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Electrochemical cell for in-situ x-ray characterization

Description: An electrochemical cell suitable for in-situ XRD analysis is presented. Qualitative information such as phase formation and phase stability can be easily monitored using the in-situ cell design. Quantitative information such as lattice parameters and kinetic behavior is also straightforward. Analysis of the LiMn&sub2;O&sub4; spinel using this cell design shows that the lattice undergoes two major structural shrinkages at approx. 4.0 V and approx. 4.07 V during charging. These shrinkages correlate well with the two electrochemical waves observed and indicate the likelihood of two separate redox processes which charging and discharging.
Date: August 4, 1998
Creator: Doughty, D.H.; Ingersoll, D. & Rodriguez, M.A.
Partner: UNT Libraries Government Documents Department

Low cost MCFC anodes

Description: This paper outlines a project, funded under a DOE SBIR grant, which tested a potentially lower cost method of manufacturing MCFC stack anodes and evaluated the feasibility of using the technology in the existing M-C Power Corp. manufacturing facility. The procedure involves adding activator salts to the anode tape casting slurry with the Ni and Cr or Al powders. Two different processes occur during heat treatment in a reducing environment: sintering of the base Ni structure, and alloying or cementation of the Cr or Al powders. To determine whether it was cost-effective to implement the cementation alloying manufacturing process, the M-C Power manufacturing cost model was used to determine the impact of different material costs and processing parameters on total anode cost. Cost analysis included equipment expenditures and facility modifications required by the cementation alloying process.
Date: December 31, 1996
Creator: Erickson, D.S.
Partner: UNT Libraries Government Documents Department

IGT Stack No. 6 (SDG{ampersand}E-1) Test Plan and Component Specification Document: Topical report, March 1996

Description: The purpose of Stack-6 (SDG{ampersand}E-1) is to scale up and demonstrate the long term performance and endurance characteristics of the IMHEX stack design and the Generation No. 2 cell components (improved pore matching electrodes) in a 20 cell subscale stack test.
Date: December 31, 1997
Partner: UNT Libraries Government Documents Department

Effect on Performance of Composition of Li-Ion Carbon Anodes Derived from PMAN/DVB Copolymers

Description: The effects on electrochemical performance of the nitrogen content of disordered carbons derived from polymethacryonitrile (PMAN)-divinylbenzene (DVB) copolymers were examined in galvanostatic cycling tests between 2 V and 0.01 V vs. Li/Li+ in lM LiPF<sub>6</sub>/ethylene carbonate (EC)-dimethyl carbonate (DMC). The first-cycle reversible capacities and coulombic efficiencies increased with increase in the level of nitrogen for samples prepared at 700&deg;C. However, the degree of fade also increased. Similar tests were performed on materials that were additionally heated at 1,000&deg; and 1,300&deg;C for five hours. Loss of nitrogen, oxygen, and hydrogen occurred under these conditions, with none remaining at the highest temperature in all cases but one. The pyrolysis temperature dominated the electrochemical performance for these samples, with lower reversible and irreversible capacities for the first intercalation cycle as the pyrolysis temperature was increased. Fade was reduced and coulombic efficiencies also improved with increase in temperate. The large irreversible capacities and high fade of these materials makes them unsuitable for use in Li-ion cells.
Date: May 14, 1999
Creator: Even, William R. & Guidotti, Ronald A.
Partner: UNT Libraries Government Documents Department

Edge reclamation in position-sensitive photomultiplier tubes

Description: We have investigated the performance of a position-sensitive, gamma-ray detector based on a CsI(Na) scintillator coupled to a Hamamatsu R3292 Position-Sensitive Photomultiplier Tube (PSPMT). The R3292 has an active area 10.0 cm in diameter (quoted). Utilization of the full active area of the photocathode is a goal that has been previously unrealized due to edge effects. Initial measurements with a 0.75 cm thick CsI(Na) crystal indicate that the performance (position resolution linearity) starts to degrade as one reaches a radius of only 3.5 cm, reducing the active area by 60%. Measuring the anode wires we have found that this fall off is not solely due to crystal edge effects, but rather is inherent to the tube crystal system. In this paper we describe the results of our measurements and how good performance can be maintained across a full 10cm of the tube face through the use of a few additional electronics channels.
Date: June 16, 1999
Creator: Nakae, L & Ziock, K
Partner: UNT Libraries Government Documents Department

Flash X-Ray Injector Study

Description: The study described in this report1 models the FXR injector from the cathode to the exit of the injector. The calculations are compared to actual experimental measurements, table 1. In these measurements the anode voltage was varied by changing the Marks-Bank charging voltage. The anode-cathode spacing was varied by adjusting the location of the cathode in hopes of finding an island of minimum emittance (none found). The bucking coil current was set for zero field on the cathode. In these measurements, a pepper-pot mask was inserted into FXR at beam bug 135 and viewed downstream via a wiggle probe diagnostic at cell gap J21, figure 1. The observed expansion of the beamlets passing through the mask of known geometric layout and hole size allow a calculation of the phase space beam properties.
Date: March 26, 2004
Creator: Paul, A C
Partner: UNT Libraries Government Documents Department


Description: The use of multi-coupled electrode arrays in various corrosion applications is discussed with the main goal of advancing the understanding of various corrosion phenomena. Both close packed and far spaced electrode configurations are discussed. Far spaced electrode arrays are optimized for high throughput experiments capable of elucidating the effects of various variables on corrosion properties. For instance the effects of a statistical distribution of flaws on corrosion properties can be examined. Close packed arrays enable unprecedented spatial and temporal information on the behavior of local anodes and cathodes. Interactions between corrosion sites can trigger or inhibit corrosion phenomena and affect corrosion damage evolution.
Date: February 23, 2006
Creator: Budiansky, N.D.; Bocher, F.; Cong, H.; Hurley, M.F. & Scully, J.R.
Partner: UNT Libraries Government Documents Department

Inert anodes and advanced smelting of aluminum

Description: This report provides a broad assessment of open literature and patents that exist in the area of inert anodes and their related cathode systems and cell designs, technologies that are relevant for the advanced smelting of aluminum. The report also discusses the opportunities, barriers, and issued associated with these technologies from a technical, environmental, and economic viewpoint. It discusses the outlook for the direct retrofit of advanced reduction technologies to existing aluminum smelters, and compares retrofits to ''brown field'' usage and ''green field'' adoption of the technologies. A number of observations and recommendations are offered for consideration concerning further research and development efforts that may be directed toward these advanced technologies. The opportunities are discussed in the context of incremental progress that is being made in conventional Hall-Heroult cell systems.
Date: July 1, 1999
Creator: Technologies, ASME Technical Working Group on Inert Anode
Partner: UNT Libraries Government Documents Department

Effect of Sulfur and Hydrocarbon Fuels on Titanate/Ceria SOFC Anodes

Description: The purpose of the project is to develop low-cost, high-performance anodes that offer low polarization resistance as well as improved tolerance for nonidealities in anode environment such as redox cycles, sulfur and other poisons, and hydrocarbons.
Date: January 27, 2005
Creator: Marina, O.A.; Pedersen, L.R. & Stevenson, J.W.
Partner: UNT Libraries Government Documents Department

Lithium-endohedral C{sub 60} complexes.

Description: High capacity, reversible, lithium intercalated carbon anodes have been prepared, 855 m.Ah/g, which exceed the capacity for stage 1 lithium intercalated carbon anodes, 372 mAh/g. Since there is very little hydrogen content in the high capacity anode, the fullerene C{sub 60} lattice is used to investigate the nature of lithium ion bonding and spacing between lithiums in endohedral lithium complexes of C{sub 60}. Three lithium-endohedral complexes have been investigated using ab initio molecular orbital calculations involving 2,3 and 5 lithium. The calculated results suggest that lithium cluster formation may be important for achieving the high capacity lithium carbon anodes.
Date: May 4, 1998
Creator: Scanlon, L. G.
Partner: UNT Libraries Government Documents Department

Determination of the Hall Thruster Operating Regimes

Description: A quasi one-dimensional (1-D) steady-state model of the Hall thruster is presented. For the same discharge voltage two operating regimes are possible -- with and without the anode sheath. For given mass flow rate, magnetic field profile and discharge voltage a unique solution can be constructed, assuming that the thruster operates in one of the regimes. However, we show that for a given temperature profile the applied discharge voltage uniquely determines the operating regime: for discharge voltages greater than a certain value, the sheath disappears. That result is obtained over a wide range of incoming neutral velocities, channel lengths and widths, and cathode plane locations. It is also shown that a good correlation between the quasi 1-D model and experimental results can be achieved by selecting an appropriate electron mobility and temperature profile.
Date: April 9, 2002
Creator: Dorf, L.; Semenov, V.; Raitses, Y. & Fisch, N.J.
Partner: UNT Libraries Government Documents Department

Electrical and Electrochemical Performance Characteristics of Small Commercial Li-Ion Cells

Description: Advanced rechargeable lithium-ion batteries are presently being developed and commercialized worldwide for use in consumer electronics, military and space applications. At Sandia National Laboratories we have used different electrochemical techniques such as impedance and charge/discharge at ambient and subambient temperatures to probe the various electrochemical processes that are occurring in Li-ion cell. The purpose of this study is to identify the component that reduces the cell performance at subambient temperatures. Our impedance data suggest that while the variation in the electrolyte resistance between room temperature and {minus}20 C is negligible the anode electrolyte interfacial resistance increases by an order of magnitude in the same temperature regime. We believe that the solid electrolyte interface (SEI) layer on the carbon anode may be responsible for the increase in cell impedance. We have also evaluated the cells in hybrid mode with capacitors. High-current operation in the hybrid mode allowed fill usage of the Li-ion cell capacity at 25 C and showed a factor of 5 improvement in delivered capacity at {minus}20 C.
Date: December 22, 1998
Creator: Ingersoll, D.; Nagasubramanian, G. & Roth, E.P.
Partner: UNT Libraries Government Documents Department

A theoretical study of a carbon lattice system for lithium intercalated carbon anodes

Description: A theoretical study was performed using computational chemistry to describe the intermolecular forces between graphite layers as well as spacing and conformation. It was found that electron correlation and a diffuse basis set were important for this calculation. In addition, the high reactivity of edge sites in lithium intercalated carbon anodes was also investigated. In this case, the reactive sites appear to strongly correlate with the relative distribution of the total atomic spin densities as well as total atomic charges. The spacing of graphite layers and lithium ion separation within an {open_quotes}approximated{close_quotes} lithium intercalated carbon anode was also investigated. The spacing of the carbon layers used in this investigation agrees most closely for that found in disordered carbon lattices.
Date: September 1, 1997
Creator: Scanlon, L.G.; Storch, D.M.; Newton, J.H. & Sandi, G.
Partner: UNT Libraries Government Documents Department

Small angle neutron and X-ray scattering studies of carbons prepared using inorganic templates

Description: Small angle neutron (SANS) and X-ray (SAXS) scattering analyses of carbons derived from organic-loaded inorganic template materials, used as anodes in lithium ion cells, have been performed. Two clays were used as templates to load the organic precursors, pillared montmorrillonite (PILC), a layered silicate clay whose sheets have been permanently propped open by sets of thermally stable molecular props, and sepiolite, a natural channeled clay. Five different organic precursors were used to load the PILC: pyrene, styrene, pyrene/trioxane copolymer, ethylene and propylene, whereas only propylene and ethylene were used to load sepiolite. Pyrolysis took place at 700{degrees}C under nitrogen. Values such as hole radius, fractal dimension, cutoff length and density of the final carbons will be compared as a function of the clay and carbon precursors.
Date: September 1, 1997
Creator: Sandi, G.; Thiyagarajan, P.; Winans, R.E. & Carrado, K.A.
Partner: UNT Libraries Government Documents Department

Zinc air refuelable battery: alternative zinc fuel morphologies and cell behavior

Description: Multicell zinc/air batteries have been tested previously in the laboratory and as part of the propulsion system of an electric bus; cut zinc wire was used as the anode material. This battery is refueled by a hydraulic transport of 0.5-1 mm zinc particles into hoppers above each cell. We report an investigation concerning alternative zinc fuel morphologies, and energy losses associated with refueling and with overnight or prolonged standby. Three types of fuel pellets were fabricated, tested and compared with results for cut wire: spheres produced in a fluidized bed electrolysis cell; elongated particles produced by gas-atomization; and pellets produced by chopping 1 mm porous plates made of compacted zinc fines. Relative sizes of the particles and cell gap dimensions are critical. All three types transported within the cell 1553 and showed acceptable discharge characteristics, but a fluidized bed approach appears especially attractive for owner/user recovery operations.
Date: January 1, 1997
Creator: Cooper, J.F. & Krueger, R.
Partner: UNT Libraries Government Documents Department

Polymer Electrolyte Fuel Cells Membrane Hydration by Direct Liquid Water Contact

Description: An effective means of providing direct liquid hydration of the membrane tends to improve performance particularly of cells with thicker membranes or at elevated temperatures. Supplying the water to the membrane from the anode flow-field through the anode backing via wicks would appear to have advantages over delivering the water through the thickness of the membrane with regards to the uniformity and stability of the supply and the use of off-the-shelf membranes or MEAs. In addition to improving cell performance, an important contribution of direct liquid hydration approaches may be that the overall fuel cell system becomes simpler and more effective. The next steps in the evolution of this approach are a demonstration of the effectiveness of this technique with larger active area cells as well as the implementation of an internal flow-field water reservoir (to eliminate the injection method). Scale-up to larger cell sizes and the use of separate water channels within the anode flow-field is described.
Date: November 1, 1998
Creator: Wilson, M.S.; Zawodzinski, C. & Gottesfeld, S.
Partner: UNT Libraries Government Documents Department

Composite Metal-hydrogen Electrodes for Metal-Hydrogen Batteries

Description: The purpose of this project is to develop and conduct a feasibility study of metallic thin films (multilayered and alloy composition) produced by advanced sputtering techniques for use as anodes in Ni-metal hydrogen batteries. The anodes could be incorporated in thin film solid state Ni-metal hydrogen batteries that would be deposited as distinct anode, electrolyte and cathode layers in thin film devices. The materials could also be incorporated in secondary consumer batteries (i.e. type AF(4/3 or 4/5)) which use electrodes in the form of tapes. The project was based on pioneering studies of hydrogen uptake by ultra-thin Pd-capped metal-hydrogen ratios exceeding and fast hydrogen charging and Nb films, these studies suggested that materials with those of commercially available metal hydride materials discharging kinetics could be produced. The project initially concentrated on gas phase and electrochemical studies of Pd-capped niobium films in laboratory-scale NiMH cells. This extended the pioneering work to the wet electrochemical environment of NiMH batteries and exploited advanced synchrotron radiation techniques not available during the earlier work to conduct in-situ studies of such materials during hydrogen charging and discharging. Although batteries with fast charging kinetics and hydrogen-metal ratios approaching unity could be fabricated, it was found that oxidation, cracking and corrosion in aqueous solutions made pure Nb films-and multiiayers poor candidates for battery application. The project emphasis shifted to alloy films based on known elemental materials used for NiMH batteries. Although commercial NiMH anode materials contain many metals, it was found that 0.24 ┬Ám thick sputtered Zr-Ni films cycled at least 50 times with charging efficiencies exceeding 95% and [H]/[M] ratios of 0.7-1.0. Multilayered or thicker Zr-Ni films could be candidates for a thin film NiMH battery that may have practical applications as an integrated power source for modern electronic devices.
Date: April 1, 1997
Creator: Ruckman, M W; Wiesmann, H; Strongin, M; Young, K & Fetcenko, M
Partner: UNT Libraries Government Documents Department

Comparison of the electrochemical properties of several commercial graphites with a templated disordered carbon

Description: A templated carbon was prepared by the pyrolysis of pyrene impregnated into pillared clay (PILC). The electrochemical performance of this was evaluated with the goal of using this material as an anode in Li-ion cells. The reversible capacity was measured as a function of C rate and the cycling characteristics were determined for various intercalation protocols. The performance of this material was compared to that of several commercial graphites tested under the same conditions. The PILC carbon shows great promise as a Li-ion anode if the fade and first-cycle losses can be controlled.
Date: April 11, 2000
Creator: Guidotti, R. A.; Reinhardt, F. W. & Sandi, G.
Partner: UNT Libraries Government Documents Department

Small angle x-ray scattering studies of carbon anodes used in lithium rechargeable batteries.

Description: In ANL laboratories, disordered carbons with predictable surface area and porosity properties have been prepared using inorganic templates containing well defined pore sizes. The carbons have been tested in electrochemical cells as anodes in lithium secondary batteries. They deliver high specific capacity and display excellent performance in terms of the number of cycles run. In situ small angle X-ray scattering (SAXS) during electrochemical cycling was carried out at the Advanced Photon Source, at ANL. In order to monitor the carbon electrode structural changes upon cycling, an electrochemical cell was specially designed to allow for the application of electrical current and the collection of SAXS data at the same time. Results show that upon cycling the structure of the carbon remains unchanged, which is desirable in reversible systems.
Date: November 16, 1999
Creator: Sandi, G.; Carrado, K. A.; Winans, R. E.; Seifert, S. & Johnson, C. S.
Partner: UNT Libraries Government Documents Department

Electrochemical Evaluation of Thin-Film Li-Si Anodes Prepared by Plasma Spraying

Description: Thin-film electrodes of a plasma-sprayed Li-Si alloy were evaluated for use as anodes in high-temperature thermally activated (thermal) batteries. These anodes were prepared using 44% Li/56% Si (w/w) material as feed material in a special plasma-spray apparatus under helium or hydrogen, to protect this air- and moisture-sensitive material during deposition. Anodes were tested in single cells using conventional pressed-powder separators and lithiated pyrite cathodes at temperatures of 400 to 550 C at several different current densities. A limited number of 5-cell battery tests were also conducted. The data for the plasma-sprayed anodes was compared to that for conventional pressed-powder anodes. The performance of the plasma-sprayed anodes was inferior to that of conventional pressed-powder anodes, in that the cell emfs were lower (due to the lack of formation of the desired alloy phases) and the small porosity of these materials severely limited their rate capability. Consequently, plasma-sprayed Li-Si anodes would not be practical for use in thermal batteries.
Date: September 8, 1999
Partner: UNT Libraries Government Documents Department

Characterization of the passivation layer on disordered carbons in lithium-ion cells

Description: Intercalation anodes of graphite or disordered carbon in rechargeable Li-ion batteries (based on aprotic organic solvents) develop a passivating film during the first intercalation of Li{sup +}. The formation of this film reduces the cycling efficiency and results in excessive consumption of Li{sup +}. The exact nature of this film is not well defined, although there are many similarities in properties to the films that form on Li anodes under similar cycling conditions. In this study we report on characterization studies of films formed during galvanostatic cycling of disordered carbons derived from polymethylacryolintrile (PMAN) in a 1M LiPF{sub 6} solution in ethylene carbonateldimethyl carbonate solution (1:1 by vol.). Complementary tests were also conducted with glass carbon, where intercalation cannot occur. Complex-impedance spectroscopy was the primary measurement technique, supplemented by cyclic voltammetry.
Date: December 1, 1995
Creator: Guidotti, R. & Johnson, B.
Partner: UNT Libraries Government Documents Department