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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.

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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Novel pyrolytic boron nitride coating to reduce graphite interactions in molten fluoride salt

Future salt reactors like the Fluoride-salt-cooled-High Temperature Reactor require varying material flavors. Graphite is required for neutron moderation and potential fuel forms, while structural metals are required for containment. Studies show graphite/metal interactions exist when both materials share a salt medium. These interactions may accelerate the corrosion of the metal and change the surface of graphite materials. A novel pyrolytic boron nitride coating on graphite is investigated for reducing graphite/metal interactions. Finally, this is the first known application of such a coating, and salt exposure tests reveal the pyrolytic boron nitride coating reduces the interactions between stainless steel and uncoated graphite.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2022

High-Temperature Thermodynamics Modeling of Graphite

We present high-temperature thermodynamic properties for graphite from first-principles anharmonic theory. The ab initio electronic structure is obtained from density-functional theory coupled to a lattice dynamics method that is used to model anharmonic lattice vibrations. This combined approach produces free energies and specific heats for graphite that compare well with available experiments and results from models that empirically represent experimental data, such as CALPHAD. We show that anharmonic theory for the phonons is essential for accurate thermodynamic quantities above about 1000 K.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Sucrose‐Based Dense, Pure, and Highly‐Crystalline Graphitic Materials for Lithium‐Ion Batteries

At present, most synthetic graphite materials commonly used as anode active ingredients in lithium-ion cells are produced by graphitization of petroleum cokes. The carbon footprint associated with synthetic graphite production is significant. Thus, bio-derived and cheap precursors, such as saccharides, would be an attractive alternative for the sustainable production of graphitic carbons. However, they are non-graphitizing at temperatures as high as 3000 °C, preserving the curved, fullerene-like structure of graphene layers and microporosity. Consequently, many lithium ions are consumed during the formation of solid electrolyte interphase films and passivated in the nanovoids. Here, a method for the production of pure, crystalline, graphitic materials based on sucrose disposed of microporosity is presented, which also works with a variety of saccharides and other organic precursors of hard carbons—generally considered incapable of such transformation. This process employs catalytic graphitization by Si particles at high temperatures. Finally, the electrochemical response of such derived sucrose-based graphite in Li-ion half-cells demonstrated its feasibility to serve as an anode active material for rechargeable Li-ion batteries.

Si particles↗
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 OSTI2024

Constrained patterning of orientated metal chalcogenide nanowires and their growth mechanism

One-dimensional metallic transition-metal chalcogenide nanowires (TMC-NWs) hold promise for interconnecting devices built on two-dimensional (2D) transition-metal dichalcogenides, but only isotropic growth has so far been demonstrated. Here we show the direct patterning of highly oriented Mo 6 Te 6 NWs in 2D molybdenum ditelluride (MoTe 2 ) using graphite as confined encapsulation layers under external stimuli. The atomic structural transition is studied through in-situ electrical biasing the fabricated heterostructure in a scanning transmission electron microscope. Atomic resolution high-angle annular dark-field STEM images reveal that the conversion of Mo 6 Te 6 NWs from MoTe 2 occurs only along specific directions. Combined with first-principles calculations, we attribute the oriented growth to the local Joule-heating induced by electrical bias near the interface of the graphite-MoTe 2 heterostructure and the confinement effect generated by graphite. Using the same strategy, we fabricate oriented NWs confined in graphite as lateral contact electrodes in the 2H-MoTe 2 FET, achieving a low Schottky barrier of 11.5 meV, and low contact resistance of 43.7 Ω µm at the metal-NW interface. Our work introduces possible approaches to fabricate oriented NWs for interconnections in flexible 2D nanoelectronics through direct metal phase patterning.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A novel fiber-fretting test for tribological characterization of the fiber/matrix interface

Ceramic matrix composites exhibit excellent high temperature properties and are candidate materials for structural applications from jet engines to nuclear fuel cladding. The strength and deformation behavior of these composites are intrinsically tied to the properties of the fiber/matrix interface. This research introduces a novel technique to evaluate the fundamental friction and wear characteristics of these interfaces. A case study on SiC f /PyC/SiC m composites applies in situ fiber fretting to investigate the kinetic friction coefficient and cyclic wear characteristics of the interphase. The experimental methodology is presented in explicit detail to encourage other researchers to explore the capabilities of this technique. Additionally, testing was carried out as a function of fiber roughness, PyC thickness (≈10, 500, 1200 nm), cycle count (10, 100, 1000), and frequency (1, 5, and 10 Hz). The friction coefficient and wear behavior changed with cycle length due to a transition from adhesive to abrasive mechanisms. SEM fractography provided insights to tribological evolution from adhesive sliding to three-body abrasive wear. The structural disorder at the tribo-surface relating to graphitic content and dangling bond density was investigated using Raman spectroscopy. Properties are contextualized with comparison to uniaxial tensile behavior of the parent composite.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Tunable mechanical behavior of graphene nanoribbon-metal composites fabricated through an electrocharge-assisted process

This work investigates the role of a carbon nanophase on the local mechanical behavior of nanocarbon metal matrix composites (NCMCs) produced through an electrocharge-assisted process. Nanoindentation experiments on single crystal Al, Al 1350 parent alloys, and Al 1350 NCMCs revealed variable mechanical properties, caused by an interplay between microstructure and graphitic reinforcements. TEM and AFM studies also reveal nanoscale structural changes based on the incorporation of a carbon nanophase. In order to decouple the effects of the aforementioned mechanical behaviors, molecular dynamics nanoindentation simulations were performed on the (111) surface of Al and Al NCMC samples containing semi-infinite graphene nanoribbons to examine the evolution of plasticity over time. Findings indicate that the arrangement of a finite graphene nanophase within a host matrix can alter plasticity mechanisms and therefore yield strength in near-surface mechanical behavior with little effect on elastic properties. Here, this understanding enables further study into tunable bulk properties of Al-based NCMCs while isolating microstructural effects and reinforcement effects of the carbon phase. Such an understanding will lead to application-specific material geometries ranging from highperforming vehicle structures to next-generation electrical devices.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Atomic cluster expansion potential for large scale simulations of hydrocarbons under shock compression

We present an Atomic Cluster Expansion (ACE) machine learned potential developed for high-fidelity atomistic simulations of hydrocarbons, targeting pressures and temperatures near and above supercritical fluid regimes for molecular fluids. A diverse set of stoichiometries were covered in training, including 1:0 (pure carbon), 1:4 (methane), and 1:1 (benzene), and rich bonding environments sampled at supercritical temperatures, hydrogen rich, reactive mixtures where metastable stoichiometries arise, including 1:2 (ethylene) and 1:3 (ethane). A high-fidelity training database was constructed by performing large-scale quantum molecular dynamic simulations [density functional theory (DFT) MD] of diamond, graphite, methane, and benzene. A novel approach to selecting structures from DFT MD is also presented, which allows for the rapid selection of unique DFT MD frames from complex trajectories. Comparisons to DFT and experimental data demonstrate that the presented ACE potential accurately reproduces isotherms, carbon melting curves, radial distribution functions, and shock Hugoniots for carbon and hydrocarbon systems for pressures up to 100 GPa and temperatures up to 6000 K for hydrocarbon systems and up to 9000 K for pure carbon systems. This work delivers a potential that can be used for accurate, large-scale simulations of shocked hydrocarbons and demonstrates a methodology for fitting and validating machine learning interatomic potentials to complex molecular environments, which can be applied to energetic materials in future works.

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

Engineering Surface Oxygenated Functionalities on Commercial Carbon toward Ultrafast Sodium Storage in Ether-Based Electrolytes

The pursuit of a high-capacity anode material has been urgently required for commercializing sodium-ion batteries with a high energy density and an improved working safety. In the absence of thermodynamically stable sodium intercalated compounds with graphite, constructing nanostructures with expanded interlayer distances is still the mainstream option for developing high-performance carbonaceous anodes. In this regard, a surface-functionalized and pore-forming strategy through a facile CO 2 thermal etching route was rationally adopted to engineer negligible oxygenated functionalities on commercial carbon for boosting the sodium storage process. Benefitted from the abundant ionic/electronic pathways and more active reaction sites in the microporous structure with noticeable pseudocapacitive behaviors, the functionalized porous carbon could achieve a highly reversible capacity of 505 mA h g -1 at 50 mA g -1 , an excellent rate performance of 181 mA h g -1 at 16,000 mA g -1 , and an exceptional rate cycle stability of 176 mA h g -1 at 3200 mA g -1 over 1000 cycles. These outstanding electrochemical properties should be ascribed to a synergistic mechanism, fully utilizing the graphitic and amorphous structures for synchronous intercalations of sodium ions and solvated sodium ion compounds, respectively. Finally, the controllable generation and evolution of a robust but thin solid electrolyte interphase film with the emergence of obvious capacitive reactions on the defective surface, favoring the rapid migration of sodium ions and solvated species, also contribute to a remarkable electrochemical performance of this porous carbon black.

25 ENERGY STORAGE↗
DOE OSTI2022

Probing the Influence of Multiscale Heterogeneity on Effective Properties of Graphite Electrodes

Graphite electrodes in the lithium-ion battery exhibit various particle shapes, including spherical and platelet morphologies, which influence structural and electrochemical characteristics. It is well established that porous structures exhibit spatial heterogeneity, and the particle morphology can influence transport properties. The impact of the particle morphology on the heterogeneity and anisotropy of geometric and transport properties has not been previously studied. Herein, this study characterizes the spatial heterogeneities of 18 graphite electrodes at multiple length scales by calculating and comparing the structural anisotropy, geometric quantities, and transport properties (pore-scale tortuosity and electrical conductivity). We found that the particle morphology and structural anisotropy play an integral role in determining the spatial heterogeneity of directional tortuosity and its dependency on pore-scale heterogeneity. Our analysis reveals that the magnitude of in-plane and through-plane tortuosity difference influences the multiscale heterogeneity in graphite electrodes.

25 ENERGY STORAGE↗
DOE OSTI2020

Evaluation of Graph Analytics Frameworks Using the GAP Benchmark Suite

The analysis of connected data is an increasingly important application in high-performance computing. Such analyses can reveal fraudulent patterns in financial transactions, optimize telecommunications networks, predict information flow in social networks, etc. However, the landscape of graph analytics is highly diverse. Graph algorithms stress processor architectures differently, and no one graph can represent all topologies. Consequently, no single approach or framework is expected to be optimal for all graph analytics problems. To help make sense of this diverse landscape, we evaluated four approaches to graph analytics: GraphBLAS, Galois, BGL17, GraphIt; and compare them against hand-tuned implementations that take advantage of hardware features on our test platform. Graph- BLAS formulates graph analytics as sparse linear algebra. Galois provides syntactic constructs for data parallelism over irregular data structures. BGL17 is a generic C++ template library for implementing graph algorithms. GraphIt provides a domain- specific language to describe and optimize graph algorithms. We use the GAP Benchmark Suite to establish baseline performance and guide the side-by-side evaluation of each framework. GAP consists of 30 tests: six graph analytics algorithms (breadth- first search, single-source shortest path, PageRank, betweenness centrality, connected components, and triangle counting) run on five graphs, each with different topological characteristics (e.g., high diameter, skewed degree distribution, high average degree). High-performance reference implementations are included for each benchmark algorithm. Because a graph can be loaded into memory a number of ways (e.g., flat file on disk, compressed sparse format, data frames, retrieved from SQL or NoSQL databases), our evaluation focused on computational performance rather than I/O. Our results show the relative strengths of each framework.

Graph algorithms, Benchmarking, shared-memory prog↗
DOE OSTI2020

Enabling Ether-Based Electrolytes for Long Cycle Life of Lithium-Ion Batteries at High Charge Voltage

Lithium-ion batteries (LIBs) with high-nickel (Ni) content LiNi x Mn y Co z O 2 ( x + y + z = 1) (NMC with Ni ≥ 0.6) cathodes operated at high charge voltages have been considered as one of the most promising candidates for addressing the challenge of increasing energy density demand. Conventional LiPF 6 –organocarbonate electrolytes exhibit incompatibility with such cell chemistries under certain testing conditions because of the instability of electrode/electrolyte interphases. In response to this challenge, ether-based electrolytes with finely tuned structure and composition of solvation sheaths were developed and evaluated in graphite (Gr)∥NMC811 cell chemistry in 2.5–4.4 V, despite ethers being conventionally considered to be unfavorable electrolyte solvents for LIBs because of their anodic instability above 4.0 V and cointercalation into Gr electrodes. Furthermore, the functional ether-based electrolytes in this work enable both excellent cycle life and high rate capability of Gr∥NMC811 cells. Mechanistic studies reveal that the unique structure and composition of the solvation sheath of the functional ether electrolytes are the main reasons behind their excellent anodic stability and effective protection of the Gr electrode and, consequently, the extraordinary cell performances when operated at high charge cutoff voltages. This work also provides a feasible approach in developing highly stable functional electrolytes for high-energy density LIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Review of Graphite Properties Relevant to Micro-Reactor Design

Microreactors are advanced reactors that are designed to be small, scalable, and portable with up to 20 MW power. These reactors could operate independently, or as part of a microgrid, without need of a frequent refueling. Micro-reactors are designed to be deployable to provide electric power in remote locations, therefore providing greater flexibility. Several micro-reactors are under development in the US. These reactors are based on advanced gas-cooled or heat-pipe concepts. While Graphite can be found in various applications, some high-temperature reactors plan to employ Graphite in their core components due to its role as a moderator and its ability to maintain its structural integrity when subjected to elevated temperatures and high neutron fluence. Although there is significant experience with use of Graphite in nuclear applications, there are still unknowns that should be addressed. Graphite properties depend on the graphite type and affected by the fabrication procedures. Material properties are functions of the temperature and irradiation dose. The fundamental properties also affected by the oxidation environment. Therefore, in-depth understanding of graphite properties, including the effect of irradiation, oxidation and other influencing parameters are required to evaluate the design accurately. This draft aims to provide a comprehensive review of material properties for Graphite relevant to micro reactor design. For this work, two distinct grades of graphite were considered, namely IG-110 and Mersen-2114. Physical, thermal, and mechanical properties for these grades were comparatively evaluated. The properties that are discussed in this draft aim to serve as a basis for design and safety analysis.

42 ENGINEERING↗
DOE OSTI2022

Revealing the Structure of Single Cobalt Sites in Carbon Nitride for Photocatalytic CO 2 Reduction

Single Co 2+ sites in graphitic carbon nitride (C 3 N 4 ) have demonstrated excellent activity and selectivity in photocatalytic CO 2 reduction. In this work, we combine computational and spectroscopic tools, including X-ray absorption spectroscopy, to probe the structure of such single Co 2+ sites. Our results indicate that the Co 2+ sites exist in the Co–N 2+2 coordination at the edges of C 3 N 4 flakes. This mode of coordination is further supported by experimental results obtained using single Co 2+ sites in C 3 N 4 materials treated with NH 3 , which contain more edge sites than untreated C 3 N 4 . In our experimental observations, doping C 3 N 4 with carbon is found to be important for the photocatalytic properties of the single Co 2+ sites. Here, a simplified model is proposed to explain the origin of the observed enhancement effect of C doping. In this model, the presence of C dopant near the metal centers results in shorter Co–N bond length and stronger Co–N binding energy. In addition to enhanced light absorption and charge separation in C-doped C 3 N 4 , the stronger Co–N binding upon C doping likely contributes to the improved catalytic properties of the single Co 2+ sites.

14 SOLAR ENERGY↗
DOE OSTI2021

Role of silicon-graphite homogeneity as promoted by low molecular weight dispersants

This study explores low molecular weight polymers with the same chemical repeat structure as high molecular weight poly acrylic acid (PAA) and lithium poly acrylic acid (LiPAA) binders which act as a dispersant to improve the silicon-graphite electrode performance. The electrodes which utilize LiPAA as a dispersant perform, on average, the best with respect to the maximum capacity (compared to theoretical), rate performance, and capacity retention with time. These electrodes also have the poorest dispersion of binder, indicating that the poor binder dispersion is essential to electrode performance. In contrast, this study shows that electrodes formulated using PAA had good dispersion and performs the worst in cycling. Finally, this work demonstrates that the binder is not uniformly distributed in the electrode, but rather resides in local regions. Overall, the results indicate these regions accommodate volume expansion during cycling.

25 ENERGY STORAGE↗
DOE OSTI2022

Bilayer hybrid graphite anodes via freeze tape casting for extreme fast charging applications

Extreme fast charging (XFC) of lithium-ion batteries is critical for continuous market adoption of electric vehicles. However, mass transport limitations and sluggish kinetics lead to lithium plating in graphite anodes under fast charging conditions. One approach to address the mass transport limitation in graphite is to design low-tortuosity electrodes to enhance ionic transport. In this study, a bilayer hybrid structured electrode with directionally aligned channels was developed via freeze tape casting, which enables faster lithium ion diffusion through the graphite electrode. A scalable roll-to-roll process was designed in which slurry can be cast on any substrates for simple processing. Additionally, electrochemical impedance spectroscopy measurements indicated that the bilayer hybrid coating had both low tortuosity and short diffusion pathways, enabling XFC charging. Rate testing for the bilayer hybrid electrode indicated superior performance over the other coatings, exhibiting a ~20% improvement in the charge capacity compared with the conventional coating at 5C and 10 min total charging time. The bilayer hybrid electrode also demonstrated a 10% improvement in capacity retention compared with the conventional electrode after 1000 cycles at XFC conditions. This study demonstrates freeze tape casting as a scalable way to fabricate low-tortuosity electrodes for XFC applications.

25 ENERGY STORAGE↗
DOE OSTI2022

Sustainable conversion of biomass to rationally designed lithium-ion battery graphite

The carbon net negative conversion of bio-char, the low value byproduct of pyrolysis bio-oil production from biomass, to high value, very high purity, highly crystalline flake graphite agglomerates with rationally designed shape and size tailored for lithium-ion battery energy storage material is reported. The process is highly efficient, 0.41 g/Wh; the energy content of its co-product of the process, bio-oil, exceeds that needed to power the process. It is shown that the shape of the starting material is retained during the transformation, allowing the ultimate morphology of the graphite agglomerates to be engineered from relatively malleable biomass. In contrast to commercial graphite production, the process can be performed at small scale with low equipment costs, enabling individual research laboratories to produce Li-ion grade graphite with customizable shape, size and porosity for Si/graphite composite and other graphite involved anodes. The mechanism of the graphitization of bio-char, a “non-graphitizable” carbon, is explored, suggesting the molten metal catalyst is absorbed into the pore structure, transported through and transforming the largely immobile biochar. Finally, the transformation of biomass to rationally designed graphite morphologies with Li-ion anode performance that closely mimic commercial shaped graphite is demonstrated.

09 BIOMASS FUELS↗
DOE OSTI2022

Microstructural and physicochemical origins of electroless copper deposition on graphite enhanced by acid pretreatment

We report Acid treatment is the most widely used surface modification method for enhancing the electroless metal deposition (EMD) on carbon reinforcement materials (CRMs) for metal matrix nanocomposites. However, specific microstructural and physicochemical origins of the enhanced EMD on carbon surfaces by acid treatments have been rarely studied. Here, we investigated the effects of the nitric acid treatment on graphite, a prototypical combination of acid treatment and CRM, on the fidelity of Cu EMD and their structural and chemical origins. Complementary materials characterizations and density functional theory calculations revealed the acid-induced formation of broken C–C/C=C graphitic bonds and resulting surface micropores on graphite; this enabled a uniform dispersion of catalytic Sn/Pd nanoparticles during pre-EMD sensitization/activation processes via spontaneous binding of Sn and Pd ions and, consequently, a much more uniform Cu layer EMD compared to the untreated graphite. We proposed a general mechanism illustrating how the acid-induced microstructural and chemical modifications of carbon surface affected the spatial uniformity of catalytic metal reduction during EMD and, finally, the quality of deposited metal layer. The results clearly reveal the origins of the enhanced EMD on carbon materials by acid treatments, providing guidelines for optimizing EMD on general CRMs for high-performance metal matrix nanocomposites.

36 MATERIALS SCIENCE↗