-liquid electrolyte in carbon-based supercapacitors and Li-ion batteries. A row-like cation–anion structure of the 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([BMP][TFSA]) ionic liquid (a popular choice for interfacial studies) on the graphite surface has been suggested on the basis of scanning tunneling microscopy images, but it is unclear if this structure is the most stable one. Herein, we explore alternative models of the [BMP][TFSA] monolayer on graphite basal plane with first-principles density functional theory. We find that the checkerboard type of structure is in fact more stable than the row-like structure. We further use simulated annealing based on classical molecular dynamics simulations to obtain more stable conformations of ions on the surface. Both charge-density-difference and noncovalent-interaction analyses show that the higher stability of the checkerboard structure than the row-like structure is due to the stronger anion–surface interactions in the former. Furthermore, our work therefore suggests a new structure of the [BMP][TFSA] monolayer on the graphite basal plane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Influence of Dissolved O 2 in Organic Solvents on CuOEP Supramolecular Self-Assembly on Graphite

The supramolecular self-assembly of copper(II) octaethylporphyrin (CuOEP) and octaethylporphyrin (H 2 OEP) on graphitic surfaces immersed in organic solvents (dichlorobenzene, dodecane) is studied using scanning tunneling microscopy (STM) and Raman spectroscopy. STM reveals that the self-assembled structure of CuOEP in 1,2-dichlorobenzene is significantly altered by dissolved oxygen within the solvent. Raman spectroscopy reveals that the presence of the oxygen alters the molecule-substrate interaction, which is attributed to the adsorption of oxygen on the Cu center of the CuOEP, which is facilitated by electron transfer from the graphitic surface. Such oxygen-induced changes are not observed for H 2 OEP, indicating that the metal center of CuOEP plays a critical role. Finally, when the solvent is dodecane, we find that solvation effects dominate. CuOEP adsorbed on graphitic surfaces provides a model system relevant to the study of the transport and activation of oxygen by enzymes and other complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, in which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2019

Spatially Resolving Lithiation in Silicon–Graphite Composite Electrodes via in Situ High-Energy X-ray Diffraction Computed Tomography

Optimizing the chemical and morphological parameters of lithium-ion (Li-ion) electrodes is extremely challenging, due in part to the absence of techniques to construct spatial and temporal descriptions of chemical and morphological heterogeneities. We present the first demonstration of combined high-speed X-ray diffraction (XRD) and XRD computed tomography (XRD-CT) to probe, in 3D, crystallographic heterogeneities within Li-ion electrodes with a spatial resolution of 1 um. The local charge-transfer mechanism within and between individual particles was investigated in a silicon(Si)-graphite composite electrode. Here, high-speed XRD revealed charge balancing kinetics between the graphite and Si during the minutes following the transition from operation to open circuit. Subparticle lithiation heterogeneities in both Si and graphite were observed using XRD-CT, where the core and shell structures were segmented, and their respective diffraction patterns were characterized.

36 MATERIALS SCIENCE↗
DOE OSTI2015

The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes

Propylene carbonate (PC) is seldom used in lithium-ion batteries (LIBs) due to its sustained co-intercalation into graphene structure and the eventual graphite exfoliation, despite potential advantages it brings, such as wider liquid range and lower cost. Here we discover that cesium cation (Cs+), originally used to suppress dendrite growth of Li metal anode, directs the formation of solid electrolyte interphase (SEI) on graphitic anode in PC-rich electrolytes through preferential solvation. Effective suppression of PC-decomposition and graphite-exfoliation was achieved when the ratio of ethylene carbonate (EC)/PC in electrolytes was so adjusted that the reductive decomposition of Cs+-(EC)m (1≤m≤2) complex precedes that of Li+-(PC)n (3≤n≤5). The interphase directed by Cs+ is stable, ultrathin and compact, leading to significant improvements in LIB performances. In a broader context, the accurate tailoring of SEI chemical composition by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions processes that once were elusive.

cesium cation↗
DOE OSTI2016

Role of Manganese Deposition on Graphite in the Capacity Fading of Lithium Ion Batteries

Lithium-ion batteries utilizing manganese based cathodes have received considerable interest in recent years for their lower cost and favorable environmental friendliness relative to their cobalt counterparts. However, Li-ion batteries using manganese based cathodes and graphite anodes suffer from severe capacity fading at higher operating temperature. In this article, we report on an astute investigation into how the dissolution of manganese impacts the capacity fading within the Li-ion batteries. Our investigation reveals that the manganese dissolves from the cathode, transports to the graphite electrode, and deposits onto the outer surface of the inner most solid electrolyte interphase (SEI) layer which is known to be a mixture of inorganic salts (e.g. Li2CO3, LiF, and Li2O). In this location, the manganese facilitates the reduction of the electrolyte and the subsequent formation of lithium containing products on the graphite which removes lithium ions from the normal operation of the cell and thereby induces the severe capacity fade.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Effective Strategy for Improving Electrocatalyst Durability by Adhesive Immobilization of Catalyst Nanoparticles on Graphitic Carbon Supports

We have found that Ta-based additive films in our catalyst system act as adhesives, which improves electrocatalyst durability by immobilizing the catalyst Pt NPs on the graphitic Vulcan carbon support. Furthermore, we suggest that this can be a general design principle in producing higher-durability electrocatalysts on graphitic supports. By electrochemically probing the contributing roles of the tantalum oxide (Ta 2 O 5 ) and the polyphosphate (PPA) components in separate samples, we show that these combine to produce the observed improvement in activity and durability of our best catalyst, the tantalum polyphosphate (TaOPO 4 )-treated sample. To control variables for a valid electrochemical comparison, such as dissimilar catalyst particle size distributions and variations in surface coverage, four new catalyst samples closely matched in every way were prepared: (1) Pt/VC, (2) Pt/[PPA/VC], (3) Pt/[Ta 2 O 5 /VC], and (4) Pt[TaOPO 4 /VC]. We present HR-TEM/HAADF-STEM, EDS elemental mapping, PXRD, XPS, and electrochemical activity and durability evidence, showing that the TaOPO4 and Ta2O5 additives act as adhesives, effectively tethering the NPs to the VC graphitic support surface. Pt/[Ta 2 O 5 /VC] exhibited 3× better durability as compared with the Pt/VC control because of better catalyst nanoparticle immobilization by the Ta 2 O 5 adhesive. Pt[TaOPO 4 /VC] is the overall best performer, exhibiting both a high MA of 0.82 A mg Pt –1, the highest ORR MA after heat treatment, as well as 1.75× greater durability over the Pt/VC control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Graphite-Conjugated Pyrazines as Molecularly Tunable Heterogeneous Electrocatalysts

Condensation of ortho-phenylenediamine derivatives with ortho-quinone moieties at edge planes of graphitic carbon generates graphite-conjugated pyrazines (GCPs) that are active for oxygen reduction electrocatalysis in alkaline aqueous electrolyte. Catalytic rates of oxygen reduction are positively correlated with the electrophilicity of the active site pyrazine unit and can be tuned by over 70-fold by appending electron-withdrawing substituents to the phenylenediamine precursors. Discrete molecular analogs containing pyrazine moieties display no activity above background under identical conditions. This simple bottom up method for constructing molecularly well-defined active sites on ubiquitous graphitic solids enables here the rational design of tunable heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗