New components for refractory metals - Alkali metal corrosion test systems
Component design for refractory metal-alkali metal corrosion test system
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Component design for refractory metal-alkali metal corrosion test system
Advanced Rankine and other proposed space power systems utilize refractory metals in contact with both single-phase and two-phase alkali metals at elevated temperatures. A number of recent compatibility experiments are described which emphasize the excellent compatibility of refractory metals with the alkali metals, lithium, sodium, and potassium, under a variety of environmental conditions. The alkali metal compatibilities of tantalum-, columbium-, molybdenum-, and tungsten-base alloys are discussed.
Alkali metals ionization by photons and atomic projectiles, discussing results in first Born approximation
The reduction of carbon dioxide to oxalate has been studied by experimental Collisionally Induced Dissociation (CID) and vibrational characterization of the alkali metal oxalates, supplemented by theoretical electronic structure calculations. The critical step in the reductive process is the coordination of the heterocumulene CO2 to an alkali metal anion, forming a metal carbonite MCO2 ablt to subsequently add a second CO2 molecule. While the energetic demand for these reactions is generally low, we find that the degree of activation of CO2 in terms of charge transfer and transition state energies is the highest for lithium and systematically decreases down the group (M - Li - Cs).
Localized superconcentrated electrolytes (LSEs) and electrochemical devices including the LSEs are disclosed. The LSE includes an active salt, a solvent in which the active salt is soluble, and a diluent in which the active salt is insoluble or poorly soluble, wherein the diluent includes a fluorinated orthoformate.
Alkali metals are regarded as the most promising candidates for advanced anode for the next-generation batteries due to their high specific capacity, low electrochemical potential, and lightweight. However, critical problems of the alkali metal anodes, especially dendrite formation and interface stabilization, remain challenging to overcome. The solid electrolyte interphase (SEI) is a key factor affecting Li and Na deposition behavior and electrochemical performances. Herein, a facile and universal approach is successfully developed to fabricate ionic conductive interfaces for Li and Na metal anodes by modified atomic layer deposition (ALD). In this process, the Li metal (or Na metal) plays the role of Li (or Na) source without any additional Li (or Na) precursor during ALD. Moreover, the key questions about the influence of ALD deposition temperature on the compositions and structure of the coatings are addressed. The optimized ionic conductive coatings have significantly improved the electrochemical performances. In addition, the electrochemical phase-field model is performed to prove that the ionic conductive coating is very effective in promoting uniform electrodeposition. Further, this approach is universal and can be potentially applied to other different metal anodes. At the same time, it can be extended to other types of coatings or other deposition techniques.
Boiling alkali metal corrosion research for Rankine cycle and thermionic power conversion systems
The mechanisms of electrode kinetics and mass transport of alkali metal oxidation and alkali metal cation reduction at the solid electrolyte/porous electrode boundary as well as alkali metal transport through porous metal electrodes has important applications in optimizing device performance in alkali metal thermal to electric converter (AMTEC) cells which are high temperature, high current density electrochemical cells. Basic studies of these processes also affords the opportunity to investigate a very basic electrochemical reaction over a wide range of conditions; and a variety of mass transport modes at high temperatures via electrochemical techniques. The temperature range of these investigations covers 700K to 1240K; the alkali metal vapor pressures range from about 10(sup -2) to 10(sup 2) Pa; and electrodes studied have included Mo, W, Mo/Na(sub 2)MoO(sub 4), W/Na(sub 2)WO(sub 4), WPt(sub x), and WRh(sub x) (1.0 < x < 6.0 ) with Na at Na-beta'-alumina, and Mo with K at K-beta'-alumina. Both liquid metal/solid electrolyte/alkali metal vapor and alkali metal vapor/solid electrolyte/vapor cells have been used to characterize the reaction and transport processes. We have previously reported evidence of ionic, free molecular flow, and surface transport of sodium in several types of AMTEC electrodes.
Solubility and corrosion resistance of refractory metals and alloys determined in liquid alkali metals
Alkali metal containing materials have become increasingly attractive in a world hunting for sustainable energy materials and green functional devices. Lithium- and sodium battery technology, lead-free piezo- and ferroelectric devices, and record-breaking alkali doped tandem perovskite solar cells are among the applications where alkali metal-containing thin films get increasing attention. Atomic layer deposition (ALD) is one of the enabling thin film deposition techniques that offer chemical and geometrical versatility to realize the implementation of such thin films on an applicable scale. The drawback has until recently been a lack of available precursor chemistry that offers self-limiting growth that is fundamental to ALD. The alkali metal tert-butoxides have been shown to exhibit the necessary properties to facilitate saturating growth for Li-, Na-, K-, and Rb-containing compounds. However, the behavior of the tert-butoxides in ALD-growth has been considered difficult to unravel, with processes exhibiting limited control and low reproducibility. Very little has been reported on trends in reaction mechanisms as the mass of the alkali metal increases. Herein, we summarize the existing literature on the use of alkali metal tert-butoxides as precursors in ALD. We consider differences in the structure and behavior of the tert-butoxides as the alkali metal cation becomes heavier. In addition, we present precursor synthesis routes and key information on precursor structure, stability, and mechanistic behavior. Finally, we provide the first ever report of Cs-containing films by ALD to complement previous work on its lighter counterparts.
Two-fold reduction of a vertically expanded functionalized pentacene with Na metal is accompanied by a loss of diatropicity in the resulting dianion and engagement of side groups in sodium ion coordination.
An alkali metal filter having a layer of metallic bismuth deposited onto the alkali metal is provided. The metallic bismuth acts to stabilize the surface of the alkali metal to prevent substantial surface migration from occurring on the alkali metal, which may degrade optical characteristics of the filter. To this end, a layer of metallic bismuth is deposited by vapor deposition over the alkali metal to a depth of approximately 5 to 10 A. A complete alkali metal filter is described along with a method for fabricating the alkali metal filter.
Finely divided particles of alkali metals are produced by combining alkali metals with certain aromatic compounds in selected solvents to form low-temperature soluble complexes from which the pure alkali metals precipitate quantitatively when the solutions are warmed. All operations must be carried out in an inert gas atmosphere.
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Abstract Doped Mott insulators are the starting point for interesting physics such as high temperature superconductivity and quantum spin liquids. For multi-band Mott insulators, orbital selective ground states have been envisioned. However, orbital selective metals and Mott insulators have been difficult to realize experimentally. Here we demonstrate by photoemission spectroscopy how Ca 2 RuO 4 , upon alkali-metal surface doping, develops a single-band metal skin. Our dynamical mean field theory calculations reveal that homogeneous electron doping of Ca 2 RuO 4 results in a multi-band metal. All together, our results provide evidence for an orbital-selective Mott insulator breakdown, which is unachievable via simple electron doping. Supported by a cluster model and cluster perturbation theory calculations, we demonstrate a type of skin metal-insulator transition induced by surface dopants that orbital-selectively hybridize with the bulk Mott state and in turn produce coherent in-gap states.
The [PW 12 O 40 ] 3− [M + (H 2 O) 16 ] 3 is a “hydrogen bonded” ion-pair complex for M = Li, Na and K, but is a “contact” ion-pair complex for M = Rb and Cs, intermolecular charge transfer from the solvated counter cations M + (H 2 O) 16 to the anion [PW 12 O 40 ] 3− .
Alkali metal-sulfur batteries, including lithium-sulfur (Li-S), sodium-sulfur (Na-S), and potassium-sulfur (K-S) systems, have garnered significant attention as promising electrochemical energy storage (EES) technologies. Among them, Li-S batteries stand out as strong contenders for next-generation energy storage, owing to their high energy density and the cost-effectiveness of sulfur-based cathodes. However, with the rapid technological advances and the escalating energy demand, lithium resources are becoming increasingly scarce, making it imperative to explore alternative metal anodes to replace lithium. Therefore, Na-S and K-S batteries, serving as counterparts to Li-S systems, are emerging as formidable contenders for next-generation energy storage technologies due to the abundant and cost-effective nature of sodium and potassium. Although Na-S and K-S batteries possess considerable potential in the energy sector, their development is still in its infancy, with performance constrained by the nascent state of electrolyte design and optimization. This review article provides a comprehensive overview of recent advancements and developments in liquid electrolytes for alkali metal-sulfur batteries. Additionally, it identifies key challenges and proposes future research directions aimed at enhancing electrolyte stability, optimizing interfacial compatibility, and improving the overall performance of alkali metal-sulfur batteries.