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At least 271 records · Page 15

Temperature-Dependent Structural Transition in Cu-Intercalated Trigonal CuYbSe 2

Rare-earth delafossites, ARCh 2 ; A = alkali metal, R = rare-earth, Ch = chalcogen which consist of intercalated rare-earth metal dichalcogenides, host frustrated triangular lattices that are fertile ground for exotic phenomena. In most cases, the triangular rare-earth sublattice arises from R-3m (No. 166) structures with three layers of rare-earth metal dichalcogenide octahedra or P6 3 /mmc (No. 194) structures with two such layers, analogous to those found in transition metal dichalcogenides. Substituting the alkali metal with Cu + yields a distinct trigonal crystal symmetry P-3m1 (No. 164) in these structures. This symmetry change alters the coordination environment from ASe 6 octahedra in R-3m AYbSe 2 to CuSe 4 tetrahedra in CuYbSe 2 , resulting in shortened rare-earth to rare-earth separations and significantly reduced interlayer distances. Using X-ray single-crystal diffraction, powder neutron diffraction, resistance, and specific heat measurements, a structural transition slightly below room temperature (258 K) is observed. The low-temperature structure is a lower-symmetry I2/m structure, accompanied by partial Cu-site vacancy ordering. The combination of Cu disorder and the triangular lattice geometry in CuYbSe 2 provides a promising platform for investigating frustrated magnetism and unconventional transport phenomena.

Chemical structure↗

Geochemical constraints on bacteriophage infectivity in terrestrial environments

Abstract Lytic phages can be potent and selective inhibitors of microbial growth and can have profound impacts on microbiome composition and function. However, there is uncertainty about the biogeochemical conditions under which phage predation modulates microbial ecosystem function, particularly in terrestrial systems. Ionic strength is critical for infection of bacteria by many phages, but quantitative data is limited on the ion thresholds for phage infection that can be compared with environmental ion concentrations. Similarly, while carbon composition varies in the environment, we do not know how this variability influences the impact of phage predation on microbiome function. Here, we measured the half-maximal effective concentrations (EC50) of 80 different inorganic ions for the infection of E. coli with two canonical dsDNA and ssRNA phages, T4 and MS2, respectively. Many alkaline earth metals and alkali metals enabled lytic infection but the ionic strength thresholds varied for different ions between phages. Additionally, using a freshwater nitrate-reducing microbiome, we found that the ability of lytic phages to influence nitrate reduction end-products depended upon the carbon source as well as ionic strength. For all phage:host pairs, the ion EC50s for phage infection exceeded the ion concentrations found in many terrestrial freshwater systems. Thus, our findings support a model where phages most influence terrestrial microbial functional ecology in hot spots and hot moments such as metazoan guts, drought influenced soils, or biofilms where ion concentration is locally or transiently elevated and nutrients are available to support the growth of specific phage hosts.

Carlson, Hans K. (ORCID:0000000215835313)↗

The influence of defects and impurities on the nucleation and growth of oriented films by evaporation

The influence of substrate imperfections on the nucleation and growth of fcc metals on alkali halides is discussed. Films deposited on well characterized substrated under well defined vacuum evaporation conditions are investigated. The experimental results of this work are correlated with similar work by other investigators. Models which have been proposed by various authors to explain experimental results are critically examined and areas of difficulty are pointed out. The influence of defects on nucleation rate and the orientation of the film is emphasized. Specific examples of impurity effects, irradiation effects and the influence of amorphous layers are discussed in detail. Evidence is shown that the formation of multiply twinned particles is a result of coalescence and growth. The only consistent model for the orienting influence of impurities is shown to be a chemical reaction effect. It is demonstrated that an alkali metal impurity is very likely responsible for the orienting influence of both water vapor exposure and irradiation. A negative result is found for the reported possibility of an orienting influence being transmitted through an amorphous layer.

Green, A. K.↗

Thermochemical water decomposition processes

Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.

Chao, R. E.↗

Status of equation of state of solids

The results of equation of state (pressure-volume-temperature) measurements for the rare gas solids, alkali metals and alkali halides are reviewed. The precision and errors associated with the techniques most commonly used to obtain measurements of volume as a function of pressure, including piston volume displacement, ultrasonic, shock wave, and Brillouin scattering techniques, length change measurement, and combined length change and ultrasonic transit techniques, are presented. The various equations of state which are normally used to represent these measurements are discussed.

Ruoff, A. L.↗

New gas phase inorganic ion cluster species and their atmospheric implications

Recent experimental laboratory observations, with high-pressure mass spectroscopy, have revealed the existence of previously unreported species involving water clustered to sodium dimer ions, and alkali metal hydroxides clustered to alkali metal ions. The important implications of these results concerning the existence of such species are here discussed, as well as how from a practical aspect they confirm the stability of certain cluster species proposed by Ferguson (1978) to explain masses recently detected at upper altitudes using mass spectrometric techniques.

Maerk, T. D.↗

H-1 NMR study of ternary ammonia-alkali metal-graphite intercalation compounds

For the first-stage ternary ammonia-alkali metal-graphite intercalation compounds M(NH3)(x)C24(x of about 4, M = K, Rb, Cs), three sets of triplet H-1 NMR spectral lines have been observed at various temperatures and orientations due to the H-1 - H-1 and N-14 - H-1 dipolar interactions. The structures of these compounds have been inferred as mobile (liquid-like) intercalant layers of planar M(NH3)4 ions in between the carbon layers. For the intercalated ammonia molecules, the potential barrier is about 0.2 eV and the molecular geometry is very close to the free NH3 in gas phase.

Tsang, T.↗

Alkali metal-sulfur secondary battery containing cathode material particulates

Provided is a rechargeable alkali metal-sulfur cell comprising an anode active material layer, an electrolyte, and a cathode active material layer comprising multiple particulates, wherein at least one of the particulates comprises one or a plurality of sulfur-containing material particles being embraced or encapsulated by a thin layer of a conductive sulfonated elastomer composite having from 0.01% to 50% by weight of a conductive reinforcement material dispersed in a sulfonated elastomeric matrix material, wherein the conductive reinforcement material is selected from graphene sheets, carbon nanotubes, carbon nanofibers, metal nanowires, conductive polymer fibers, or a combination thereof and the composite has a recoverable tensile strain from 2% to 500%, a lithium ion conductivity from 10−7 S/cm to 5×10−2 S/cm, and a thickness from 0.5 nm to 10 μm. This battery exhibits an excellent combination of high sulfur content, high sulfur utilization efficiency, high energy density, and long cycle life.

Zhamu, Aruna↗

Multi-element liquid metal battery

An electrochemical cell including: a negative electrode including calcium and an alkali metal; a positive electrode including one or more elements selected from the group consisting of Al, Si, Zn, Ga, Ge, Cd, In, Sn, Sb, Hg, Tl, Pb, Bi, Te, Bi, Pb, Sb, Zn, Sn and Mg; and an electrolyte including a salt of calcium and a salt of the alkali metal. The electrolyte is configured to allow the cations of the calcium and alkali metal to be transferred from the negative electrode to the positive electrode during discharging and to be transferred from the positive electrode to the negative electrode during charging. The electrolyte exists as a liquid phase and one or both of the negative electrode and the positive electrode exists as liquid or partially liquid phases at operating temperatures of the electrochemical cell.

Ouchi, Takanari↗

Thermal Polymorphism in CsCB11H12

Thermal polymorphism in the alkali-metal salts incorporating the icosohedral monocarba-hydridoborate anion, CB11H12−, results in intriguing dynamical properties leading to superionic conductivity for the lightest alkali-metal analogues, LiCB11H12 and NaCB11H12. As such, these two have been the focus of most recent CB11H12− related studies, with less attention paid to the heavier alkali-metal salts, such as CsCB11H12. Nonetheless, it is of fundamental importance to compare the nature of the structural arrangements and interactions across the entire alkali-metal series. Thermal polymorphism in CsCB11H12 was investigated using a combination of techniques: X-ray powder diffraction; differential scanning calorimetry; Raman, infrared, and neutron spectroscopies; and ab initio calculations. The unexpected temperature-dependent structural behavior of anhydrous CsCB11H12 can be potentially justified assuming the existence of two polymorphs with similar free energies at room temperature: (i) a previously reported, ordered R3 polymorph stabilized upon drying and transforming first to R3c symmetry near 313 K and then to a similarly packed but disordered I43d polymorph near 353 K and (ii) a disordered Fm3 polymorph that initially appears from the disordered I43d polymorph near 513 K along with another disordered high-temperature P63mc polymorph. Quasielastic neutron scattering results indicate that the CB11H12− anions in the disordered phase at 560 K are undergoing isotropic rotational diffusion, with a jump correlation frequency [1.19(9) × 1011 s−1] in line with those for the lighter-metal analogues.

36 MATERIALS SCIENCE↗

Sodium Transport Modes in AMTEC Electrodes

Transport of alkali metal atoms through porous cathodes of alkali metal thermal-to-electric converter (AMTEC) cells is responsible for significant, reducible losses in the electrical performance of these cells.

Sodium↗

Electric propulsion system technology

The work performed in fiscal year (FY) 1991 under the Propulsion Technology Program RTOP (Research and Technology Objectives and Plans) No. (55) 506-42-31 for Low-Thrust Primary and Auxiliary Propulsion technology development is described. The objectives of this work fall under two broad categories. The first of these deals with the development of ion engines for primary propulsion in support of solar system exploration. The second with the advancement of steady-state magnetoplasmadynamic (MPD) thruster technology at 100 kW to multimegawatt input power levels. The major technology issues for ion propulsion are demonstration of adequate engine life at the 5 to 10 kW power level and scaling ion engines to power levels of tens to hundreds of kilowatts. Tests of a new technique in which the decelerator grid of a three-grid ion accelerator system is biased negative of neutralizer common potential in order to collect facility induced charge-exchange ions are described. These tests indicate that this SAND (Screen, Accelerator, Negative Decelerator) configuration may enable long duration ion engine endurance tests to be performed at vacuum chamber pressures an order of magnitude higher than previously possible. The corresponding reduction in pumping speed requirements enables endurance tests of 10 kW class ion engines to be performed within the resources of existing technology programs. The results of a successful 5,000-hr endurance of a xenon hollow cathode operating at an emission current of 25 A are described, as well as the initial tests of hollow cathodes operating on a mixture of argon and 3 percent nitrogen. Work performed on the development of carbon/carbon grids, a multi-orifice hollow cathode, and discharge chamber erosion reduction through the addition of nitrogen are also described. Critical applied-field MPD thruster technical issues remain to be resolved, including demonstration of reliable steady-state operation at input powers of hundreds to thousands of kilowatts, achievement of thruster efficiency and specific impulse levels required for missions of interest, and demonstration of adequate engine life at these input power, efficiency, and specific impulse levels. To address these issues we have designed, built, and tested a 100 kW class, radiation-cooled applied-field MPD thruster and a unique dual-beam thrust stand that enables separate measurements of the applied- and self-field thrust components. We have also initiated the development of cathode thermal and plasma sheath models that will eventually be used to guide the experimental program. In conjunction with the cathode modeling, a new cathode test facility is being constructed. This facility will support the study of cathode thermal behavior and erosion mechanisms, the diagnosis of the near-cathode plasma and the development and endurance testing of new, high-current cathode designs. To facilitate understanding of electrode surface phenomenon, we have implemented a telephoto technique to obtain photographs of the electrodes during engine operation. In order to reduce the background vacuum tank pressure during steady-state engine operation in order to obtain high fidelity anode thermal data, we have developed and are evaluating a gas-dynamic diffuser. A review of experience with alkali metal propellants for MPD thrusters led to the conclusion that alkali metals, particularly lithium, offer the potential for significant engine performance and lifetime improvements. These propellants are also condensible at room temperature, substantially reducing test facility pumping requirements. The most significant systems-level issue is the potential for spacecraft contamination. Subsequent experimental and theoretical efforts should be directed toward verifying the performance and lifetime gains and characterizing the thruster flow field to assess its impact on spacecraft surfaces. Consequently, we have begun the design and development of a new facility to study engine operation with alkali metal propellants.

Brophy, John R.↗

Enhanced electrochemical performance and extended cycling of resorcinol-formaldehyde derived N-doped carbon xerogel for alkali metal-ion (Li/Na/K) batteries

Resorcinol formaldehyde-derived carbon xerogel (RFC) is a versatile material with tuneable properties, synthesized through a simple sol-gel method. This study presents nitrogen-doped RF carbon xerogel (N-RFC) with 11.8 at% nitrogen doping, offering a microporous architecture ideal for alkali metal-ion (Li, Na, K) batteries. The porous N-doped framework enhances electrochemical performance by improving ion transport, increasing active storage sites, and significantly boosting metal-ion adsorption, particularly through pyrrolic nitrogen, as revealed by first-principles calculations supported by XPS analysis. N-RFC anodes showed excellent cycling stability, high-capacity retention, and fast charge/discharge capabilities, rendering them suitable for commercial applications. Notably, the N-RFC anode demonstrates high-rate long-term cycling stability, retaining its capacity of 83.5 % (188 mAh/g at 2 C-rate) and 50 % (133 mAh/g at 1250 mA/g) over 1000 cycles for Li and Na-ion batteries, respectively, favorable for commercial battery applications. Additionally, N-RFC demonstrates a reversible capacity of 120 mAh/g after 394 cycles with a retention of 82 % for K-ion batteries. The ability of the material to accommodate larger ions like Na + and K + further emphasizes its versatility and potential application in diverse alkali metal-ion battery systems.

25 ENERGY STORAGE↗

Fire extinguishant materials

Fire extinguishant composition comprising a mixture of a finely divided aluminum compound and alkali metal, stannous or plumbous halide is provided. Aluminum compound may be aluminum hydroxide, alumina or boehmite but preferably it is an alkali metal dawsonite. The metal halide may be an alkali metal, e.g. potassium iodide, bromide or chloride or stannous or plumbous iodide, bromide or chloride. Potassium iodide is preferred.

Altman, R. L.↗

Chemo-Mechanical Instabilities in Lithium Cobalt Oxide at Higher State-Of-Charge in Li-Ion Batteries

Transition metal oxide cathodes are widely used in commercial Li-ion batteries. However, their practical charge capacity is limited due to severe chemo-mechanical instabilities at higher charge voltage, and state-of-charge condition. Here, in situ stress and strain measurements were synchronized to probe mechanical deformations in the lithium cobalt oxide (LCO) cathode via a multi-beam stress sensor and digital image correlation, respectively. In situ mechanical measurements revealed how Li removal from the electrode structure induces deformations on the LCO composite cathodes during cycling. The structure and morphology of the LCO cathodes were further investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) studies. Two distinct electrochemical and mechanical behaviors were identified when the LCO was charged up to 4.65 V. The LCO undergoes a compressive stress generation when charged up to 4.2 V and surface fractures on the LCO particles were detected by SEM. LCO cathode experienced significantly large contractions (negative strains) when charged up to 4.65 V, where intergranular crack formation and phase transformation were detected on the LCO particles via SEM and XRD, respectively. Overall, the study bridges complicated structural deformations with in situ analysis of mechanical degradations in LCO cathodes charged at higher voltages. The correlation is vital to understanding instability mechanisms in transition metal oxides at high voltages for alkali metal ion batteries.

higher state-of-charge↗

Mixed metal sorbents for CO 2 /H 2O displacement desorption

The disclosure generally relates to CCS sorbents, particularly for CO 2 /H 2O displacement desorption process. The sorbents include an aluminum oxide support that includes two alkali metal salts impregnated on the support. The two alkali metals include a potassium metal salts and a second alkali metal salt which is not potassium. The second metal salt disrupts poisoning effects that degrade sorbent lifetime. The sorbents demonstrate improved CO 2 loadings and better H 2O /CO 2 ratios, as well as improved stability. Compositions and methods of making are disclosed.

Bai, Chuansheng↗

Elucidating the Role of Hydroxide Electrolyte on Anion-Exchange-Membrane Water Electrolyzer Performance

Many solid-state devices, especially those requiring anion conduction, often add a supporting electrolyte to enable efficient operation. The prototypical case is that of anion-exchange-membrane water electrolyzers (AEMWEs), where addition of an alkali metal solution improves performance. However, the specific mechanism of this performance improvement is currently unknown. This work investigates the functionality of the alkali metal solution in AEMWEs using experiments and mathematical models. The results show that additional hydroxide plays a key role not only in ohmic resistance of the membrane and catalyst layer but also in the reaction kinetics. The modeling suggests that the added liquid electrolyte creates an additional electrochemical interface with the electrocatalyst that provides ion-transport pathways and distributes product gas bubbles; the total effective electrochemical active surface area in the cell with 1 M KOH is 5 times higher than that of the cell with DI water. In the cell with 1 M KOH, more than 80% of the reaction current is associate with the liquid electrolyte. These results indicate the importance of high pH of electrolyte and catalyst/electrolyte interface in AEMWEs. The understanding of the functionality of the alkali metal solution presented in this study should help guide the design and optimization of AEMWEs.

25 ENERGY STORAGE↗