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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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NLR will help ACE Green Recycling evaluate and develop its processes for environmentally friendly and low-cost recycling of graphite, lithium-iron phosphate (LFP), and other cathode materials from spent lithium-ion batteries.
Space power systems for Space Station Freedom will be exposed to the harsh environment of low earth orbit (LEO). Neutral atomic oxygen is the major constituent in LEO and has the potential of severely reducing the efficiency of solar dynamic power systems through degradation of the concentrator surfaces. Several transparent dielectric thin films have been found to provide atomic oxygen protection, but atomic oxygen undercutting at inherent defect sites is still a threat to solar dynamic power system survivability. Leveling coatings smooth microscopically rough surfaces, thus eliminating potential defect sites prone to oxidation attack on concentrator surfaces. The ability of leveling coatings to improve the atomic oxygen durability of concentrator surfaces was investigated. The application of a EPO-TEK 377 epoxy leveling coating on a graphite epoxy substrate resulted in an increase in solar specular reflectance, a decrease in the atomic oxygen defect density by an order of magnitude and a corresponding order of magnitude decrease in the percent loss of specular reflectance during atomic oxygen plasma ashing.
Over 200 graphite/aluminum and graphite/magnesium composites were flown on the leading and trailing edges of LDEF on the Advanced Composites Experiment. The performance of these composites was evaluated by performing scanning electron microscopy and x-ray photoelectron spectroscopy of exposed surfaces, optical microscopy of cross sections, and on-orbit and postflight thermal expansion measurements. Graphite/aluminum and graphite/magnesium were found to be superior to graphite/polymer matrix composites in that they are inherently resistant to atomic oxygen and are less susceptible to thermal cycling induced microcracking. The surface foils on graphite/aluminum and graphite/magnesium protect the graphite fibers from atomic oxygen and from impact damage from small micrometeoroid or space debris particles. However, the surface foils were found to be susceptible to thermal fatigue cracking arising from contamination embrittlement, surface oxidation, or stress risers. Thus, the experiment reinforced requirements for carefully protecting these composites from prelaunch oxidation or corrosion, avoiding spacecraft contamination, and designing composite structures to minimize stress concentrations. On-orbit strain measurements demonstrated the importance of through-thickness thermal conductivity in composites to minimize thermal distortions arising from thermal gradients. Because of the high thermal conductivity of aluminum, thermal distortions were greatly reduced in the LDEF thermal environment for graphite/aluminum as compared to graphite/magnesium and graphite/polymer composites. The thermal expansion behavior of graphite/aluminum and graphite/magnesium was stabilized by on-orbit thermal cycling in the same manner as observed in laboratory tests.
Conversion of methanol and dimethyl ether to high-octane gasoline catalyzed by beta zeolite (BEA) provides an opportunity for the production of high-quality fuels from renewable carbon sources (e.g., gasified biomass). Recent research demonstrated that a Cu-modified BEA zeolite catalyst (Cu/BEA) offered advantages over the unmodified BEA catalyst due to multifunctional Cu species that enabled incorporation of co-fed H2, reactivation of light alkanes, and reduction of products from the aromatic hydrocarbon pool. The shift in hydrocarbon pool chemistry has the potential to influence the identity and relative composition of surface carbon species that are often linked to deactivation. A detailed understanding of these carbon species is important to develop an effective and efficient regeneration procedure that can enable the transition from fundamental catalyst development to commercial application. Here, we applied complementary ex situ and in situ characterization techniques to compare the structures of surface carbon species on post-reaction Cu/BEA and unmodified BEA catalysts. Both catalysts contained acyclic and aromatic hydrocarbons along with graphitic carbon species. However, the post-reaction Cu/BEA catalyst had a lower polycyclic aromatic content, and further, the graphitic species were more hydrogenated and defective. It was also found that the presence of Cu promoted carbon removal at lower temperatures than for unmodified BEA through activation of O2 by Cu during thermal oxidation. The fundamental insight into the composition of surface carbon species enabled the design of an effective and efficient regeneration strategy for the DME homologation reaction over Cu/BEA, resulting in full recovery of the catalyst activity.
A new class of fluorinated sulfones, β-fluorinated sulfones, were designed and synthesized as electrolyte solvents for high voltage lithium-ion batteries. While the oxidation potential of β-fluorinated sulfones is slightly lower than that of α-fluorinated sulfones, it is still significantly higher than the oxidation potential of regular sulfones, which already possess fairly high anodic stability. However, β-fluorinated sulfones exhibit a significant decrease in reduction potential compared to α-fluorinated sulfones, rendering them more stable towards graphite anodes. Moreover, the reduced lithium solvating power of β-fluorinated sulfones compared to regular sulfones mitigates the transition metal dissolution of cathodes. Taken together, these middle ground properties of β-fluorinated sulfone-based electrolytes enable the very stable long-term cycling of graphite||LiNi 0.6 Co 0.2 Mn 0.2 O 2 full cells. Finally, the outstanding performance of β-fluorinated sulfones designed by applying the “golden middle way” paves a new path for the development of an effective electrolyte system.
Carbon materials containing metal nanoparticles that can form an alloy with lithium were tested for their capacity and cycle life to store and release lithium electrochemically. Metal nanoparticles may provide the additional lithium storage capacity as well as additional channels to conduct lithium in carbon. The cycle life of this carbon-metal composite can be long because the solid-electrolyte interface (SEI) on the carbon surface may protect both lithium and the metal particles in the carbon interior. In addition, the voids in the carbon interior may accommodate the nanoparticle's volume change, and such volume change may not cause much internal stress due to small sizes of the nanoparticles. This concept of improving carbon's performance to store and release lithium was demonstrated using experimental cells of C(Pd)/0.5M Lil-50/50 (vol.%) EC and DMC/Li, where C(Pd) was graphitized carbon fibers containing palladium nanoparticles, EC was ethylene carbonate, and DMC was dimethyl carbonate. However, such improvement was not observed if the Pd nanoparticles are replaced by aluminum, possibly because the aluminum nanoparticles were oxidized in air during storage, resulting in an inert oxide of aluminum. Further studies are needed to use this concept for practical applications.
Abstract Developing functionally complex carbon materials from small aromatic molecules requires an understanding of how the chemistry and structure of its constituent molecules evolve and crosslink, to achieve a tailorable set of functional properties. Here, molecular dynamics (MD) simulations are used to isolate the effect of methyl groups on condensation reactions during the oxidative process and evaluate the impact on elastic modulus by considering three monodisperse pyrene‐based systems with increasing methyl group fraction. A parameter to quantify the reaction progression is designed by computing the number of new covalent bonds formed. Utilizing the previously developed MD framework, it is found that increasing methylation leads to an almost doubling of bond formation, a larger fraction of the new bonds oriented in the direction of tensile stress, and a higher basal plane alignment of the precursor molecules along the direction of tensile stress, resulting in enhanced tensile modulus. Additionally, via experiments, it is demonstrated that precursors with a higher fraction of methyl groups result in a higher alignment of molecules. Moreover, increased methylation results in the lower spread of single molecule alignment which may lead to smaller variations in tensile modulus and more consistent properties in carbon materials derived from methyl‐rich precursors.
Four basically different approaches were considered: gasification of fibers, retention in the matrix, clumping to prevent entrainment, and electrical insulation of fibers. The techniques used to achieve them are described in some detail. These involved surface treatment of fibers to improve the wettability of fibers and coating the fibers with the selected substances before laying them up for composite fabrication. Thermogravimetric analyses were performed on the plain and treated fibers in inert (nitrogen, argon) and reactive (air) atmospheres. The treated fibers embedded in epoxy were ignited in a Bunsen flame to determine the efficiency of these treatments. A simple apparatus was assembled to detect the time for the first short circuit (in a typical electrical circuit) when exposed to the combustion products from a graphite fiber composite fire. The state-of-the-art and treated fibers cast in typical epoxy were burned and ranked for potential success. It was inferred that the gasification schemes appear promising when reduction or oxidation is tried. It was also found that some very promising candidates were available for the clumping and for the electrical insulation of fibers.
Electrochemical Oxidation (ECO) offers promise as a low-temperature, atmospheric pressure method for safe destruction of hazardous organic chemical wastes in water. Anode materials tend to suffer corrosion in the intensely oxidizing environment of the ECO cell. There is a need for cheaper, more resistant materials. In this experiment, a system is described for testing anode materials, with examples of several common anodes such as stainless steel, graphite, and platinized titanium. The ECO system is simple and safe to operate and the experiment can easily be expanded in scope to study the effects of different solutions, temperatures, and organic materials.
Fluids generated from subducted slabs participate in the cycling of deep carbon in the crust and upper mantle. In these fluids, aqueous carbon species vary in oxidation state between +IV and -IV depending on whether the fluids are oxidizing or reducing, respectively. Most studies of subduction-zone fluids have focused on oxidized carbon species. However, recent studies of natural samples have demonstrated the occurrence of deep, reducing fluids, generated in both subducted oceanic upper mantle and crustal rocks. CH 4 -H 2 -rich fluid inclusions in subducted carbonated serpentinites have demonstrated the existence of abiotic, immiscible, hydrocarbon fluids at upper mantle conditions. To investigate the formation of such immiscible hydrocarbon fluids during the evolution of subducted carbonated serpentinites, we used equilibrium constants from the Deep Earth Water model to carry out predictive chemical mass transfer modeling to simulate the alteration reactions. A novel feature of the models was the inclusion of an immiscible hydrocarbon fluid containing six components (CH 4,f , C 2 H 6,f , C 3 H 8,f , isoC 4 H 10,f , CO 2,f , H 2,f ). This feature enabled prediction of the formation of a separate immiscible fluid in equilibrium with aqueous species and minerals. We developed a predictive reaction path model of invasive H 2,f reacting with carbonated serpentinites and interstitial aqueous fluids for comparison with the natural samples from the Lanzo Massif, western Italian Alps. Over a range of temperatures and pressures, immiscible hydrocarbon fluids formed in association with altered mineral assemblages. Reaction progress caused the transformation of carbonated serpentinites and the formation of clinopyroxene, brucite, graphite, and hydrocarbon fluids, along with changes of pH, logfO 2 , and aqueous species. CH 4,f was the most abundant hydrocarbon species in all the models. The overall results at 2.0 GPa and 400 to 450 °C were consistent with the natural samples from the Lanzo Massif. Interestingly, large amounts of H 2 O formed due to oxidation of H 2 . More hydrocarbons and H 2 O formed in models with lower fluid/rock mass ratios or with more reactant H 2 . Models at different pressure and temperature conditions showed similar results with some variation in the relative stabilities of aragonite, graphite and olivine solid solution, and associated differences in mineral sequences, hydrocarbon fluids, values of aqueous species, and the final log fO 2 and pH. As a result, our models strongly support the laboratory and field evidence that reduction of carbonated serpentinites by infiltrating H 2 fluids can cause the formation of immiscible, abiotic hydrocarbon fluids in subduction zones.
Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.
Particle fuel forms generally consist of a dispersion of fuel, such as tristructural isotropic (TRISO) particles, within a refractory matrix (e.g., graphite or silicon carbide). The density of matrix materials for particle fuel forms is of interest for modeling fuel form strength and thermal properties and may be specified as a quality control parameter, depending on reactor design. Some of the uncertainty associated with traditional, manual approaches can be eliminated by performing x-ray computed tomography (XCT) on the fuel forms and applying image processing methods to generate a precise count of the number of particles. This also removes the need to include determination of particle count within each individual fuel form during fabrication. Unfortunately, reconstruction artifacts from high-Z uranium-bearing kernels prevent accurate measurement of individual particle volumes using this approach, so the use of mean particle mass and volume are still necessary for computation of average fuel form matrix density. This method of using XCT to count particles in individual fuel form for determination of average matrix density was applied to three archived compacts from the Advanced Gas Reactor Fuel Development and Qualification (AGR)-1 campaign, four archived compacts with uranium carbide/uranium oxide (UCO) TRISO from the AGR-2 campaign, and three archived UO 2 -TRISO compacts from the AGR-2 campaign. The resulting density values were compared with those previously reported, showing slight changes due to uncertainties in the previously used number of particles in each of these cylindrical, graphite matrix compacts.
Abstract Lithium‐metal batteries (LMB) employing cobalt‐free layered‐oxide cathodes are a sustainable path forward to achieving high energy densities, but these cathodes exhibit substantial transition‐metal dissolution during high‐voltage cycling. While transition‐metal crossover is recognized to disrupt solid‐electrolyte interphase (SEI) formation on graphite anodes, experimental evidence is necessary to demonstrate this for lithium‐metal anodes. In this work, advanced high‐resolution 3D chemical analysis is conducted with time‐of‐flight secondary‐ion mass spectrometry (TOF‐SIMS) to establish spatial correlations between the transition metals and electrolyte decomposition products found on cycled lithium‐metal anodes. Insights into the localization of various chemistries linked to crucial processes that define LMB performance, such as lithium deposition, SEI growth, and transition‐metal deposition are deduced from a precise elemental and spatial analysis of the SEI. Heterogenous transition‐metal deposition is found to perpetuate both heterogeneous SEI growth and lithium deposition on lithium‐metal anodes. These correlations are confirmed across various lithium‐metal anodes that are cycled with different cobalt‐free cathodes and electrolytes. An advanced electrolyte that is stable to higher voltages is shown to minimize transition‐metal crossover and its effects on lithium‐metal anodes. Overall, these results highlight the importance of maintaining uniform SEI coverage on lithium‐metal anodes, which is disrupted by transition‐metal crossover during operation at high voltages.
Lithium halides cathodes potentially offer a high energy density at a low cost for rechargeable batteries. However, these cathodes suffer from quick capacity decay in organic electrolytes and the failiure mechanism remains elusive. Here, we report that liquefying the halogen or interhalogen compounds is a prerequisite for achieving high reversibility for the lithium halides cathodes. The gas or solid halogen can be liquefied by using interhalogen compounds with different electronegativity or changing the temperature. As a proof of concept, reversible LiCl conversion-intercalation chemistry in organic electrolyte is demonstrated by using either redox coupling with less electronegative I/Br to form liquid ICl/BrCl or reducing the temperature to -30oC. Further, the LiCl-LiBr-graphite cathodes in 1.6M lithium difluoro(oxalato)borate/1.6M lithium triflate in diglyme electrolytes achieve a high reversible specific capacity of 250 mAh/g at 3.7 V with an energy density being comparable to or higher than transition metal oxide cathodes at a much lower cost.
Owing to their high specific capacity and suitably low operating potential, silicon-based anodes are an attractive alternative to graphite in next-generation lithium-ion batteries. However, silicon anodes suffer from low initial coulombic efficiency and fast capacity decay, limiting their widespread application. Pre-lithiation strategies are highly appealing to compensate for irreversible active lithium loss and to boost the cell energy density. In this work, we maximize the cell energy density by direct pre-lithiation of the NMC (LiNi 0.5 Mn 0.3 Co 0.2 O 2 ) cathode to Li 1+x NMCO 2 without introducing inactive deadweight to either electrode. First, we demonstrate that Li 1+x NMCO 2 can be synthesized chemically, via reaction between NMC and lithium napthalide, and electrochemically. The NMC cathode is tolerant of a one-time over-lithiation up to 60 mA h g NMC -1 , giving capacity retention on par with untreated NMC in half cell electrochemical cycling. Using synchrotron X-ray absorption spectroscopy (ex situ) and diffraction (in situ), we demonstrate that higher amounts of over-lithiation lead to local structure distortion – driven by transition metal reduction to Jahn–Teller active Mn 3+ and Co 2+ – as well as bulk structural hysteresis during over-lithiation and layer “buckling” that increases the amount of lithium extracted from the structure in the charged state. The Li 1+x NMCO 2 with low-to-moderate over-lithiation capacity (23, 46, and 70 mA h g NMC -1 ) is proven to be a highly effective dual-purpose lithium source and cathode material in full cell tests with a commercially relevant Si–graphite anode. These cells show higher capacity, superior cycle life, and improved coulombic efficiencies when compared to those with stoichiometric NMC cathodes. Finally, this study introduces a new and simple method to pre-lithiate layered transition metal oxide cathodes, opening up new possibilities for the development of high energy density lithium-ion batteries with next-generation anodes.
Metal-rich asteroids and iron meteorites are considered core remnants of differentiated planetesimals and/or products of oxygen-depleted accretion. Investigating the origins of iron-rich planetesimals could provide key insights into planet formation mechanisms. Using differentiation models, we evaluate the interior structure and composition of representative-sized planetesimals (~200 km diameter), while varying oxygen fugacity and initial bulk meteoritic composition. Under the oxygen-poor conditions that likely existed early in the inner regions of the Solar System and other protoplanetary disks, core fractions remain relatively consistent across a range of bulk compositions (CI, H, EH, and CBa). Some of these cores could incorporate significant amounts of silicon (10–30 weight%) and explain the metal fractions of Fe-rich bodies in the absence of mantle stripping. Conversely, planetesimals forming under more oxidizing conditions, such as beyond snow lines, could exhibit smaller cores, enriched in carbon, sulfur (>1 wt%), and oxides. Sulfur-rich cores, like those formed from EH and H bulk compositions, could remain partly molten, sustain dynamos, and even drive sulfur-rich volcanism. Additionally, bodies with high carbon contents, such as CI compositions, can form graphitic outer layers. These variations highlight the importance of initial formation conditions in shaping planetesimal structures. Future missions, such as NASA’s Psyche mission, offer an opportunity to measure the relative abundances of key elements (Fe, Ni, Si, and S) necessary to distinguish among formation scenarios and structure models for Fe-rich and reduced planetesimals.
Fullerenes are composed of carbon atoms arranged in approximately spherical or ellipsoidal cages resembling the geodesic domes designed by Buckminster Fuller, after whom the molecules were named. The approximately spherical fullerene, which resembles a soccer ball and contains sixty atoms (C60), is called buckminsterfullerene. The fullerene containing seventy carbon atoms (C70) is approximately ellipsoidal, similar to a rugby ball. Fullerenes were first detected in 1985, in carbon vapor produced by laser evaporation of graphite. The closed shell structure, which has no edge atoms vulnerable to reaction, was proposed to explain the observed high stability of certain carbon clusters relative to that of others at high temperatures and in the presence of an oxidizing gas.
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.