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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 667 records · Page 37

Singly Reduced Iridium Chromophores: Synthesis, Characterization, and Photochemistry

One-electron reduced photosensitizers have been invoked as crucial intermediates in photoredox catalysis, including multiphoton excitation and electrophotocatalytic processes. However, such reduced chromophores have been less investigated, limiting mechanistic studies of their associated electron transfer processes. Here, we report a total of 11 different examples of isolable singly reduced iridium chromophores. Chemical reduction of a cyclometalated iridium complex with potassium graphite affords a 19-electron species. Structural and spectroscopic characterizations reveal a ligand-centered reduction product. The reduced chromophore absorbs a wide range of light from ultraviolet to near-infrared and exhibits photoinduced bimolecular electron transfer reactivity. Furthermore, these studies shed light on elusive reduced iridium chromophores in both ground and excited states, providing opportunities to investigate a commonly invoked intermediate in photoredox catalysis.

14 SOLAR ENERGY↗

Effect of in-situ oxygen on the electronic properties of graphene grown by carbon molecular beam epitaxy grown

We report that graphene grown by molecular beam epitaxy from solid carbon (CMBE) on (0001) SiC in the presence of unintentional oxygen exhibits a small bandgap on the order of tens of meV. The presence of bandgaps is confirmed by temperature dependent Hall effect and resistivity measurements. X-ray photoelectron spectroscopy (XPS) measurements suggest that oxygen incorporates into the SiC substrate in the form of O-Si-C and not into the graphene as graphene oxide or some other species. The effect is independent of the carrier type of the graphene. Temperature dependent transport measurements show the presence of hopping conduction in the resistivity and a concurrent disappearance of the Hall voltage. Interactions between the graphene layers and the oxidized substrate are believed to be responsible for the bandgap.

36 MATERIALS SCIENCE↗

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differences with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.

25 ENERGY STORAGE↗

Highly Ordered Hierarchical Anodes for Extreme Fast Charging Batteries (Final Report)

The goal of this project is to enable extreme fast charging (XFC) of Li-ion batteries, which was accomplished through a combination of 1) rational design and manufacturing of hierarchically structured anode architectures; 2) blending graphite/hard carbon into a bulk hybrid anode; 3) engineering artificial solid-electrolyte interphase (SEI) coatings with reduced interphase impedance; 4) computational modeling of coupled transport, kinetic, and electrochemical phenomena; and 5) improved fundamental understanding of lithium plating through operando analysis. This work integrated structural, compositional, and surface modification of graphite anodes, multi-physics modeling of ion transport, electrochemical activity, and heat transfer, advanced strategies to detect Li plating, and semi-automated roll-to-roll cell assembly. The unique facilities at the University of Michigan (UM) and Sandia National Laboratories (SNL) were leveraged to manufacture, prototype, and characterize commercially relevant >2Ah and >180 Wh/kg cells with a target of <20% capacity fade over 500 XFC cycles.

25 ENERGY STORAGE↗

Electrodes for sealed secondary batteries

Self-supporting membrane electrode structures, in which active ingredients and graphite are incorporated in a polymeric matrix, improve performance of electrodes in miniature, sealed, alkaline storage batteries.

Boies, D. B.↗

Hybridized polymer matrix composites

The extent to which graphite fibers are released from resin matrix composites that are exposed to fire and impact conditions was determined. Laboratory simulations of those conditions that could exist in the event of an aircraft crash and burn situation were evaluated. The effectiveness of various hybridizing concepts in preventing this release of graphite fibers were also evaluated. The baseline (i.e., unhybridized) laminates examined were prepared from commercially available graphite/epoxy, graphite/polyimide, and graphite/phenolic materials. Hybridizing concepts investigated included resin fillers, laminate coatings, resin blending, and mechanical interlocking of the graphite reinforcement. The baseline and hybridized laminates' mechanical properties, before and after isothermal and humidity aging, were also compared. It was found that a small amount of graphite fiber was released from the graphite/epoxy laminates during the burn and impact conditions used in this program. However, the extent to which the fibers were released is not considered a severe enough problem to preclude the use of graphite reinforced composites in civil aircraft structure. It also was found that several hybrid concepts eliminated this fiber release. Isothermal and humidity aging did not appear to alter the fiber release tendencies.

House, E. E.↗

Fillers for improved graphite fiber retention by polymer matrix composites

The results of a program designed to determine the extent to which elemental boron and boron containing fillers added to the matrix resin of graphite/epoxy composites prevent the release of graphite fibers when the composites are exposed to fire and impact conditions are described. The fillers evaluated were boron, boron carbide and aluminum boride. The conditions evaluated were laboratory simulations of those that could exist in the event of an aircraft crash and burn situation. The baseline (i.e., unfilled) laminates evaluated were prepared from commercially available graphite/epoxy. The baseline and filled laminates' mechanical properties, before and after isothermal and humidity aging, also were compared. It was found that a small amount of graphite fiber was released from the baseline graphite/epoxy laminates during the burn and impact conditions used in this program. However, the extent to which the fibers were released is not considered a severe enough problem to preclude the use of graphite reinforced composites in civil aircraft structure. It also was found that the addition of boron and boron containing fillers to the resin matrix eliminated this fiber release. Mechanical properties of laminates containing the boron and boron containing fillers were lower than those of the baseline laminates. These property degradations for two systems: boron (5 micron) at 2.5 percent filler loading, and boron (5 micron) at 5.0 percent filler loading do not appear severe enough to preclude their use in structural composite applications.

House, E. E.↗

Multifunctional Carbon Foams for Aerospace Applications

Carbon foams produced by the controlled thermal decomposition of inexpensive coal extracts exhibit a combination of structural and thermal properties that make them attractive for aerospace applications. Their thermal conductivity can be tailored between 0.5 and 100 W/mK through precursor selection/modification and heat treatment conditions; thus, they can serve in either thermal protection or heat transfer systems such as heat exchangers. Because their structure is essentially a 3D random network of graphite-like members, they also can be considered low-cost, easily fabricated replacements for multi-directional structural carbon fiber preforms. Strengths of over 4000 psi in compression are common. Their density can be designed between 0.1 and 0.8 g/cc, and they can be impregnated with a variety of matrices or used, unfilled, in sandwich structures. These foams also exhibit intriguing electrochemical properties that offer potential in high-efficiency fuel cell and battery applications, mandrels and tooling for composite manufacture, ablative performance, and fire resistance. This paper presents the results of research conducted under NASA SBIR Topic 99.04.01, General Aviation Technology, supported from Langley Research Center. The potential of foam design through precursor selection, cell size and density control, density grading, and heat treatment is demonstrated.

Rogers, D. K.↗

A systematic approach to generating accurate neural network potentials: the case of carbon

Abstract Availability of affordable and widely applicable interatomic potentials is the key needed to unlock the riches of modern materials modeling. Artificial neural network-based approaches for generating potentials are promising; however, neural network training requires large amounts of data, sampled adequately from an often unknown potential energy surface. Here we propose a self-consistent approach that is based on crystal structure prediction formalism and is guided by unsupervised data analysis, to construct an accurate, inexpensive, and transferable artificial neural network potential. Using this approach, we construct an interatomic potential for carbon and demonstrate its ability to reproduce first principles results on elastic and vibrational properties for diamond, graphite, and graphene, as well as energy ordering and structural properties of a wide range of crystalline and amorphous phases.

Chemistry↗

Investigation of new superhard carbon allotropes with promising electronic properties

During the systematic search for a new superhard carbon allotrope, we predicted three structures with promising physical properties. Our electronic structure calculations show that these materials have a semiconducting band gap and a high carrier mobility comparable with diamond. The simulated x-ray diffraction patterns of the proposed materials are in a good agreement with the experimental X-ray spectra. Evaluated phase transition pressures from graphite to the new proposed carbon phases are smaller than 25 GPa and close to the experimental values.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Thermal stability of Pt nanoclusters interacting to carbon sublattice

The catalytic activity of Pt clusters is dependent not only on the nanoparticle size and its composition, but also on its internal structure. To determine the real structure of the nanoparticles used in catalysis, the boundaries of the thermal structure stability of Pt clusters to 8.0 nm in diameter interacting with carbon substrates of two types: a fixed α-graphite plane and a mobile substrate with the diamond structure. The effect of a substrate on the processes melting of Pt nanoclusters is estimated. The role of the cooling rate in the formation of the internal structure of Pt clusters during crystallization is studied. The regularities obtained in the case of “free” Pt clusters and Pt clusters on a substrate are compared. It is concluded that platinum nanoparticles with diameter D ≤ 4.0 nm disposed on a carbon substrate conserve the initial fcc structure during cooling.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Effect of the graphite electrode material on the characteristics of molten salt electrolytically produced carbon nanomaterials

The electrochemical erosion of a graphite cathode during the electrolysis of molten lithium chloride salt may be used for the preparation of nano-structured carbon materials. It has been found that the structures and morphologies of these carbon nanomaterials are dependent on those of the graphite cathodes employed. A combination of tubular and spherical carbon nanostructures has been produced from a graphite with a microstructure of predominantly planar micro-sized grains and a minor fraction of more irregular nano-sized grains, whilst only spherical carbon nanostructures have been produced from a graphite with a microstructure of primarily nano-sized grains. Based on the experimental results, a best-fit regression equation is proposed that relates the crystalline domain size of the graphite reactants and the carbon products. The carbon nanomaterials prepared possess a fairly uniform mesoporosity with a sharp peak in pore size distribution at around 4 nm. The results are of crucial importance to the production of carbon nanomaterials by way of the molten salt electrolytic method. - Highlights: {yields} Carbon nanomaterials are synthesised by LiCl electrolysis with graphite electrodes. {yields} The degree of crystallinity of graphite reactant and carbon product are related. {yields} A graphite reactant is identified that enables the preparation of carbon nanotubes. {yields} The carbon products possess uniform mesoporosity with narrow pore size distribution.

36 MATERIALS SCIENCE↗

Ferrix Chloride-Graphite Intercalation Compounds Prepared From Graphite Flouride

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp(sup 3) electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp(sup 2) electronic structure and are electrical conductors. They contain first-stage FeCl3 intercalated graphite. Some of the products contain FeCl2 (center dot) 2H2O, others contain FeF3, in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearance of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol%), this new GIC deintercalates without losing its molecular structure. However, when the compounds are exposed to 800 C N2, in a quartz tube, they lost most of their halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber.

Hung, Ching-Cheh↗

Lightweight Space Tug body structure

Lightweight honeycomb sandwich construction using a wide variety of metal and fibrous composite faceskins was used in the design of a typical Space Tug skirt structure. Relatively low magnitude combined loading of axial compression and torsion resulted in designs using ultrathin faceskins, lightweight honeycomb cores, and thin faceskin/core adhesive bond layers. Two of the designs with metal faceskins (aluminum and titanium) and four with fibrous composite faceskins (using combinations of fiberglass, boron, and graphite) were evaluated through the fabrication and structural test of a series of small development panels. The two most promising concepts with aluminum and graphite/epoxy faceskins, were further evaluated through the fabrication and structural test of larger compression and shear panels. All panels tested exceeded design ultimate load levels, thereby, verifying the structural integrity of the selected designs. Projected skirt structural weights for the graphite/epoxy and aluminum concepts fall within original weight guidelines established for the Space Tug vehicle.

Lager, J. R.↗

Development of Ti 3 SiC 2 MAX phase tubular structures for solar receiver applications

Solar receiver tubes are key components of concentrating solar-thermal power (CSP) systems that harvest solar energy. For better efficiency, the Gen3 CSP receivers, which collect heat into a heat transfer fluid, require a temperature exceeding 700 °C during operation and need to perform under extreme conditions of high temperature and high thermal stress. Operators are seeking CSP designs using new high-temperature structural materials with high thermal conductivity and high creep resistance to achieve a design life of 30 years and thus help recover the plant capital cost sooner. MAX phase materials, which consist of an early transition metal element, an A-group element, and carbon or nitrogen, are expected to exhibit high creep resistance as well as high fracture toughness. Here, in this paper, we describe fabricating both (1) dense Ti 3 SiC 2 MAX phase disks and (2) short-length tubes using field-assisted sintering technology (FAST). First, the disk samples that we fabricated are fully dense and contain ≈90 % Ti 3 SiC 2 MAX phase materials and ≈10 % TiC phase materials. We determined a flexure strength of 519 ± 32 MPa by conducting a four-point bending test at room temperature with rectangular bar samples of ≈100 % density. The thermal conductivity of the Ti 3 SiC 2 MAX phase samples, measured by light flashing analysis, decreases linearly from a value of 41 W . m -1 . K -1 at room temperature to a value of 36 W . m -1 . K -1 at 650 °C. A solar reflectance measurement of the Ti 3 SiC 2 MAX phase revealed that, temperature increases from 400 to 1400 °C, thermal emittance increases from 0.39 to 0.49, while selectivity decreases from 1.8 to 1.4, respectively. Whereas the surface oxidized MAX phase samples after 100 h exposure to air at 1000 °C exhibit that of SiC. Next, we discuss fabrication of the crack-free Ti 3 SiC 2 MAX phase tubular structures accomplished by using FAST processing in graphite bedding. A Ti 3 SiC 2 MAX phase content of > 95 % with traceable ≈3% remaining TiC phase and ≈15 % porosity were demonstrated after high-temperature annealing. An average fracture strength of ≈250 MPa was determined with Ti 3 SiC 2 MAX phase tubes of ≈85 % density by diametral compression testing at room temperature. Our work demonstrated that using FAST processing to produce Ti 3 SiC 2 MAX phase tubular structures for CSP receiver applications is a viable approach.

14 SOLAR ENERGY↗

Microwave exfoliated graphene oxide/TiO{sub 2} nanowire hybrid for high performance lithium ion battery

Lithium ion battery (LIB) is a key solution to the demand of ever-improving, high energy density, clean-alternative energy systems. In LIB, graphite is the most commonly used anode material; however, lithium-ion intercalation in graphite is limited, hindering the battery charge rate and capacity. To date, one of the approaches in LIB performance improvement is by using porous carbon (PC) to replace graphite as anode material. PC's pore structure facilitates ion transport and has been proven to be an excellent anode material candidate in high power density LIBs. In addition, to overcome the limited lithium-ion intercalation obstacle, nanostructured anode assembly has been extensively studied to increase the lithium-ion diffusion rate. Among these approaches, high specific surface area metal oxide nanowires connecting nanostructured carbon materials accumulation have shown promising results for enhanced lithium-ion intercalation. Herein, we demonstrate a hydrothermal approach of growing TiO{sub 2} nanowires (TON) on microwave exfoliated graphene oxide (MEGO) to further improve LIB performance over PC. This MEGO-TON hybrid not only uses the high surface area of MEGO but also increases the specific surface area for electrode–electrolyte interaction. Therefore, this new nanowire/MEGO hybrid anode material enhances both the specific capacity and charge–discharge rate. Scanning electron microscopy and X-ray diffraction were used for materials characterization. Battery analyzer was used for measuring the electrical performance of the battery. The testing results have shown that MEGO-TON hybrid provides up to 80% increment of specific capacity compared to PC anode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗