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Novel synthesis process and structure refinements of Li{sub 4}Mn{sub 5}O{sub 12} for rechargeable lithium batteries

Description: Well crystallized Li4Mn5O12 was prepared from LiOAc-Mn(NO3)2 under flowing oxygen. Rietveld refinement with XRD and neutron powder diffraction indicated that Li4Mn5O12 has cubic spinel structure in which the Li ions occupy both the tetrahedral sites 8a and part of the octahedral sites 16d but not the 16c sites, while all the Mn ions occupy the 16d sites of the space group Fd{bar 3}m. The lattice parameter was found to be sensitive to synthesis temperature owing to variation in Mn valence. Sample prepared at 500 C showed better electrode performance: a rechargeable capacity of 135 mAh/g for the cell Li/Li4Mn5O12 at cell voltages 2.5-3.6 V. It is found that Mn oxidation state in Li4Mn5O12 has a strong effect on electrode performance of Li/Li4Mn5O12 cell.
Date: December 31, 1996
Creator: Takada, Toshimi; Hayakawa, Hiroshi; Akiba, Etsuo; Izumi, Fujio & Chakoumakos, B.C.
Partner: UNT Libraries Government Documents Department

Physical properties of Li ion conducting polyphosphazene based polymer electrolytes

Description: We report a systematic study of the transport properties and the underlying physical chemistry of some polyphosphazene (PPhz)-based polymer electrolytes. We synthesized MEEP and variants which employed mixed combinations of different length oxyethylene side-chains. We compare the conductivity and ion-ion interactions in polymer electrolytes obtained with lithium triflate and lithium bis(trifluoromethanesulfonyl)imide (TFSI) salts added to the polymer. The combination of the lithium imide salt and MEEP yields a maximum conductivity of 8 x 10{sup -5} {Omega}{sup -1} cm{sup -1} at room temperature at a salt loading of 8 monomers per lithium. In one of the mixed side-chain variations, a maximum conductivity of 2 x 10{sup -4} {Omega}{sup -1} cm{sup -1} was measured at the same molar ratio. Raman spectral analysis shows some ion aggregation and some polymer - ion interactions in the PPhz-LiTFSI case but much less than observed with Li CF{sub 3}SO{sub 3}. A sharp increase in the Tg as salt is added corresponds to concentrations above which the conductivity significantly decreases and ion associations appear.
Date: December 31, 1996
Creator: Sanderson, S.; Zawodzinski, T.; Hermes, R.; Davey, J. & Dai, Hongli
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

Lithium intercalation behavior of surface modified carbonaceous materials

Description: The surface properties of several well-characterized commercial carbon materials were modified by thermal and chemical treatments. The reversible capacities for lithium intercalation of a sponge green coke and a fuel green coke for lithium intercalation increased by as much as 25% after heat treatment in both reducing (5% H{sub 2}/Ar) and oxidizing (CO{sub 2}) environments. The irreversible capacity loss increased significantly with CO{sub 2} treatment at 800{degrees}C. The trend of larger capacity losses with CO{sub 2} treatment is also observed with a synthetic graphite (SFG6) which was produced by heat treatment at about 3000{degrees}C. Carbon fibers that were first impregnated with LiOH solution followed by reaction with CO{sub 2} to form Li{sub 2}CO{sub 3} tended to show lower irreversible capacity losses.
Date: July 17, 1997
Creator: Tran, T. D.; Murguia, L. X.; Song, X. & Kinoshita, K.
Partner: UNT Libraries Government Documents Department

Structural diversity in lithium aryloxides, Part 2

Description: A series of arylalcohols [H-OAr where OAr = OC{sub 6}H{sub 5} (OPh), OC{sub 6}H{sub 4}(2-Me) (oMP), OC{sub 6}H{sub 3}(2,6-Me){sub 2} (DMP), OC{sub 6}H{sub 4}(2-Pr{prime}) (oPP), OC{sub 6}H{sub 3}(2,6-Pr{prime}){sub 2} (DIP), OC{sub 6}H{sub 4}(2-Bu{prime}) (oBP), OC{sub 6}H{sub 3}(2,6-Bu{prime}){sub 2} (DBP) where Me = CH{sub 3}, Pr{prime} = CHMe{sub 2}, and Bu{prime} = CMe{sub 3}] were reacted with LiN(SiMe{sub 3}){sub 2} in pyridine (py) to generate the appropriate ``Li(OAr)(py){sub x}'' complex. The resultant products were characterized by single crystal X-ray diffraction as: [Li(OPh)(py){sub 2}]{sub 2} (1), [Li(oMP)(py){sub 2}]{sub 2} (2), [Li(DMP)(py){sub 2}]{sub 2} (3), [Li(oPP)(py){sub 2}]{sub 2} (4), [Li(DIP)(py){sub 2}]{sub 2} (5), [Li(oBP)(py){sub 2}]{sub 2} (6), and [Li(DBP)(py)]{sub 2} (7). Compounds 1--6 adopt a dinuclear, edge-shared tetrahedral complex. For 7, due to the steric crowding of the DBP ligand, only one py is coordinated yielding a dinuclear fused trigonal planar arrangement. Two additional structure types were also characterized for the DIP ligand as [Li(DIP)(H-DIP)(py)]{sub 2} (5b) and [Li{sub 2}(DIP){sub 2}(py){sub 3}] (5c). {sup 6,7}Li and {sup 13}C NMR solid state MAS spectroscopy indicated that the bulk powder was consistent with the crystalline material. Solution state NMR spectroscopy revealed a symmetric molecule existed in solution for 1--7.
Date: June 6, 2000
Partner: UNT Libraries Government Documents Department

Broadly Turnable Pump-Resonant Diode-Pumped CW PPLN OPO

Description: We have observed low threshold operation of a broadly tunable (2.18-3.4 µm) pump-resonant cw periodically poled lithium niobate (PPLN) optical parametric oscillator (OPO). When pumped at 806 nm with 410 mW from a custom-built diode laser the OPO generated 20 mW of idler output at 3.3 µm.
Date: April 29, 1999
Creator: Alford, W.J.; Bowers, Mark S.; Raymond, T.D. & Seamans, J.F.
Partner: UNT Libraries Government Documents Department

Characterization of lithium phosphorous oxynitride thin films

Description: Electrical and electrochemical properties of an amorphous thin-film lithium electrolyte, lithium phosphorous oxynitride (Lipon), have been studied with emphasis on the stability window vs Li metal and the behavior of the Li/Lipon interface. Ion conductivity of Lipon exhibits Arrhenius behavior at {minus}26 to +140 C, with a conductivity of 1.7 {times} 10{sup {minus}6}S/cm at 25 C and an activity energy of 0.50 {plus_minus} 0.01 eV. A stability window of 5.5 V was observed with respect to a Li{sup +}/Li reference, and no detectable reaction or degradation was evident at the Li/Lipon interface upon lithium cycling.
Date: January 1, 1996
Creator: Yu, Xiaohua; Bates, J. B. & Jellison, G. E., Jr.
Partner: UNT Libraries Government Documents Department

Special properties of optical parametric oscillators

Description: Optical parametric oscillators (OPOS) are useful devices to generate tunable radiation. The tuning characteristics of OPOs can lead to their utility in remote sensing applications. We have investigated injection-seeded OPOs to generate narrow-band Mid-JR radiation for this purpose. OPOs exhibit a resonance structure similar to that of a laser`s cavity limiting the frequency choices available. Also, the coupling of the electric fields of the three interacting waves can generate cavity resonances for OPOs which have no cold cavity resonances (i.e. non-resonant OPOS). The potential for generating multiple frequencies simultaneously from a single OPO is discussed. The generation of multiple output frequencies is accomplished by injecting either multiple signal or multiple pump frequencies to the OPO. A seeded SRO is found to be well-suited to generating spectrally pure and stable multi-line output when the input pump field is multiple frequency. The generation of sideband frequencies during multiple seeding is also observed experimentally and addressed theoretically. The spectral purity of the OPO output is related to the frequency separation of the multi-line input as compared to the OPO cavity resonance structure.
Date: February 27, 1996
Creator: Neuman, W.A. & Velski, S.P.
Partner: UNT Libraries Government Documents Department

Transient radiation-induced absorption in materials for the DOI laser

Description: This is the final report on a series of experiments concerned with transient radiation-induced absorption in materials for a Cr,Nd:GSGG laser. Both the Sandia National Laboratories SPR III pulsed reactor and the Hermes III pulsed X-ray machine are used as radiation sources. The time dependence and the magnitude of the induced absorption in filter glasses and in doped and undoped LiNbO{sub 3} Q-switch materials have been measured. Gain has been observed in Cr,Nd:GSGG, the laser medium, when it is irradiated by X-rays.
Date: January 1, 1995
Creator: Brannon, P. J.
Partner: UNT Libraries Government Documents Department

Self-activating and doped tantalate phosphors.

Description: An ideal red phosphor for blue LEDs is one of the biggest challenges for the solid-state lighting industry. The appropriate phosphor material should have good adsorption and emission properties, good thermal and chemical stability, minimal thermal quenching, high quantum yield, and is preferably inexpensive and easy to fabricate. Tantalates possess many of these criteria, and lithium lanthanum tantalate materials warrant thorough investigation. In this study, we investigated red luminescence of two lithium lanthanum tantalates via three mechanisms: (1) Eu-doping, (2) Mn-doping and (3) self-activation of the tantalum polyhedra. Of these three mechanisms, Mn-doping proved to be the most promising. These materials exhibit two very broad adsorption peaks; one in the UV and one in the blue region of the spectrum; both can be exploited in LED applications. Furthermore, Mn-doping can be accomplished in two ways; ion-exchange and direct solid-state synthesis. One of the two lithium lanthanum tantalate phases investigated proved to be a superior host for Mn-luminescence, suggesting the crystal chemistry of the host lattice is important.
Date: January 1, 2011
Creator: Nyman, May Devan & Rohwer, Lauren Elizabeth Shea
Partner: UNT Libraries Government Documents Department


Description: Lithium borohydride, magnesium hydride and the 2:1 'destabilized' ball milled mixtures (2LiBH{sub 4}:MgH{sub 2}) underwent liquid phase hydrolysis, gas phase hydrolysis and air oxidation reactions monitored by isothermal calorimetry. The experimentally determined heats of reaction and resulting products were compared with those theoretically predicted using thermodynamic databases. Results showed a discrepancy between the predicted and observed hydrolysis and oxidation products due to both kinetic limitations and to the significant amorphous character of observed reaction products. Gas phase and liquid phase hydrolysis were the dominant reactions in 2LiBH{sub 4}:MgH{sub 2} with approximately the same total energy release and reaction products; liquid phase hydrolysis displayed the maximum heat flow for likely environmental exposure with a peak energy release of 6 (mW/mg).
Date: March 13, 2008
Creator: Brinkman, K; Donald Anton, D; Joshua Gray, J & Bruce Hardy, B
Partner: UNT Libraries Government Documents Department


Description: The design and evaluation of media based hydrogen storage systems requires the use of detailed numerical models and experimental studies, with significant amount of time and monetary investment. Thus a scoping tool, referred to as the Acceptability Envelope, was developed to screen preliminary candidate media and storage vessel designs, identifying the range of chemical, physical and geometrical parameters for the coupled media and storage vessel system that allow it to meet performance targets. The model which underpins the analysis allows simplifying the storage system, thus resulting in one input-one output scheme, by grouping of selected quantities. Two cases have been analyzed and results are presented here. In the first application the DOE technical targets (Year 2010, Year 2015 and Ultimate) are used to determine the range of parameters required for the metal hydride media and storage vessel. In the second case the most promising metal hydrides available are compared, highlighting the potential of storage systems, utilizing them, to achieve 40% of the 2010 DOE technical target. Results show that systems based on Li-Mg media have the best potential to attain these performance targets.
Date: July 18, 2011
Creator: Hardy, B.; Corgnale, C.; Tamburello, D.; Garrison, S. & Anton, D.
Partner: UNT Libraries Government Documents Department

Self-Assembled Silica Nano-Composite Polymer Electrolytes: Synthesis, Rheology & Electrochemistry

Description: The ultimate objectives of this research are to understand the principles underpinning nano-composite polymer electrolytes (CPEs) and facilitate development of novel CPEs that are low-cost, have high conductivities, large Li+ transference numbers, improved electrolyte-electrode interfacial stability, yield long cycle life, exhibit mechanical stability and are easily processable. Our approach is to use nanoparticulate silica fillers to formulate novel composite electrolytes consisting of surface-modified fumed silica nano-particles in polyethylene oxides (PEO) in the presence of lithium salts. We intend to design single-ion conducting silica nanoparticles which provide CPEs with high Li+ transference numbers. We also will develop low-Mw (molecular weight), high-Mw and crosslinked PEO electrolytes with tunable properties in terms of conductivity, transference number, interfacial stability, processability and mechanical strength
Date: January 24, 2007
Creator: Khan, Saad A.: Fedkiw Peter S. & Baker, Gregory L.
Partner: UNT Libraries Government Documents Department

Polymer electrolytes for a rechargeable li-Ion battery

Description: Lithium-ion polymer electrolyte battery technology is attractive for many consumer and military applications. A Li{sub x}C/Li{sub y}Mn{sub 2}O{sub 4} battery system incorporating a polymer electrolyte separator base on novel Li-imide salts is being developed under sponsorship of US Army Research Laboratory (Fort Monmouth NJ). This paper reports on work currently in progress on synthesis of Li-imide salts, polymer electrolyte films incorporating these salts, and development of electrodes and cells. A number of Li salts have been synthesized and characterized. These salts appear to have good voltaic stability. PVDF polymer gel electrolytes based on these salts have exhibited conductivities in the range 10{sup -4} to 10{sub -3} S/cm.
Date: October 1, 1996
Creator: Argade, S.D.; Saraswat, A.K.; Rao, B.M.L.; Lee, H.S.; Xiang, C.L. & McBreen, J.
Partner: UNT Libraries Government Documents Department

A rapid method for the determination of lithium transference numbers

Description: Lithium ion-conducting polymer electrolytes are of increasing interest for use in lithium-polymer batteries. Lithium transference numbers, the net fraction of current carried by lithium in a cell, are key figures of merit for potential lithium battery electrolytes. The authors describe the Electrophoretic NMR (ENMR) method for the determination of lithium ion transference numbers (T{sub Li}). The work presented is a proof-of-concept of the application of the ENMR method to lithium ion transference measurements for several different lithium salts in gelled electrolytes. The NMR method allows accurate determination of T{sub Li} values, as indicated by the similarity of T{sub Li} in the gelled electrolytes to those in aqueous electrolyte solutions at low salt concentration. Based on calculated tradeoffs of various experimental parameters, they also discuss some conclusions concerning the range of applicability of the method to other electrolytes with lower lithium mobility.
Date: May 1, 1997
Creator: Zawodzinski, T.A. Jr.; Dai, H.; Sanderson, S.; Davey, J. & Uribe, F.
Partner: UNT Libraries Government Documents Department

Investigation of Mn Implanted LiNbO{sub 3} applying electron paramagnetic resonance technique

Description: The effect of ion implantation on the LiNbO{sub 3} crystal is studied using electron paramagnetic resonance spectroscopy (EPR). EPR measurements on these crystals were performed as a function of ion species Mn and Fe and fluence at room temperature. Also the effect of the laser illumination on the EPR signal was determined by illuminating the crystal in situ and measuring the decay and growth of the EPR signal. LiNbO{sub 3}:Mn{sup 2+} at a depth of approximately 200 nm was formed by implantation of 2.5 {times} 10{sup 14} Mncm{sup 2} and 1 {times} 10{sup 17} Mn/cm{sup 2} at 2 MeV. The implanted samples were compared with bulk doped crystals. It was found that the decay and growth of Mn EPR for the implanted crystal is very small compared with the bulk doped LiNbO{sub 3}:Mn crystal. This was found to be primarily due to the spin concentration on the crystals. On the other, hand the decay time of the high fluence is about 40% slower than the decay of the low fluence implanted crystal.
Date: October 1, 1997
Creator: Darwish, A.; Ila, D.; Poker, D.B. & Hensley, D.K.
Partner: UNT Libraries Government Documents Department