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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Prediction of Quantum Anomalous Hall Insulator in half-fluorinated GaBi Honeycomb

Using first-principles electronic structure calculations, we predict half-fluorinated GaBi honeycomb under tensile strain to harbor a quantum anomalous Hall (QAH) insulator phase. We show that this QAH phase is driven by a single inversion in the band structure at the Γ point. Moreover, we have computed the electronic spectrum of a half-fluorinated GaBi nanoribbon with zigzag edges, which shows that only one edge band crosses the Fermi level within the band gap. In conclusion, our results suggest that half-fluorination of the GaBi honeycomb under tensile strain could provide a new platform for developing novel spintronics devices based on the QAH effect.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2013

Tunable Electrochemical Properties of Fluorinated Graphene

The structural and electrochemical properties of fluorinated graphene have been investigated by using a series of graphene fluorides (CFx, x=0.47, 0.66, 0.89). Fluorinated graphene exhibited high capacity retentions of 75-81% of theoretical capacity at moderate rates as cathode materials for primary lithium batteries. Specifically, CF0.47 maintained a capacity of 356 mAhg-1 at a 5C rate, superior to that of traditional fluorinated graphite. The discharged graphene fluorides also provide an electrochemical tool to probe the chemical bonding on the parent graphene substrate.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2015

Fluorinated bottlebrush polymers based on poly(trifluoroethyl methacrylate): Synthesis and characterizations

Bottlebrush polymers are densely grafted polymers with long side-chains attached to a linear polymeric backbone. Their unusual structures endow them with a number of unique and potentially useful properties in solution, in thin films, and in bulk. Despite the many studies of bottlebrushes that have been reported, the structure–property relationships for this class of materials are still poorly understood. In this contribution, we report the synthesis and characterization of fluorinated bottlebrush polymers based on poly(2,2,2-trifluoroethyl methacrylate). The synthesis was achieved by atom transfer radical polymerization (ATRP) using an α-bromoisobutyryl bromide functionalized norbornene initiator, followed by ring-opening metathesis polymerization (ROMP) using a third generation Grubbs’ catalyst (G3). Rheological characterization revealed that the bottlebrush polymer backbones remained unentangled as indicated by the lack of a rubbery plateau in the modulus. By tuning the size of the backbone of the bottlebrush polymers, near-spherical and elongated particles representing single brush molecular morphologies were observed in a good solvent as evidenced by TEM imaging, suggesting a semi-flexible nature of their backbones in dilute solutions. Thin films of bottlebrush polymers exhibited noticeably higher static water contact angles as compared to that of the macromonomer reaching the hydrophobic regime, where little differences were observed between each bottlebrush polymer. Further investigation by AFM revealed that the surface of the macromonomer film was relatively smooth; in contrast, the surface of bottlebrush polymers displayed certain degrees of nano-scale roughness (R q = 0.8–2.4 nm). The enhanced hydrophobicity of these bottlebrushes likely results from the preferential enrichment of the fluorine containing end groups at the periphery of the molecules and the film surface due to the side chain crowding effect. Furthermore, our results provide key information towards the design of architecturally tailored fluorinated polymers with desirable properties.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Direct experimental observation of mesoscopic fluorous domains in fluorinated room temperature ionic liquids

Fluorinated room temperature ionic liquids (FRTILs) represent a class of solvent media that are attracting great attention due to their IL-specific properties as well as features stemming from their fluorous nature. Medium-to-long fluorous tails constitute a well-defined apolar moiety in the otherwise polar environment. Similarly to the case of alkyl tails, such chains are expected to result in the formation of self-assembled fluorous domains. So far, however, no direct experimental observation has been made of the existence of such structural heterogeneities on the nm scale. We report here the first experimental evidence of the existence of mesoscopic spatial segregation of fluorinated domains, on the basis of highly complementary X-ray and neutron scattering data sets (highlighting the importance of the latter probe) and NMR spectroscopy. Data are interpreted using atomistic molecular dynamics simulations, emphasizing the existence of a self-assembly mechanism that delivers segregated fluorous domains, where preferential solubilisation of fluorinated compounds can occur, thus paving the way for several smart applications.

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

Oxidatively stable fluorinated sulfone electrolytes for high voltage high energy lithium-ion batteries

New fluorinated sulfones were synthesized and evaluated in high voltage lithium-ion batteries using LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode. Fluorinated sulfones with an α-trifluoromethyl group exhibit enhanced oxidation stability, reduced viscosity and superior separator wettability as compared to their non-fluorinated counterparts. Finally, the improved performance in high voltage cells makes it a promising high voltage electrolyte for 5-V lithium-ion chemistry.

25 ENERGY STORAGE↗
DOE OSTI2020

Effect of fluorination and Li-excess on the Li migration barrier in Mn-based cathode materials

Disordered rocksalt (DRX) Li-rich transition metal (TM) oxides, especially those based on Mn, are prospective high-energy-density cathode materials for the next generation of Li-ion batteries that use earth abundant metals. Fluorine substitution on the oxygen sublattice has been shown to reduce oxygen redox by lowering the average anion valence and increasing the amount of redox-active TM, and simultaneously improve energy density, average voltage and capacity retention. While these benefits of fluorination are well established, it is not well understood how F affects Li transport and therefore the rate performance of Mn-based DRX cathodes. Herein, we investigate the effects of both F substitution and the accompanying Li-excess on Li migration barriers using first-principles calculations. Finally, we demonstrate that F has a small negative effect on Li migration barriers while Li-excess decreases Li migration barriers. Because fluorination enables more Li-excess, these results do not predict any detrimental impact on Li transport.

25 ENERGY STORAGE↗
DOE OSTI2025

Dynamics of fluorinated imide-based ionic liquids using nuclear magnetic resonance techniques

There is increasing interest in studying molecular motions in ionic liquids to gain better insights into their transport properties and to expand their applications. Here, in this study, we have employed the fast field cycling relaxometry and pulsed field gradient nuclear magnetic resonance techniques to investigate the rotational and translational dynamics of fluorinated imide-based ionic liquids (ILs) at different temperatures. We have studied a total of six ILs composed of the 1-butyl-3-methylimidazolium cation ([BMIM] + ) combined with chemically modified analogs of the bis((trifluoromethyl)sulfonyl)imide anion ([NTf 2 ] − or [TFSI] − ). The primary objective of this paper is to broaden the understanding of how the anion's conformational flexibility, fluorination, and mass affect the molecular dynamics of cations and anions. Our results indicate that flexibility has the most significant impact on the rotational and translational motions of ions. Meanwhile, the effect of fluorination and mass is only relevant when conformational flexibility does not change significantly between the ILs being compared.

25 ENERGY STORAGE↗
DOE OSTI2024

Robust battery interphases from dilute fluorinated cations

Controlling solid electrolyte interphase (SEI) in batteries is crucial for their efficient cycling. Herein, we demonstrate an approach to enable robust battery performance that does not rely on high fractions of fluorinated species in electrolytes, thus substantially decreasing the environmental footprint and cost of high-energy batteries. In this approach, we use very low fractions of readily reducible fluorinated cations in electrolyte (~0.1 wt%) and employ electrostatic attraction to generate a substantial population of these cations at the anode surface. As a result, we can form a robust fluorine-rich SEI that allows for dendrite-free deposition of dense Li and stable cycling of Li-metal full cells with high-voltage cathodes. Our approach represents a general strategy for delivering desired chemical species to battery anodes through electrostatic attraction while using minute amounts of additive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Improved organic p-i-n type solar cells with n-doped fluorinated hexaazatrinaphthylene derivatives HATNA-F{sub 6} and HATNA-F{sub 12} as transparent electron transport material

We study new electron transport materials (ETM) to replace the reference material C{sub 60} in p-i-n type organic solar cells. A comprehensive material characterization is performed on two fluorinated hexaazatrinaphthylene derivatives, HATNA-F{sub 6} and HATNA-F{sub 12}, to identify the most promising material for the application in devices. We find that both HATNA derivatives are equally able to substitute C{sub 60} as ETM as they exhibit large optical energy gaps, low surface roughness, and sufficiently high electron mobilities. Furthermore, large electron conductivities of 3.5×10{sup −5} S/cm and 2.0×10{sup −4} S/cm are achieved by n-doping with 4 wt. % W{sub 2}(hpp){sub 4}. HOMO levels of (7.72 ± 0.05) eV and (7.73 ± 0.05) eV are measured by ultraviolet photoelectron spectroscopy and subsequently used for estimating LUMO values of (4.2 ± 0.8) eV and (4.3 ± 0.8) eV. Both fluorinated HATNA derivatives are successfully applied in p-i-n type solar cells. Compared to identical reference devices comprising the standard material C{sub 60}, the power conversion efficiency (PCE) can be increased from 2.1 % to 2.4 % by using the new fluorinated HATNA derivatives.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Towards commercialization of fluorinated cation-disordered rock-salt Li-ion cathodes

Cation-disordered rock-salt cathodes (DRX) are promising materials that could deliver high capacities (>250 mAh g −1 ) with Earth abundant elements and materials. However, their electrochemical performances, other than the capacity, should be improved to be competitive cathodes, and many strategies have been introduced to enhance DRXs. Fluorination has been shown to inhibit oxygen loss and increase power density. Nevertheless, fluorinated cation-disordered rock-salts still suffer from rapid material deterioration and low scalability which limit their practical applications. This mini-review highlights the key challenges for the commercialization of fluorinated cation-disordered rock-salts, discusses the underlying reasons behind material failure and proposes future development directions.

25 ENERGY STORAGE↗
NASA NTRS1973

Fluorine lubricated bearing technology

An experimental program was conducted to evaluate and select materials for ball bearings intended for use in liquid fluorine and/or FLOX. The ability of three different ball-separator materials, each containing nickel, to form and transfer a nickel fluoride film to provide effective lubrication at the required areas of a ball bearing operating in liquid fluorine was evaluated. In addition, solid lubrication of a ball bearing operating in liquid fluorine by either a fused fluoride coating applied to all surfaces of the ball separator or by a fluoride impregnation of porous sintered material ball separators was evaluated. Less bearing wear occurred when tests were conducted in the less reactive FLOX. Bearings fabricated from any of the materials tested would have relatively short wear lives and would require frequent replacement in a reusable engine.

Mallaire, F. R.↗
NASA NTRS1974

Hydrogen and fluorine in the surfaces of lunar samples

The resonant nuclear reaction F-19 (p, alpha gamma)0-16 has been used to perform depth sensitive analyses for both fluorine and hydrogen in lunar samples. The resonance at 0.83 MeV (center-of-mass) in this reaction has been applied to the measurement of the distribution of trapped solar protons in lunar samples to depths of about 1/2 micrometer. These results are interpreted in terms of terrestrial H2O surface contamination and a redistribution of the implanted solar H which has been influenced by heavy radiation damage in the surface region. Results are also presented for an experiment to test the penetration of H2O into laboratory glass samples which have been irradiated with 0-16 to simulate the radiation damaged surfaces of lunar glasses. Fluorine determinations have been performed in a 1 pm surface layer on lunar samples using the same F-19 alpha gamma)0-16 resonance. The data are discussed from the standpoint of lunar fluorine and Teflon contamination.

Leich, D. A.↗
NASA NTRS1975

Fluorine photochemistry in the stratosphere

The photochemistry of fluorine in the stratosphere is surveyed in order to estimate the effect on ozone of fluorine atoms released by the breakdown of chlorofluoromethanes. The catalytic efficiency for ozone destruction by fluorine is found to be less than .0001 that of chlorine in the altitude range from 25 to 50 km.

Stolarski, R. S.↗
NASA NTRS1978

Thermal analysis of a high energy propulsion system /hydrazine and liquid fluorine/ for a rover class Mars Orbiter

Maintaining cryogenic fluorine at a -189 C during the interplanetary cruise period to Mars is a major thermal problem. At this low temperature the heat rejection by radiation is severely limited and the allowable thermal load to the fluorine tank is less than approximately 8 watts. Previous studies generally constrain the spacecraft to an inline tank configuration which tends to maximize the fluorine tank's view and heat rejection to space. With the Inertial Upper Stage, sufficient stack height may not be available on the Shuttle for an inline tank configuration. Therefore, this study addresses the more thermally constraining side by side tank configuration.

Stultz, J. W.↗
NASA NTRS1979

Experience with fluorine and its safe use as a propellant

The industrial and the propulsion experience with fluorine and its derivatives is surveyed. The hazardous qualities of fluorine and safe handling procedures for the substance are emphasized. Procedures which fulfill the safety requirements during ground operations for handling fluorinated propulsion systems are discussed. Procedures to be implemented for use onboard the Space Transportation System are included.

Bond, D. L.↗
NASA NTRS1980

The hollow-cathode helium-fluorine laser

It is possible to obtain uniform stable long-pulse excitation (in excess of 100 microsec) in gas mixtures involving highly electronegative constituents (SF6, CCl4, NF3, and I2). Such a system was used to investigate the atomic fluorine laser. In the hollow cathode, lasing on fluorine transitions in the doublet system lasted for up to 80 microsec with no signs of the self-termination as reported previously in positive-column devices. The excitation process of the laser appears to depend heavily upon the fluorine donor utilized. For instance, a single-step process is involved when NF3 is used whereas a two-step process is evident for SF6. The details are discussed.

Crane, J. K.↗
NASA NTRS1988

Two-photon-excited fluorescence spectroscopy of atomic fluorine at 170 nm

Two-photon-excited fluorescence spectroscopy of atomic fluorine is reported. A doubled dye laser at 286-nm is Raman shifted in H2 to 170 nm (sixth anti-Stokes order) to excite ground-state 2P(0)J fluorine atoms to the 2D(0)J level. The fluorine atoms are detected by one of two methods: observing the fluorescence decay to the 2PJ level or observing F(+) production through the absorption of an additional photon by the excited atoms. Relative two-photon absorption cross sections to and the radiative lifetimes of the 2D(0)J states are measured.

Herring, G. C.↗
NASA NTRS1991

Two-dimensional model calculation of fluorine-containing reservoir species in the stratosphere

Two-dimensional model calculations have been carried out of the distributions of the fluorine-containing reservoir species HF, CF2O, and CFClO. HF constitutes the largest fluorine reservoir in the stratosphere, but CF2O also makes an important contribution to the inorganic fluorine budget. CFClO amounts are most important in the tropical lower stratosphere. HF amounts increase with altitude throughout the stratosphere, while those of CF2O and CFClO fall off above their mixing ratio peaks due to photolysis. The model is in good qualitative agreement with observed vertical profiles of HF and CF2O but tends to underestimate the total column of HF. The calculated CFClO distribution is in good agreement with the very limited data. The disagreement in the HF columns is likely due to small inaccuracies in the model's treatment of lower stratospheric photolysis of chlorofluorocarbons. The model results support the suggestion that CF2O may be heterogeneously converted to HF on the surface of polar stratospheric cloud particles. The model results also suggest that the quantum yield for photolysis of CF2O is near unity.

Kaye, Jack A.↗