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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Formation of LiF Surface Layer During Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes

Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance and cyclability. In this study we use a fluidized bed reactor to fluorinate a model Lirich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode’s structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to formation of LiF surface films which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high voltage cathodes by tuning the material’s surface chemistry.

Co-free disordered rock-salt cathode, direct fluor↗
DOE OSTI2016

Improving Photoconductance of Fluorinated Donors with Fluorinated Acceptors

This work investigates the influence of fluorination of both donor and acceptor materials on the generation of free charge carriers in small molecule donor/fullerene acceptor BHJ OPV active layers. A fluorinated and non-fluorinated small molecule analogue were synthesized and their optoelectronic properties characterized. The intrinsic photoconductance of blends of these small molecule donors was investigated using time-resolved microwave conductivity. Blends of the two donor molecules with a traditional non-fluorinated fullerene (PC70BM) as well as a fluorinated fullerene (C60(CF3)2-1) were investigated using 5% and 50% fullerene loading. We demonstrate for the first time that photoconductance in a 50:50 donor:acceptor BHJ blend using a fluorinated fullerene can actually be improved relative to a traditional non-fluorinated fullerene by fluorinating the donor molecule as well.

14 SOLAR ENERGY↗
DOE OSTI2018

Efficient Cytosolic Delivery Using Crystalline Nanoflowers Assembled from Fluorinated Peptoids

The design and synthesis of biocompatible nanomaterials as cargoes for the intracellular delivery of therapeutic proteins or genes have attracted intense attention because of their promise for use in therapeutics. Despite the advances in this area, very few nanomaterials can be efficiently delivered to the cytosol. To address these challenges, we designed and synthesized crystalline nanoflower-like particles from fluorinated sequence-defined peptoids; the crystallinity and fluorination of these particles enabled highly efficient cytosolic delivery with minimal cytotoxicity. We delivered these particles, 80% appear to diffuse in the cytosol. Furthermore, these nanocrystals can carry mRNA for instance and effectively delivered into cytosol for gene transfection, demonstrating the generality of our nanocrystals. Our results indicate that self-assembly of crystalline nanomaterials from fluorinated peptoids paves a new way toward development of nanocargoes with efficient cytosol gene delivery. Y. Song and M. Wang contributed equally to this work. This work was supported by start-up funds from Washington State University. Peptoid synthesis work was supported by the Materials Synthesis and Simulation Across Scales (MS3) Initiative through the LDRD fund at Pacific Northwest National Laboratory (PNNL). Assembly of peptoid particles and their structural characterizations were supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Biomolecular Materials Program at PNNL. XRD work was conducted at the Advanced Light Source with support from the Molecular Foundry, at Lawrence Berkeley National Laboratory, both of which are supported by the Office of Science, under Contrast No. DE-AC02-05CH11231. PNNL is multi-program national laboratory operated for Department of Energy by Battelle under Contract No. DE-AC05-76RL01830.

peptoids, nanocrystal, cytosol delivery, endosome ↗
DOE OSTI2021

Effects of fluorinated solvents on electrolyte solvation structures and electrode/electrolyte interphases for lithium metal batteries

Electrolyte is very critical to the performance of the high-voltage lithium (Li) metal battery (LMB), which is one of the most attractive candidates for the next generation high-density energy storage systems. Electrolyte formulation and structure determine the physical properties of the electrolytes and their interfacial chemistries on the electrode surfaces. Localized high-concentration electrolytes (LHCEs) outperform state-of-the-art carbonate electrolytes in many aspects in LMBs due to their unique solvation structure. Types of fluorinated co-solvents used in LHCEs are investigated here in searching for the most suitable diluent for high concentration electrolytes (HCEs). Non-solvating solvents (including fluorinated ethers, fluorinated borate and fluorinated orthoformate) added in HCEs enable the formation of LHCEs with high-concentration solvation structures. However, low solvating fluorinated carbonate will coordinate with Li+ ions and form a second solvation shell or a pseudo-LHCE which diminishes the benefits of LHCE. In addition, it is evident that the diluent has significant influence on the electrode/electrolyte interphases (EEIs) beyond retaining the high-concentration solvation structures. Diluent molecules surrounding the high-concentration clusters could accelerate or decelerate the anion decomposition through co-participation of diluent decomposition in the EEI formation. The varied interphase features lead to significantly different battery-performance. This study points out the importance of diluents and their synergetic effects with the conductive salt and the solvating solvent in designing LHCEs. These systematic comparisons and fundamental insights into LHCEs using different types of fluorinated solvents can guide further development of advanced electrolytes for high-voltage LMBs.

Cao, Xia↗
DOE OSTI2014

A new solar fluorine abundance and a fluorine determination in the two open clusters M67 and NGC 6404

We present a new determination of the solar fluorine abundance together with abundance measurements of fluorine in two Galactic open clusters. We analyzed a sunspot spectrum, observed by L. Wallace and W. Livingston with the Fourier Transform Spectrometer at the McMath/Pierce Solar Telescope situated on Kitt Peak, and spectra of four giants in the old cluster M67 (∼4.5 Gyr) and three giants in the young cluster NGC 6404 (∼0.5 Gyr), obtained with the CRIRES spectrograph at the Very Large Telescope. Fluorine was measured through the synthesis of the available HF lines. We adopted the recent set of experimental molecular parameters of HF delivered by the HITRAN database, and found a new solar fluorine abundance of A(F) = 4.40 ± 0.25, in good agreement with the M67 average fluorine abundance of A(F) = 4.49 ± 0.20. The new solar abundance is in a very good agreement with the meteoritic value. The modern spectrosynthesis tools used and the agreement with the meteoritic value and with the results in open cluster M67, known to be a solar analogue, make our solar determination very robust. At the same time, the fluorine measurement in the above-mentioned open clusters is the first step toward understanding its evolution during the last ∼10 Gyr in the Galactic disk. In order to develop this project, a larger sample of open clusters is required, in order to allow us to trace the evolution of fluorine as a function of time and, in turn, to better understand its origin.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2013

Water Oxidation and Oxygen Monitoring by Cobalt-Modified Fluorine-Doped Tin Oxide Electrodes

Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5

Kent, CA↗
DOE OSTI2019

Fluorine chemistry at extreme conditions: possible synthesis of $HgF_4$

By irradiating a pressurized mixture of a fluorine-bearing compound ($XeF_2$) and $HgF_2$ with synchrotron hard x-rays (>7 keV) inside a diamond anvil cell, we have observed dramatic changes in the far-infrared spectrum within the 30-35 GPa pressure range which suggest that we may have formed $HgF_4$ in the following way: $XeF_2 \xrightarrow{hv} Xe + F_2$ (photochemically) and $HgF_2 + F_2 \rightarrow HgF_4$ (30 GPa < P < 35 GPa). This lends credence to recent theoretical calculations by Botana et al. that suggest that Hg may behave as a transition metal at high pressure in an environment with an excess of molecular fluorine. The spectral changes were observed to be reversible during pressure cycling above and below the above mentioned pressure range until a certain point when we suspect that molecular fluorine diffused out of the sample at lower pressure. Upon pressure release, $HgF_2$ and trace $XeF_2$ were observed to be remaining in the sample chamber suggesting that much of the $Xe$ and $F_2$ diffused and leaked out from the sample chamber. Received: 29 October 2018, Accepted: 18 January 2019; Edited by: A. Goñi, A. Cantarero, J. S. Reparaz; DOI: http://dx.doi.org/10.4279/PIP.110001 Cite as: M Pravica, S Schyck, B Harris, P Cifligu, E Kim, B Billinghurst, Papers in Physics 11, 110001 (2019). This paper, by M Pravica, S Schyck, B Harris, P Cifligu, E Kim, B Billinghurst, is licensed under the Creative Commons Attribution License 4.0.

Pravica, Michael G.↗
DOE OSTI2021

Fluorination-Enhanced Surface Stability of Cation-Disordered Rocksalt Cathodes for Li-Ion Batteries

Cation-disordered rocksalt (DRX) materials have emerged as a class of novel high-capacity cathodes for Li-ion batteries. However, commercialization of DRX cathodes will require reducing their capacity decay, which has been associated with oxygen loss during cycling. Recent studies have shown that fluorination of DRX cathodes can effectively reduce the oxygen loss and improve the cycling stability; however, the underlying atomic-scale mechanisms remain elusive. Herein, using a combination of electrochemical measurements, scanning transmission electron microscopy, and electron energy loss spectroscopy, we examine the correlation between the electrochemical properties and structural evolution in Mn-redox-based DRX cathodes, Li1.2Ti0.4-xMn0.4+xO2.0-xFx (x = 0 and 0.2). We find that fluorination strongly suppresses structural amorphization and void formation initiated from the particle surface, therefore greatly enhancing the cyclability of the cathode. We further reveal a novel rocksalt-to-spinel-like structural transformation in the DRX bulk, which surprisingly contributes to a gradual capacity increase during cycling. Our results provide important insight for the design of novel DRX cathodes with high capacity and long cycle life.

Li, Linze↗
DOE OSTI2017

Coupled Cluster and Density Functional Studies of Atomic Fluorine Chemisorption on Coronene as Model Systems for Graphene Fluorination

Potential energy curves (PECs) of atomic fluorine adsorption on coronene as a model for graphene or nanocarbon surfaces have been computed. The PECs were obtained by scanning the fluorine atom distance to one of the center carbon atoms of the coronene molecule as model system in a “top” position from 4.0 to1.0 Å in intervals of 0.1 Å using a variety of quantum chemical methods. Various density functional theory (DFT) functionals, such as B3LYP, PBE, PBE0, CAM-B3LYP, and LC-ωPBE; approximate DFT methods such as several levels of the density-functional tight-binding (DFTB) method, as well as ab initio wave function theory methods such as MP2, CCSD, CCSD(T), and G2MS extrapolations, were used to evaluate energies for B3LYP/cc-pVDZ PEC geometries. G2MS is an approximation to the highly accurate CCSD(T)/cc-pVTZ level of theory in our work. We found that fluorine is chemically adsorbed on coronene with a binding energy of 22.9 and 23.3 kcal/mol at the B3LYP/cc-pVDZ and G2MS levels of theory, respectively, and 18.3 and 19.3 kcal/mol after counterpoise correction. Here, we found that pure DFT functionals and their DFTB approximations fail to predict the correct dissociation limit due to the DFT-inherent self-interaction error and various limitations in the DFTB approximation itself.

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

Note: Loading method of molecular fluorine using x-ray induced chemistry

We have successfully loaded molecular fluorine into a diamond anvil cell at high pressure using the synchrotron x-ray induced decomposition of perfluorohexane (C{sub 6}F{sub 14}). “White” x-ray radiation from the Advanced Photon Source was used to initiate the chemical decomposition of C{sub 6}F{sub 14}, which resulted in the in situ production of F{sub 2} as verified via Raman spectroscopy. Due to the toxic nature of fluorine, this method will offer significant advantages in the ability to easily load a relatively nontoxic and inert substance into a chamber (such as a diamond anvil cell) that, when sealed with other reactants and irradiate with hard x-rays (>7 keV), releases highly reactive and toxic fluorine into the sample/reaction chamber to enable novel chemical synthesis under isolated and/or extreme conditions.

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

Efficient Fluorinating Agent through Topochemical Fluorination of Co-Fe Layered Double Hydroxides

Mixed-metal inorganic fluoride, Co 0.60 Fe 0.40 F 3 , solid solutions are obtained through topochemical reactions of Co 2 FeCl(OH) 6 ·2H 2 O LDH with molecular fluorine, F 2 , at temperatures as low as 100 °C. This solid solution possesses interesting F • -releasing ability, and its efficiency as a solid-state fluorinating agent is demonstrated on a commercial polyethylene film. 19 F solid state NMR and contact angle measurements underline the efficient fluorination of this polymer.

Louvain, Nicolas↗
DOE OSTI2016

Growth and characterization of Al{sub 2}O{sub 3} films on fluorine functionalized epitaxial graphene

Intelligent engineering of graphene-based electronic devices on SiC(0001) requires a better understanding of processes used to deposit gate-dielectric materials on graphene. Recently, Al{sub 2}O{sub 3} dielectrics have been shown to form conformal, pinhole-free thin films by functionalizing the top surface of the graphene with fluorine prior to atomic layer deposition (ALD) of the Al{sub 2}O{sub 3} using a trimethylaluminum (TMA) precursor. In this work, the functionalization and ALD-precursor adsorption processes have been studied with angle-resolved photoelectron spectroscopy, low energy electron diffraction, and X-ray photoelectron spectroscopy. It has been found that the functionalization process has a negligible effect on the electronic structure of the graphene, and that it results in a twofold increase in the adsorption of the ALD-precursor. In situ TMA-dosing and XPS studies were also performed on three different Si(100) substrates that were terminated with H, OH, or dangling Si-bonds. This dosing experiment revealed that OH is required for TMA adsorption. Based on those data along with supportive in situ measurements that showed F-functionalization increases the amount of oxygen (in the form of adsorbed H{sub 2}O) on the surface of the graphene, a model for TMA-adsorption on graphene is proposed that is based on a reaction of a TMA molecule with OH.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗