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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 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Covalent Attachment of Diphosphine Ligands to Glassy Carbon Electrodes via Cu-Catalyzed Alkyne-Azide Cycloaddition. Metallation with Ni(II)

Covalent tethering of PPh2NC6H4C=CH2 ligands (PPh2NC6H4C=CH2 = 1,5-di-(4-ethynylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) to planar, azide-terminated glassy carbon electrode surfaces has been accomplished using a CuI-catalyzed alkyne-azide cycloaddition (CuAAC) as the coupling reaction, using a BH3?P protection-deprotection strategy. Deprotected, surface-confined ligands were metallated using [NiII(MeCN)6](BF4)2. X-ray photoelectron spectroscopic measurements demonstrate that metallation introduced 1.3 equivalents NiII per diphosphine onto the electrode surface. Exposure of the surface to a second diphosphine ligand, PPh2NPh2, resulted in the removal of Ni from the surface. Protection, coupling, deprotection, and metallation conditions were optimized using solution-phase model systems, with benzyl azide as a model for the azide-terminated carbon surface; these reactions generate a [NiII(diphosphine)2]2+ complex. Acknowledgment. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. The XPS measurements were performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the U. S. Department of Energy, Office of Science, Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The x-ray crystal structure analysis was carried out by S.L., who was supported by a grant to Wendy J. Shaw from the Early Career Research Program through the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

electrocatalysis, surface attachment, XPS↗
DOE OSTI2015

The migration mechanism of transition metal ions in LiNi 0.5 Mn 1.5 O 4

The migration of transition metal ions in the oxygen framework was recently proposed to be responsible for the continuous loss of average working potential of high energy density layered–layered composite cathodes for lithium-ion batteries. The potential migration pathway in a model material, LiNi 0.5 Mn 1.5 O 4 spinel, was investigated using in situ high-energy X-ray diffraction and in situ neutron diffraction during the solid state synthesis process. It was found that the migration of transition metal ions among octahedral sites is possible by using tetrahedral vacancies as intermediate sites. It was also suggested that the number of electrons in 3d orbitals has a significant impact on their mobility in the hosting oxygen framework.

25 ENERGY STORAGE↗
DOE OSTI2020

Developing high safety Li-metal anodes for future high-energy Li-metal batteries: strategies and perspectives

Developing high-safety Li-metal anodes (LMAs) is extremely important for the application of high-energy Li-metal batteries (LMBs), especially Li–S and Li–O 2 battery systems. However, the notorious Li-dendrite growth problem results in serious safety concerns for any energy storage application. Through a recent combination of interface-based science, nanotechnology-based solutions and characterization methods, the LMA is now primed for a technological boom. In this review, the recent emerging strategies and perspectives on LMAs are summarized, following which the current huge evolution in interfacial chemistry regulation, optimizing electrolyte components, designing a rational ‘host’ for lithium metal, optimizing “solid-state electrolytes” and other emerging strategies for developing high-safety LMAs is highlighted. Furthermore, several state-of-the-art in situ/operando synchrotron-based X-ray techniques for high safety LMB research are introduced. With the further development of LMAs in the future, subsequent application in high energy LMBs is to be expected.

25 ENERGY STORAGE↗
DOE OSTI2021

Correlating Nanoscale Secondary Ion Mass Spectrometry and Atom Probe Tomography Analysis of Uranium Enrichment in Metallic Nuclear Fuel

Distribution and enrichment of 235U within nuclear fuels are essential to material performance and reactor safety. With the development of metallic U fuels, understanding 235U homogeneity has become increasingly important, however, it is difficult to map with high spatial, and mass resolution to analyze both matrix and secondary phase precipitates. Here, we analyze 235U enrichment in matrix and carbide phases in LEU-Mo via two chemical imaging modalities: nanoscale secondary ion mass spectrometry (nanoSIMS) and atom probe tomography (APT). NanoSIMS and APT provided consistent results, with no statistically significant difference between measured and nominal enrichment (19.75 % 235U).

U-10Mo, atom probe tomography, nanoscale secondary↗
DOE OSTI2020

Lithium oxidation and electrolyte decomposition at Li-metal/liquid electrolyte interfaces

In this work, we examine the evolution of events occurring when a Li metal surface is in contact with a 2 M solution of a Li salt in a solvent or mixture of solvents, via classical molecular dynamics simulations with a reactive force field allowing bond breaking and bond forming. The main events include Li oxidation and electrolyte reduction along with expansion of the Li surface layers forming a porous phase that is the basis for the formation of the solid-electrolyte interphase (SEI) components. Nucleation of the main SEI components (LiF, Li oxides, and some organics) is characterized. The analysis clearly reveals the details of these physical–chemical events as a function of time, during 20 nanoseconds. The effects of the chemistry of the electrolyte on Li oxidation and dissolution in the liquid electrolyte, and SEI nucleation and structure are identified by testing two salts: LiPF 6 and LiCF 3 SO 3 , and various solvents including ethers and carbonates and mixtures of them. The kinetics and thermodynamics of Li 6 F, the core nuclei in the LiF crystal, are studied by analysis of the MD trajectories, and via density functional theory calculations respectively. The SEI formed in this computational experiment is the “native” film that would form upon contact of the Li foil with the liquid electrolyte. As such, this work is the first in a series of computational experiments that will help elucidate the intricate interphase layer formed during battery cycling using metal anodes.

25 ENERGY STORAGE↗
DOE OSTI2024

Understanding 2p core-level excitons of late transition metals by analysis of mixed-valence copper in a metal–organic framework

The L 2,3 -edge X-ray absorption spectra of late transition metals such as Cu, Ag, and Au exhibit absorption onsets lower in energy for higher oxidation states, which is at odds with the measured spectra of earlier transition metals. Time-dependent density functional theory calculations for Cu 2+ /Cu + reveal a larger 2p core-exciton binding energy for Cu 2+ , overshadowing shifts in single-particle excitation energies with respect to Cu + . Finally, we explore this phenomenon in a Cu + metal–organic framework with ~12% Cu 2+ defects and find that corrections with self-consistent excited-state total energy differences provide accurate XAS peak alignment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Local order, disorder, and everything in between: using 91 Zr solid-state NMR spectroscopy to probe zirconium-based metal–organic frameworks

Characterization of metal centers in metal–organic frameworks (MOFs) is critical for rational design and further understanding of structure–property relationships. The short-range structure about Zr atoms is challenging to properly elucidate in many Zr MOFs, particularly when local disorder is present. Static 91 Zr solid-state NMR spectra of the seven zirconium MOFs UiO-66, UiO-66-NH 2 , UiO-67, MOF-801, MOF-808, DUT-68 and DUT-69 have been acquired at high magnetic fields of 35.2 T and 19.6 T, yielding valuable information on the local structure, site symmetry and order about Zr. 91 Zr NMR is very sensitive to differences in MOF short-range structure caused by guest molecules, linker substitution and post-synthetic treatment. Complementary density functional theory (DFT) calculations assist in the interpretation and assignment of 91 Zr solid-state NMR spectra, lend insight into structural origins of 91 Zr NMR parameters and enable determination of local Zr coordination environments. This approach can be extended to many other materials containing zirconium.

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

Catalytic Reactions by Heterobimetallic Carbonyl Complexes with Polar Metal–Metal Interactions

Abstract Heterobinuclear catalysts capable of bimetallic cooperative bond activation provide an alternative pathway to approach the discovery of novel and unique reactivity and selectivity in catalytic transformations, complementing more traditional mononuclear precious metal catalysts. This review summarizes recent advances in homogenous catalysis using heterobimetallic carbonyl catalysts with polar metal–metal interactions. 1 Introduction 2 Hydrogenation and Hydrofunctionalization 3 Carbonylation and Carboxylation 4 Oxidative Transformations 5 Conclusion and Outlook

Chemistry↗
DOE OSTI2015

Redox-active on-surface polymerization of single-site divalent cations from pure metals by a ketone-functionalized phenanthroline

Metallic iron, chromium, or platinum mixing with a ketone-functionalized phenanthroline ligand on a single crystal gold surface demonstrates redox activity to a well-defined oxidation state and assembly into thermally stable, one dimensional, polymeric chains. The diverging ligand geometry incorporates redox-active sub-units and bi-dentate binding sites. The gold surface provides a stable adsorption environment and directs growth of the polymeric chains, but is inert with regard to the redox chemistry. These systems are characterized by scanning tunnelling microscopy, non-contact atomic force microscopy, and X-ray photoelectron spectroscopy under ultra-high vacuum conditions. The relative propensity of the metals to interact with the ketone group is examined, and it is found that Fe and Cr more readily complex the ligand than Pt. The formation and stabilization of well-defined transition metal single-sites at surfaces may open new routes to achieve higher selectivity in heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Enhancing conductivity of metallic carbon nanotube networks by transition metal adsorption

The conductivity of carbon nanotube thin films is mainly determined by carbon nanotube junctions, the resistance of which can be reduced by several different methods. We investigate electronic transport through carbon nanotube junctions in a four-terminal configuration, where two metallic single-wall carbon nanotubes are linked by a group 6 transition metal atom. The transport calculations are based on the Green’s function method combined with the density-functional theory. The transition metal atom is found to enhance the transport through the junction near the Fermi level. However, the size of the nanotube affects the improvement in the conductivity. The enhancement is related to the hybridization of chromium and carbon atom orbitals, which is clearly reflected in the character of eigenstates near the Fermi level. The effects of chromium atoms and precursor molecules remaining adsorbed on the nanotubes outside the junctions are also examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Numerical simulation of systems of shear bands in ductile metal with inclusions

We develop a method for numerical simulations of high strain-rate loading of mesoscale samples of ductile metal with inclusions. Because of its small-scale inhomogeneity, the composite material is prone to localized shear deformation (adiabatic shear bands). This method employs the Generalized Method of Cells of Paley and Aboudi [Mech. Materials, vol. 14, pp. 127–139, 1992] to ensure that the micro mechanical behavior of the metal and inclusions is reflected properly in the behavior of the composite at the mesoscale. To find the effective plastic strain rate when shear bands are present, we extend and apply the analytic and numerical analysis of shear bands of Glimm, Plohr, and Sharp [Mech. Materials, vol. 24, pp. 31–41, 1996]. Our tests of the method focus on the stress/strain response in uniaxial-strain flow, both compressive and tensile, of depleted uranium metal containing silicon carbide inclusions. We use the Preston-Tonks-Wallace viscoplasticity model [J. Appl. Phys., vol. 93, pp. 211–220, 2003], which applies to the high strain-rate regime of an isotropic viscoplastic solid. In results, we verify the elevated temperature and thermal softening at shear bands in our simulations of pure DU and DU/SiC composites. We also note that in composites, due the asymmetry caused by the inclusions, shear band form at different times in different subcells. In particular, in the subcells near inclusions, shear band form much earlier than they do in pure DU.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Spin Hall effects in metallic antiferromagnets – perspectives for future spin-orbitronics

We investigate angular dependent spin-orbit torques from the spin Hall effect in a metallic antiferromagnet using the spin-torque ferromagnetic resonance technique. The large spin Hall effect exists in PtMn, a prototypical CuAu-I-type metallic antiferromagnet. By applying epitaxial growth, we previously reported an appreciable difference in spin-orbit torques for c- and a-axis orientated samples, implying anisotropic effects in magnetically ordered materials. In this work we demonstrate through bipolar-magnetic-field experiments a small but noticeable asymmetric behavior in the spin-transfer-torque that appears as a hysteresis effect. We also suggest that metallic antiferromagnets may be good candidates for the investigation of various unidirectional effects related to novel spin-orbitronics phenomena.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Controlled modulation of hard and soft X-ray induced tunneling currents utilizing coaxial metal-insulator-metal probe tips

Here, the effect of a local external electric field on the barrier potential of a tunneling gap is studied utilizing an emerging technique, synchrotron x-ray scanning tunneling microscopy. Here, we demonstrate that the shape of the potential barrier in the tunneling gap can be altered by a localized external electric field, generated by voltages placed on the metallic outer shield of a nanofabricated coaxial metal-insulator-metal tip, resulting in a controlled linear modulation of the tunneling current. Experiments at hard and soft x-ray synchrotron beamlines reveal that both the chemical contrast and magnetic contrast signals measured by the tip can be drastically enhanced, resulting in improved local detection of chemistry and magnetization at the surface.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Semi-metallic SrIrO 3 films using solid-source metal-organic molecular beam epitaxy

Perovskite SrIrO 3 films and its heterostructures are very promising, yet less researched, avenues to explore interesting physics originating from the interplay between strong spin–orbit coupling and electron correlations. Elemental iridium is a commonly used source for molecular beam epitaxy (MBE) synthesis of SrIrO 3 films. However, elemental iridium is extremely difficult to oxidize and evaporate while maintaining an ultra-high vacuum and a long mean free path. Here, we calculated a thermodynamic phase diagram to highlight these synthesis challenges for phase-pure SrIrO 3 and other iridium-based oxides. We addressed these challenges using a novel solid-source metal-organic MBE approach that rests on the idea of modifying the metal-source chemistry. Phase-pure, single-crystalline, coherent, epitaxial (001) pc SrIrO 3 films on (001) SrTiO 3 substrate were grown. Films demonstrated semi-metallic behavior, Kondo scattering, and weak antilocalization. Our synthesis approach has the potential to facilitate research involving iridate heterostructures by enabling their atomically precise syntheses.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A liquid metal dropper for experiments on the wettability of liquid metals on plasma facing components

A liquid metal dropper has been developed as a part of the Ion-Gas-Neutral Interactions with Surfaces 2 (IGNIS-2) facility at The Pennsylvania State University. The dropper has the capability of directly applying drops to candidate plasma facing materials for nuclear fusion reactors to enable measurements of their liquid metal wetting properties. The results presented here are specific to the use of lithium in the dropper. This paper discusses the design choices of the liquid metal dropper and its chamber, including the heating and temperature control and the dropper’s motorized operation. Lithium drops of masses ranging from 0.05 g up to 0.13 g, equivalent to drop diameters between 5.6 mm to 1 cm, have been consistently dispensed by the dropper. A new algorithm is developed and used to automate the analysis of the contact angle between the liquid drops and substrate material for efficient analysis of video data recorded to study the wetting properties of candidate plasma-facing components.

Instruments & Instrumentation↗
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 OSTI2019

Local metallic and structural properties of the strongly correlated metal $\mathrm{LaNiO_3}$ using $\mathrm{^8Li β-NMR}$

We report β-detected NMR of ion-implanted $\mathrm{^8Li}$ in a single crystal and thin film of the strongly correlated metal $\mathrm{LaNiO_3}$. Spin-lattice relaxation measurements reveal two distinct local environments, both metallic as evident from $T$-linear Korringa $\mathrm{1/T_1}$ below $\mathrm{200K}$ with slopes comparable to other metals. A small approximately temperature-independent Knight shift of $\mathrm{~74 ppm}$ is observed, yielding a normalized Korringa product characteristic of substantial antiferromagnetic correlations.We find no evidence for a magnetic transition from 4 to $\mathrm{310 K}$. The similarity of these features in the two very different samples indicates that they are intrinsic and unrelated to dilute oxygen vacancies. We attribute the two environments to two distinct but similar crystallographic $\mathrm{^8Li}$ sites and not to any form of phase inhomogeneity, but this is inconsistent with the conventional rhombohedral structure of $\mathrm{LaNiO_3}$, and also cannot be simply explained by the common alternative orthorhombic or monoclinic distortions.

36 MATERIALS SCIENCE↗