Search NASA⌕ Search

SEARCH · Search NASA

Results for “ALKALINE EARTH METAL”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗
DOE OSTI2025

The Many-Body Expansion for Metals: II. Nonadditive Terms in Clusters Composed of Metals with n s 1 , n s 2 , and n s 2 p 1 Configurations

The many-body expansion (MBE) was applied to homometallic and heterometallic trimers of metals with ns 1 , ns 2 , and ns 2 p 1 configurations to investigate its convergence, the magnitude and nature (stabilizing/destabilizing) of the individual terms and seek an understanding of their variation across the different families of clusters. In particular, we examined the series of alkali metals (Li 3 , Na 3 , K 3 , Li 2 Na, LiNa 2 ), alkali metal borides (Li 2 B and LiB 2 ), and alkaline earth metals (Be 3 , Be 2 Mg, BeMg 3 , and Mg 3 ) trimers, as well as sodium clusters Na n , n = 2–5. Here, we found that there is no uniform contribution (stabilizing or destabilizing) across the series in the different families of trimers. For instance, the 2-B term stabilizes the ground states of the Na 3 (doublet), Na 4 (singlet), and Na 5 (doublet) clusters, and the 3-B term destabilizes them; however, the opposite holds for the quartet state of the Li 3 , Li 2 Na, LiNa 2 , and Na 3 clusters (destabilizing 2-B, stabilizing 3-B). Substituting Li with B in the quartet state of Li 3 results in a significant reduction of the 3-B term amounting to 16% (Li 2 B) and 5% (LiB 3 ) of the binding energy. On the contrary, the ground states of the alkaline earth metal clusters (Be 3 , Be 2 Mg, BeMg 3 , and Mg 3 ) are stabilized by the 3-B term, while the 2-B term destabilizes them. Overall, we find that the 3-B terms significantly stabilize the high-spin multiplicity states of the ns 1 configurations and the low-spin states of the ns 2 configurations. Finally, as the size of the metal increases, the contribution of the 3-B term to the binding energy decreases due to the longer metal–metal bond distances.

Alkali metals↗
NASA NTRS2014

Rapid Solid-State Metathesis Routes to Nanostructured Silicon-Germainum

Methods for producing nanostructured silicon and silicon-germanium via solid state metathesis (SSM). The method of forming nanostructured silicon comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and an alkaline earth metal silicide into a homogeneous powder, and initating the reaction between the silicon tetraiodide (SiI4) with the alkaline earth metal silicide. The method of forming nanostructured silicon-germanium comprises the steps of combining a stoichiometric mixture of silicon tetraiodide (SiI4) and a germanium based precursor into a homogeneous powder, and initiating the reaction between the silicon tetraiodide (SiI4) with the germanium based precursors.

Kaner, Richard B.↗
DOE OSTI2022

Determination of transition metal ions in fossil fuel associated wastewaters using chelation ion chromatography

Here, this study outlines the development and subsequent validation of a method using chelation ion chromatography (CIC) pretreatment followed by traditional ion chromatography (IC) and post column UV/vis detection to measure transition metals in fossil fuel wastewaters, such as oil & gas (O&G) brines and coal mine drainage (CMD) waters. Measurement of transition metals is often an important characterization step in the research of environmental and energy systems. IC represents one way to measure these metals with the advantages of being versatile, simple and relatively low cost compared to other analytical methods. However, high concentrations of alkali and alkaline earth metals present in fossil fuel wastewaters will decrease IC detectability of transition metals in these waters. In this study, a CIC method was developed for the analysis of transition metal ions (Fe 3+ , Cu 2+ , Ni 2+ , Zn 2+ , Co 2+ , Mn 2+ , and Fe 2+ ) in fossil fuel associated wastewaters such as Appalachian CMD and O&G wastewaters from the Permian and Bakken shale basins in the United States. CIC system incorporated an on-line chelator column (e.g., the MetPac CC-1) with high selectivity for transition metals over alkali and alkaline earth metals for salt matrix removal prior to transition metal separation and detection. Additional method developments also included acidifying all samples to 2% v/v HCl and using gradient elution rather than isocratic. The recoverability of transition metals in simple salt solutions commonly found in CMD and brine samples (e.g. NaCl, Na 2 SO 4 , CaCl 2 ) using CIC was evaluated and compared to that using traditional IC. Our results found that the CIC system significantly improved transition metal recoveries for samples in 10,000 mg/L CaCl 2 matrix, reaching 87%-108% recovery for all analytes, as opposed to 2-323% recovery in traditional IC. The limits of detection in this study achieved 10.09 – 161.2 μg/L, comparable to reported values in similar IC studies. The developed method was also verified with certified water samples, resulting in 89% - 111% recoveries in samples with higher analyte concentrations (i.e. >4x the LoDs). The developed method achieved 87% -112% recoveries for most analytes in CMD samples and 72%-138% recoveries for Bakken shale samples, relative to ICP-MS values. Overall, the current IC method can be a very good screening tool for fast and cheap analysis for transition metals at mg/L level, to facilitate selection of samples for more detailed ICP-MS analysis.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Ternary borides and borohydrides for hydrogen storage and method of synthesis

A method and a system is provided for obtaining solid-state hydrogen storage and release in materials with at least theoretical loaded hydrogen densities of 11 wt % or greater that can deliver hydrogen and be recharged at moderate temperatures enabling incorporation into hydrogen storage systems suitable for transportation applications. These materials comprise ternary boride materials comprising certain light transition metals and alkaline or alkaline earth metals, and ideally have no or very little phase separation. A process of making these materials is also provided.

Stavila, Vitalie↗
DOE OSTI2025

Carbonation and Sulfidation of Mg- and Ni-Containing Solutions: Implications for Carbon Mineralization and Critical Element Recovery

Carbonation of alkaline earth metals ( e.g. , magnesium (Mg)) and sulfidation of nickel (Ni) are promising methods to achieve concurrent carbon mineralization and selective Ni recovery. However, the coexistence of alkaline earth metals and Ni from silicate ores or mining wastewater complicates the carbonation and sulfidation owing to cation coprecipitation. To better understand simultaneous metal carbonation and Ni-sulfide formation, we used Mg- and Ni-containing solutions and systematically investigated the Mg and Ni coprecipitates’ phase transformation during sequential/concurrent carbonation and sulfidation. During a single carbonation process, hydromagnesite dehydrated and formed magnesite over time. Nickel bicarbonate formed and became a Mg–Ni carbonate solid solution because of their similar ionic radii. During a single sulfidation process, the pH did not affect Ni-sulfide formation, but it controlled Mg behavior. Specifically, at pH 9.6, brucite formed, while at pH 7.8, Mg 2+ remained in the solution. For the sequential carbonation–sulfidation process, Ni-carbonate formed during carbonation converted to Ni-sulfide because of the low Ni-sulfide K sp . For the sulfidation–carbonation process, Ni-sulfide remained the same even after carbonation and Mg-carbonate precipitates. For the concurrent carbonation and sulfidation process, Mg-carbonate and Ni-sulfide formed simultaneously. Finally, this study develops a scientific foundation of carbonation and sulfidation processes, benefiting coupled CO 2 storage and sulfide-enabled resource recovery.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Highly selective cross ketonization of renewable acids over magnesium oxide

The rising demand for linear alkylbenzene surfactants (LAS) poses an environmental threat as LAS are industrially produced from petroleum using corrosive acid catalysts. Cross ketonization is a promising route of converting furans and fatty acids to oleo-furansulfonates, precursors for renewable, performance-enhanced LAS replacements. Here, we explore various alkaline earth metals and mixed metal oxides for the cross-ketonization reaction and find that MgO achieves ~90% yield by minimizing the decarboxylation side reaction. Here, we illustrate the role of molecular structure on the cross-ketonization reaction and the role of complex formation over alkaline-earth metal oxides in minimizing side reactions. We overcome catalyst deactivation by regeneration over multiple runs. This research demonstrates the effectiveness of heterogeneous catalysts for cross ketonization toward developing renewable surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hybrid Molecular Beam Epitaxy for Single-Crystalline Oxide Membranes with Binary Oxide Sacrificial Layers

The advancement in thin-film exfoliation for synthesizing oxide membranes has led to possibilities for creating artificially assembled heterostructures with structurally and chemically incompatible materials. The sacrificial layer method is a promising approach to exfoliate as-grown films from a compatible material system, allowing for their integration with dissimilar materials. Nonetheless, the conventional sacrificial layers often possess an intricate stoichiometry, thereby constraining their practicality and adaptability, particularly when considering techniques such as molecular beam epitaxy (MBE). This is where easy-to-grow binary alkaline-earth-metal oxides with a rock salt crystal structure are useful. These oxides, which include (Mg, Ca, Sr, Ba)O, can be used as a sacrificial layer covering a much broader range of lattice parameters compared to conventional sacrificial layers and are easily dissolvable in deionized water. In this study, we show the epitaxial growth of the single-crystalline perovskite SrTiO 3 (STO) on sacrificial layers consisting of crystalline SrO, BaO, and Ba 1–x Ca x O films, employing a hybrid MBE method. Our results highlight the rapid (≤5 min) dissolution of the sacrificial layer when immersed in deionized water, facilitating the fabrication of millimeter-sized STO membranes. Using high-resolution X-ray diffraction, atomic-force microscopy, scanning transmission electron microscopy, impedance spectroscopy, and scattering-type near-field optical microscopy (SNOM), we demonstrate single-crystalline STO membranes with bulk-like intrinsic dielectric properties. The employment of alkaline earth metal oxides as sacrificial layers is likely to simplify membrane synthesis, particularly with MBE, thus expanding the research and application possibilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Methods of making YSZ supported catalyst, and methods of using the same

The present invention relates to catalysts, methods of making catalysts, and methods of using catalysts, where the catalysts include: at least one of a transition metal and a transition metal oxide supported by yttria-stabilized zirconia (YSZ), where the transition metal is promoted by at least one of an alkali metal and an alkaline-earth metal.

Way, James Douglas↗
DOE OSTI2026

Diffusion and Solvation Dynamics of Ions in Water: Beyond the Brownian Approximation

The coupled dynamics of ions and water molecules in their first hydration shell impact a variety of processes including ion diffusion, selective ion transport in water-filled nanopores, and the kinetics of ion-pairing, ion adsorption, and metal-ligand binding reactions. In this work, we study these coupled dynamics for alkali metals (Li, Na, K, Rb, Cs), alkaline Earth metals (Mg, Ca, Sr, Ba), and chloride through the lens of their dependence on ion isotopic mass. Results are validated against previous measurements of the isotopic mass-dependence of ion diffusion coefficients in water and previous ab initio calculations of ion high-frequency dynamics in water. We find that the vibrational power spectra of ions in water consistently exhibit either two or three peaks, i.e., ions have several rattling frequencies within their solvations shells as previously reported for a subset of the species examined here. These frequencies have different sensititivies to isotopic mass that may serve as signatures of ion solvation processes (such as the tendency of ions to orient their first-shell water molecules) and that also may relate to Hofmeister-like effects including the relative affinity of different metals for ribonucleic acid (RNA).

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

Toward Ultracold Organic Chemistry: Prospects of Laser Cooling Large Organic Molecules

Ultracold organic chemistry enables studies of reaction dynamics and mechanisms in quantum regime. Access to ultracold molecules hinges on the ability to efficiently scatter multiple photons via quasi-closed cycling transitions. Optical cycling in polyatomic molecules is challenging due to their complex electronic structure. Using equation-of-motion coupled-cluster calculations, we demonstrate that an alkaline earth metal attached to various aromatic ligands (such as benzene, phenol, cyclopentadienyl, and pyrrolide) offer nearly closed cycling transitions with only a few additional repump lasers. Here, we also show that aromatic ligands such as benzene can accommodate multiple cycling centers in various geometrical arrangements, opening new avenues in quantum information science, precision measurements, and ultracold chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Solvent-Driven Transformation of Zn/Cd 2+ -Deoxycholate Assemblies

Deoxycholic acid (DOC) is a unique, biologically derived surfactant with facial amphiphilicity that has been exploited, albeit minimally, in supramolecular assembly of materials. Here, we present the synthesis and structural characterization of three hybrid metal (Zn 2+ and Cd 2+ )-DOC compounds. Analysis by single-crystal Xray diffraction reveals the many interactions that are possible between these facial surfactants and the influence of solvent molecules that drive the assembly of materials. These structures are the first metal- DOC complexes besides those obtained from alkali and alkaline earth metals. We isolated polymeric chains of both Cd and Zn (Zn poly -DOC and Cd poly -DOC) from water. Major interactions between DOC molecules in these phases are hydrophobic in nature. Cd poly -DOC exhibits unique P1 symmetry, with complete interdigitation of the amphiphiles between neighboring polymeric chains. Zn 4 -DOC, obtained from methanol dissolution of Zn poly -DOC, features the OZn 4 tetrahedron, widely known in basic zinc acetate and MOF-5 (metal organic framework). We document a solvent-driven, roomtemperature transition between Zn poly -DOC and Zn 4 -DOC (in both directions) by scanning and transmission electron microscopies in addition to small-angle X-ray scattering, powder X-ray diffraction, and infrared spectroscopy. These studies show the methanoldriven transition of Zn poly -DOC to Zn 4 -DOC occurs via an intermediate with no long-range order of the Zn 4 clusters, indicating the strongest interactions driving assembly are intramolecular. On the contrary, water-driven solid-to-solid transformation from Zn 4 -DOC to Zn poly -DOC exhibits crystal-to-crystal transformation. Zn poly -DOC is robust, easy to synthesize, and comprised of biologically benign components, so we demonstrate dye absorption as a proxy for water treatment applications. It favors absorption of positively charged dyes. These studies advance molecular level knowledge of the supramolecular assembly of facial surfactants that can be exploited in the design of organic-inorganic hybrid materials. This research also highlights the potential of solvent for tuning supramolecular assembly processes, leading to new hybrid materials featuring facial surfactants.

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

Surface treatment for lithium battery electrode materials

Electrode materials for electrochemical cells and batteries and methods of producing such materials are disclosed herein. A method of preparing an active lithium metal oxide material suitable for use in an electrode for a lithium electrochemical cell comprises the steps of: (a) contacting the lithium metal oxide material with an aqueous acidic solution containing one or more metal cations; and (b) heating the so-contacted lithium metal oxide from step (a) to dryness at a temperature below 200° C. The metal cations in the aqueous acidic solution comprise one or more metal cations selected from the group consisting of an alkaline earth metal ion, a transition metal ion, and a main group metal ion.

25 ENERGY STORAGE↗
DOE OSTI2022

Lithium battery electrodes

Electrode materials for electrochemical cells and batteries and methods of producing such materials are disclosed herein. The electrode materials comprise an active lithium metal oxide material prepared by: (a) contacting the lithium metal oxide material with an aqueous acidic solution containing one or more metal cations; and (b) heating the so-contacted lithium metal oxide from step (a) to dryness at a temperature below 200° C. The metal cations in the aqueous acidic solution comprise one or more metal cations selected from the group consisting of an alkaline earth metal ion, a transition metal ion, and a main group metal ion.

25 ENERGY STORAGE↗
NASA NTRS1982

Gasifiable carbon-graphite fibers

Fine, carbon-graphite fibers do not combust during the combustion of a composite and are expelled into the air as fine conductive particles. Coating of the fibers with a salt of a metal having a work function below 4.2 eV such as an alkaline earth metal salt, e.g., calcium acetate, catalytically enhances combustion of the fibers at temperatures below 1000.degree. C. such that the fibers self-support combustion and burn to produce a non-conductive ash. Fire-polishing the fibers before application of the coating is desirable to remove sizing to expose the carbon surface to the catalyst.

Humphrey, Marshall F.↗
DOE OSTI2026

Supramolecular assembly of molecular wires alternating crown ethers and metal–halide complexes

Metal–halide complexes serve as key emissive centres in halide perovskites; however, precise control over their spatial organization through bottom-up assembly is challenging. Here we show that a crown-ether-assisted supramolecular assembly strategy can alternatingly connect metal–halide complexes and (crown ether@A) 2+ (where ‘A’ is an alkaline earth metal cation) complexes into a one-dimensional molecular wire, which can then be packed into a hexagonal crystal structure. This process resulted in the creation of an (18C6@Ba)MnBr 4 single crystal with green emission, achieving over 80% photoluminescence quantum yield and a narrow full width at half maximum. In addition, the non-centrosymmetric crystal structure gave rise to strong nonlinear optical responses, including second-harmonic generation. This versatile supramolecular assembly approach could be generalized to create various [M(I)X 2 ] − , [M(I)X 3 ] 2− , [M(II)X 4 ] 2− and [M(III)X 5 ] 2− molecular wires, broadening the potential for diverse emission colours and distinct optical properties. This strategy provides a general design principle for constructing supramolecular metal–halide building blocks with diverse optical functionalities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

Schottky-Barrier Photocell With Intermediate Metal Layer

Device output and durability increased. Photosensitive GaAs Schottkybarrier device modified by addition of intermediate layer of refractory or alkaline earth metal. Photovoltaic cells and photosensors made with new design put out higher short-circuit currents and better able to withstand rigors of handling and connection to other circuit components.

Alcorn, G. E.↗