Victor A. Maroni

(De)Lithiation Mechanism of Li/SeSx (x = 0–7) Batteries Determined by in Situ Synchrotron X-ray Diffraction and X-ray Absorption Spectroscopy

Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

Surface-Enhanced Infrared Spectroscopy: A Comparison of Metal Island Films with Discrete and Nondiscrete Surface Plasmons:

A study of the surface-enhanced infrared absorption (SEIRA) spectroscopy of para-nitrobenzoic acid (PNBA) adsorbed on thermally evaporated silver films has been conducted to determine the effect of film architecture on the magnitude of the SEIRA enhancement. Ordered arrays of uniformly sized silver nanoparticles, termed periodic particle arrays (PPAs), were prepared on several different infrared transparent substrates (germanium, silicon, and mica) by nanosphere lithography (NSL). It was found that the ordered arrays deposited by NSL produced well-defined and intense surface plasmon resonance (SPR) bands in the infrared at frequencies between 1500 and 4000 cm−1. The peak frequency of these infrared SPR bands depended on the array architecture and the substrate material. By appropriate design of the nanoparticle array, the infrared SPR band can be made to be coincident with the SEIRA sensitive infrared bands of the PNBA. The trends in the infrared SPR peak frequencies and band shapes were consistent with predictions from electrodynamic theory. The SEIRA responses per unit area of deposited metal obtained with the PPA-type films were at best comparable to results obtained with disordered silver and gold films deposited on the same substrate materials by thermal evaporation (i.e., in the absence of any NSL masking spheres). The results of this study are most consistent with theories and models that attribute SEIRA to the dielectric constant and optical extinction spectrum of the metal film.

Kinetics and mechanism of the (B1,Pb)2Sr2Ca2Cu3O10 formation reaction in silver-sheathed pires

Abstract A detailed kinetic and mechanistic analysis of the growth of the (Bi 2− x Pb x )Sr 2 Ca 2 Cu 3 O 10 phase in silver-sheathed wires has been performed by an isothermal equilibration method. Silver tubes loaded with precursor powders were processed into wires using established metallurgical techniques. The wire specimens were immersed in a preheated equilibration apparatus, heat-treated at the desired temperature in 7.5% O 2 , for varying periods of time, then quenched in a room-temperature silicone oil bath. The results indicated that the kinetic data followed a nucleation growth mode1 derived for a reaction at the interface between thin sheets and a fine powder or a fluid. Transmission electron microscopy confirmed the two-dimensional reaction geometry and revealed the presence of an amorphous phase at grain boundaries, where rapid transport diffusion appears to occur due to the absence of the stabilizing influence of the regular lattice. A reduction in activation energy was observed at temperatures 2819°C which is tentatively attributed to the onset of a liquid-phase-controlled reaction (i.e. a phase boundary crossing). The effects of powder processing parameters and precursor particle size on the kinetic behavior and the growth rate of the (Bi 2− Pb x )Sr 2 Ca 2 Cu 3 O 10 phase are also discussed.

Enhanced flux pinning in MOCVD-YBCO films through Zr additions: systematic feasibility studies

Systematic effects of Zr additions on the structural and flux pinning properties of YBa{sub 2}Cu{sub 3}O{sub 7-{delta}} (YBCO) films deposited by metal-organic chemical vapor deposition (MOCVD) have been investigated. Detailed characterization, conducted by coordinated transport, x-ray diffraction, scanning and transmission electron microscopy analyses, and imaging Raman microscopy have revealed trends in the resulting property/performance correlations of these films with respect to varying mole percentages (mol%) of added Zr. For compositions {le} 7.5 mol%, Zr additions lead to improved in-field critical current density, as well as extra correlated pinning along the c-axis direction of the YBCO films via the formation of columnar, self-assembled stacks of BaZrO{sub 3} nanodots.

Thermostability and decomposition of the (Bi,Pb)2Sr2Ca2Cu3O10 phase in silver‐clad tapes

The stability of the Bi2−xPbxSr2Ca2Cu3O10 (Pb‐2223) phase contained in silver‐sheathed oxide‐powder‐in‐tube specimens has been investigated by x‐ray diffraction, transmission electron microscopy, and energy dispersive x‐ray analysis. Silver tubes loaded with Pb‐2223 precursor powders were processed into tapes using established metallurgical techniques. The tapes were heat‐treated in a specially designed equilibration apparatus at selected temperatures (800–845 °C) for a range of times (10–5500 min) and quenched in liquid gallium held at ∼40 °C. The results showed that the Pb‐2223 phase is stable in a limited temperature interval between 810 and 830 °C in 7.5% oxygen. At 800 °C, this phase decomposes to Bi2Sr2CaCu2O8 (2212), Ca2PbO4, and CuO; while at temperatures ≥840 °C it partially melts with precipitation of Bi2Sr2CuO6 (2201) and Ca2CuO3. The effects of the silver cladding on the Pb‐2223 phase stability and microstructure are also discussed.

Hydrogen permeation characteristics of some austenitic and nickel-base alloys

The hydrogen permeabilities of 321-SS, 316-SS, Inconel-625, and Inconel-718 have been measured for hydrogen driving pressures in the range from 10−3 to 104 Pa and for temperatures between 350 and 1050 K. It was found that the use of active hydrogen purity control measures, which included direct hydrogen supply by a temperature-controlled uranium hydride bed and the implementation of a throttled ion pump, greatly increased the capability to obtain unperturbed permeation data at low driving pressures, i.e., <10 Pa. For all four alloys studied, a half-power dependence of permeability on hydrogen driving pressure was obtained at the higher end of the pressure range studied. Also, the pressure at which deviations from a half-power dependence occurred was found to depend to a great extent on upstream hydrogen purity. In general, the Inconel alloys appeared slightly more sensitive to impurities (such as H2O and O2) than the austenitic alloys, quite possibly because of the presence of small amounts of aluminum in the Inconels.

Vibrational Frequencies and Force Constants for Tetrahedral MgX4−2 (X=Cl, Br, and I) in MgX2–KX Melts

Raman spectra are reported for the species present in MgX2–KX melts (X=Cl, Br, and I) with X−1/Mg+2 mole ratios near 4.0. The observation of one polarized band and three depolarized bands for each halide melt is consistent with the existence of the tetrahedral complexes MgCl4−2, MgBr4−2, and MgI4−2. All the observed frequencies are calculated within 1 cm−1 using a Urey—Bradley force field which consists of an Mg–X stretching constant, an X–Mg–X bending constant, and an X ··· X repulsion constant.

Doped graphene nanohole arrays for flexible transparent conductors

Graphene nanohole arrays (GNAs) were fabricated using nanoimprint lithography. The improved optical transmittance of GNAs is primarily due to the reduced surface coverage of graphene from the nanohole fabrication. Importantly, the exposed edges of the nanoholes provided effective sites for chemical doping using thionyl chloride was shown to enhance the conductance by a factor of 15–18 in contrast to only 2-4 for unpatterned graphene. GNAs can provide a unique scheme for improving both optical transmittance and electrical conductivity of graphene-based transparent conductors.

Materials considerations in tritium handling systems

Abstract The interaction of tritium with materials of construction is a key area of consideration in addressing tritium handling and containment requirements for fusion systems. In this context, dissolution, diffusion, and permeation of hydrogen isotopes are the dominant properties of interest. The factors which nest heavily influence these properties relate to choice of material, surface and bulk microstructure, impurity interactions, and radiolytic effects (in the case of tritium). The interactions of tritium with normetallic materials are not nearly as well understood as those between tritium and metals, and substantial impetus exists for research in this area. The basis for selecting and qualifying materials for tritium service in fusion facilities is reasonably well established, but must be expanded and focused towards the specific needs of the fusion program.

Influence of silver cladding on the formation and alignment of the (Bi2−xPbx)Sr2Ca2Cu3O10+δ phase

Cross‐section transmission electron microscopy was used to investigate the interaction of silver with (Bi,Pb)‐Sr‐Ca‐Cu‐O phases during the formation of (Bi2−xPbx)Sr2Ca2Cu3O10+δ (Bi‐2223) in a silver‐sheathed wire containing a powder composed of (Bi,Pb)2Sr2CaCu2O8+δ (Bi‐2212) plus second phases. Observations of the interfacial regions of samples quenched at different stages of conversion revealed that (1) Bi‐2212 is initially in direct contact with silver, with the (001) planes parallel to the interface; (2) an amorphous layer between Bi‐2212 and silver appears during the induction period that precedes the conversion reaction; and (3) Bi‐2223 is detected at the silver/powder interface hundreds of minutes before it begins to appear in regions of the powder away from the interface. The implications of these results are presented and discussed.