Selective para metalation of unprotected 3-methoxy and 3,5-dimethoxy benzoic acids with n-butyl lithium-potassium tert-butoxide (LIC-KOR): synthesis of 3,5-dimethoxy-4-methyl benzoic acid

The potassium salt of 3-methoxy and 3,5-dimethoxy benzoic acids undergoes deprotonation at the position para to the carboxylate group selectively when treated with LIC-KOR in THF at -78 degrees C and it has been extended to the synthesis of 3,5-dimethoxy-4-methyl benzoic acid. (C) 2000 Elsevier Science Ltd. All rights reserved.

Effect of Nanostructuring and Ex situ Amorphous Carbon Coverage on the Lithium Storage and Insertion Kinetics in Anatase Titania

Implications of nanostructuring and conductive carbon interface on lithium insertion/removal capacity and insertion kinetics innanoparticles of anatase polymorph of titania is discussed here.Sol-gel synthesized nanoparticles of titania (particle size similar to 6 nm) were hydrothermally coated ex situ with a thin layer of amorphous carbon (layer thickness: 2-5 nm) and calcined at a temperature much higher than the sol-gel synthesis temperature. The carbon-titania composite particles (resulting size similar to 10 nm) displayed immensely superior cyclability and rate capability (higher current rates similar to 4 g(-1)) compared to unmodified calcined anatase titania. The conductive carbon interface around titania nanocrystal enhances the electronic conductivity and inhibits crystallite growth during electrochemical insertion/removal thus preventing detrimental kinetic effects observed in case of unmodified anatase titania. The carbon coating of the nanoparticles also stabilized the titania crystallographic structure via reduction in the accessibility of lithium ions to the trapping sites. This resulted in a decrease in the irreversible capacity observed in the case of nanoparticles without any carbon coating.

Effect of V2O5 on the Surface and Structural Characteristics of Potassium Lithium Niobate

It has been suggested that materials with interesting and useful bulk non-linear optical properties might result by substituting vanadium, the lightest element in the group V of periodic table, for Nb or Ta atoms along with Li and three oxygens. It is with this motivation that we have been making attempts to grow single crystals of LiNbO3 doped with various concentrations of V2O5. Unfortunately the results obtained on the ceramic samples of this material have not been very encouraging, owing to their hygroscopic nature. However, our attempts to prepare both ceramic and single-crystalline samples of potassium lithium niobate (K3Li2Nb5O15; KLN) doped V2O5 were successful. In this letter we report the preliminary results concerning our studies on the effect of V2O5 doping on the structural as well as topographic features of both ceramic and single-crystalline samples of KLN.

Silicon tetrafluoride : Preparation and reduction with lithium aluminium hydride

Pure silicon tetrafluoride can be prepared in 66% yield from silicon tetrachloride by refluxing with lead fluoride in acetonitrile. The gas can be reduced to pure silane by lithium aluminum hydride in diethyl ether.

Soft matter electrolytes based on polymethylmetacrylate dispersions in lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids

Ion transport in a polymer-ionic liquid (IL) soft matter composite electrolyte is discussed here in detail in the context of polymer-ionic liquid interaction and glass transition temperature The dispersion of polymethylmetacrylate (PMMA) in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) resulted in transparent composite electrolytes with a jelly-like consistency The composite ionic conductivity measured over the range -30 C to 60 C was always lower than that of the neat BMITFSI/BMIPF6 and LiTFSI-BMITFSI/LiTFSI-BMIPF6 electrolytes but still very high (>1 mS/cm at 25 degrees C up to 50 wt% PMMA) While addition of LiTFSI to IL does not influence the glass T-g and T-m melting temperature significantly dispersion of PMMA (especially at higher contents) resulted in increase in T-g and disappearance of T-m In general the profile of temperature-dependent ionic conductivity could be fitted to Vogel-Tamman-Fulcher (VTF) suggesting a solvent assisted ion transport However for higher PMMA concentration sharp demarcation of temperature regimes between thermally activated and solvent assisted ion transport were observed with the glass transition temperature acting as the reference point for transformation from one form of transport mechanism to the other Because of the beneficial physico-chemical properties and interesting ion transport mechanism we envisage the present soft matter electrolytes to be promising for application in electrochromic devices (C) 2010 Elsevier Ltd All rights reserved

Ab initio molecular orbital calculations on ion-molecule and ion pair-molecule complexes of the water-lithium cyanide system

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets were performed on a series of ion-molecule and ion pair-molecule complexes for the H2O + LiCN system. Stabilisation energies (with counter-poise corrections), geometrical parameters, internal force constants and harmonic vibrational frequencies were evaluated for 16 structures of interest. Although the interaction energies are smaller, the geometries and relative stabilities of the monohydrated contact ion pair are reminiscent of those computed for the complexes of the individual ions. Thus, interaction of the oxygen lone pair with lithium leads to a highly stabilised C2v structure, while the coordination of water to the cyanide ion involves a slightly non-linear hydrogen bond. Symmetrical bifurcated structures are computed to be saddle points on the potential energy surface, and to have an imaginary frequency for the rocking mode of the water molecule. On optimisation the geometries of the solvent shared ion pair structures (e.g. Li+cdots, three dots, centered OH2cdots, three dots, centered CN−) revealed a proton transfer from the water molecule leading to hydrogen bonded forms such as Li-O-Hcdots, three dots, centered HCN. The variation in the force constants and harmonic frequencies in the various structures considered are discussed in terms of ion-molecular and ion pair-molecule interactions.

Electron-beam weld microstructures and properties of aluminium-lithium alloy 8090

Lithium-containing aluminium alloys are of considerable current interest in the aerospace and aircraft industries because lithium additions to aluminium improve the modulus and decrease the density compared to conventional aluminium alloys. Few commercial aluminium-lithium alloys have emerged for use in the aerospace industry. One such candidate is 8090, a precipitation-hardenable Al-Li-Cu-Mg alloy. The influence of electron-beam welding on the microstructure and mechanical properties of alloy 8090 material has been evaluated through microscopical observations and mechanical tests. Microscopic observations of the electronbeam welds revealed an absence of microporosity and hot cracking, but revealed presence of microporosity in the transverse section of the weld. Mechanical tests revealed the electronbeam weld to have lower strength, elongation and joint efficiency. A change in microscopic fracture mode was observed for the welded material when compared to the unwelded counterpart. An attempt is made to rationalize the behaviour in terms of competing mechanistic effects involving the grain structure of the material, the role of matrix deformation characteristics, grain-boundary chemistry and grain-boundary failure.

Influence of water and thermal history on ion transport in lithium salt-succinonitrile plastic crystalline electrolytes

Important issues of water and thermal history affecting ion transport in a representative plastic crystalline lithium salt electrolyte: succinonitrile (SN)-lithium perchlorate (LiClO4) are discussed here. Ionic conductivity of electrolytes with high lithium salt amounts (similar to 1 M) in SN at a particular temperature is known to be influenced both by the trans-gauche isomerism and ion association (solvation), the two most important intrinsic parameters of the plastic solvent. In the present study both water and thermal history influence SN and result in enhancement of ionic conductivity of 1 M LiClO4-SN electrolyte. Systematic observations reveal that the presence of water in varying amounts promote ion-pair dissociation in the electrolyte. While trace amounts (approximate to 1-15 ppm) do not affect the trans-gauche isomerism of SN, the presence of water in large amounts (approximate to 5500 ppm) submerges the plasticity of SN. Subjugating the electrolyte to different thermal protocol resulted in enhancement of trans concentration only. This is an interesting observation as it demonstrates a simple and effective procedure involving utilization of an optimized set of external parameters to decouple solvation from trans-gauche isomerism. Observations from the ionic conductivity of various samples were accounted by changes in signature isomer and ion-association bands in the mid-IR regime and also from plastic to normal crystal transition temperature peak obtained from thermal studies. (C) 2010 Elsevier B.V. All rights reserved.

A crosslinked ``polymer-gel'' rechargeable lithium-ion battery electrolyte from free radical polymerization using nonionic plastic crystalline electrolyte medium

A cross-linked polymer-gel soft matter electrolyte with superior electrochemical, thermal and mechanical properties obtained from free radical polymerization of vinyl monomers in a semi-solid organic nonionic plastic crystalline electrolyte for application in rechargeable lithium-ion batteries is discussed here.

Ac conductivity studies of lithium thioborate glasses

The variation in the exponent s in σa.c. agr ωs as a function of temperature is reported for lithium thioborate glasses. The origin of the observed minimum in s is discussed using the diffusion-controlled relaxation (DCR) model. An entirely new model for the a.c. conductivity of highly modified ionic glasses has been proposed and expressions for relaxation identical with those of the DCR model have been obtained, providing a new explanation for the temperature behaviour of s. The origin of two activation barriers generally observed in a.c. conductivity studies is examined in the light of the new model.

The role of additives in a complex lithium silicate glass-ceramic

Several glass-ceramic compositions based on lithium silicates have been examined using thermal expansivity, X-ray diffraction, electrical conductivity, electron microscopy and solid state NMR studies. Role of P2O5 in nucleation and of Al2O3 in smoothening expansion behaviour have been particularly highlighted. Magic angle spinning NMR has been used to ascertain presence of Al in tetrahedral positions in the glassy phase

Improved lithium cyclability and storage in a multi-sized pore (''differential spacers'') mesoporous SnO2

A wide pore distribution mesoporous morphology stabilizes SnO2 structure during lithium insertion and removal and in the process remarkably enhances the lithium storage and cyclability.