Energy-savvy solid-state and sonochemical synthesis of lithium sodium titanate as an anode active material for Li-ion batteries

Lithium sodium titanate insertion-type anode has been synthesized by classical solid-state (dry) and an alternate solution-assisted (wet) sonochemical synthesis routes. Successful synthesis of the target compound has been realized using simple Na- and Li-hydroxide salts along with titania. In contrast to the previous reports, these energy-savvy synthesis routes can yield the final product by calcination at 650 -750 degrees C for limited duration of 1-10 h. Owing to the restricted calcination duration (dry route for 1-2 h and wet route for 1-5 h), they yield homogeneous nanoscale lithium sodium titanate particles. Sono-chemical synthesis reduces the lithium sodium titanate particle size down to 80-100 nm vis-a-vis solid-state method delivering larger (200-500 nm) particles. Independent of the synthetic methods, the end products deliver reversible electrochemical performance with reversible capacity exceeding 80 mAh.g(-1) acting as a 1.3 V anode for Li-ion batteries. (C) 2015 Elsevier B.V. All rights reserved.

Electronic Structure of Vacancy Ordered Spinels, $GaMo_{4}S_{8}$ and $GaV_{4}S_{8}$, from ab Initio Calculations

We report ab initio calculations for the band dispersions and total as well as partial densities of states for vacancy ordered, clustered spinels, GaMo4S8 and GaV4S8. Results are presented for the high temperature cubic phase for both compounds. Additionally, we discuss results of similar calculations for GaMo4S8 in an idealized cubic structure, as well as the nonmagnetic and the ferromagnetic states of the low temperature rhombohedral structure. Comparison of these results allows us to discuss the unusual aspects of the electronic structure of this interesting class of compounds, and provide estimates of the crystal-field and exchange splitting strengths.

Energetics of rare earth manganese perovskites A1-xA ' xMnO3 (A = La, Nd, Y and A ' = Sr, La) systems

High temperature reaction calorimetry using molten lead berate as solvent has been used to study the thermochemistry of NdMnO3, YMnO3, La1-xSrxMnO3 (with 0 < x < 0.5), and Ln(0.5)Ca(0.5)MnO(3) (with Ln = La, Nd, Y), The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution, The energetic stability of the perovskite depends on the size of the A cation, The enthalpy of formation of YMnO3 (smallest A cation) is more endothermic than those of NdMnO3 and LaMnO3. The energetics of the perovskite also depends on the oxidation state of the B site's ions. In the La1-xSrxMnO3 system, the energetic stability of the structure increases with the Mn4+/Mn3+ ratio, The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability diagram of the lanthanum-manganese-oxygen system in the temperature range 300-1100 K, The LaMnO3/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et nl. calculated from thermogravimetric and conductivity measurements.

Hybrid framework iron(II) phosphate-oxalates

Two inorganic-organic hybrid framework iron phosphate-oxalates, I, [N2C4H12](0.5)[Fe-2(HPO4)(C2O4)(1.5)] and II, [Fe-2(OH2)PO4(C2O4)(0.5)] have been synthesized by hydrothermal means and the structures determined by X-ray crystallography. Crystal Data: compound I, monoclinic, spacegroup = P2(1)/c (No. 14), a=7.569(2) Angstrom, b=7.821(2) Angstrom, c=18.033(4) Angstrom, beta=98.8(1)degrees, V=1055.0(4) Angstrom(3), Z=4, M=382.8, D-calc=2.41 g cm(-3) MoK alpha, R-F=0.02; compound II, monoclinic, spacegroup=P2(1)/c (No. 14), a=10.240(1) b=6.375(3) Angstrom, 9.955(1) Angstrom, beta=117.3(1)degrees, V=577.4(1) Angstrom(3), Z=4, M=268.7, D-calc=3.09 g cm(-3) MoK alpha, R-F=0.03. These materials contain a high proportion of three-coordinated oxygens and [Fe2O9] dimeric units, besides other interesting structural features. The connectivity of Fe2O9 is entirely different in the two materials resulting in the formation of a continuous chain of Fe-O-Fe in II. The phosphate-oxalate containing the amine, I, forms well-defined channels. Magnetic susceptibility measurements show Fen to be in the high-spin state (t(2g)(4)e(g)(2)) in II, and in the intermediate-spin state (t(2g)(5)e(g)(1)) in I.

In search of inorganic nonlinear optical materials for second harmonic generation

In a search for inorganic oxide materials showing second-order nonlinear optical (NLO) susceptibility, we investigated several berates, silicates, and a phosphate containing trans-connected MO6, octahedral chains or MO5 square pyramids, where, M = d(0): Ti(IV), Nb(V), or Ta(V), Our investigations identified two new NLO structures: batisite, Na2Ba(TiO)(2)Si4O12, containing trans-connected TiO5 octahedral chains, and fresnoite, Ba2TiOSi2O7, containing square-pyramidal TiO5. Investigation of two other materials containing square-pyramidal TiO5 viz,, Cs2TiOP2O7 and Na4Ti2Si8O22. 4H(2)O, revealed that isolated TiO5, square pyramids alone do not cause a second harmonic generation (SHG) response; rather, the orientation of TiO5 units to produce -Ti-O-Ti-O- chains with alternating long and short Ti-O distances in the fresnoite structure is most likely the origin of a strong SHG response in fresnoite,

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.

Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Gibbs Energy of Formation of Cobalt Divanadium Tetroxide

The Gibbs energy of formation of V2O3-saturated spinel CoV2O4 has been measured in the temperature range 900–1700 K using a solid state galvanic cell, which can be represented as Pt, Co + CoV2O4 + V2O3/(CaO) ZrO2/Co + CoO, Pt. The standard free energy of formation of cobalt vanadite from component oxides can be represented as CoO (rs) + V2O3 (cor) → CoV2O4 (sp), ΔG° = −30,125 − 5.06T (± 150) J mole−1. Cation mixing on crystallographically nonequivalent sites of the spinel is responsible for the decrease in free energy with increasing temperature. A correlation between “second law” entropies of formation of cubic 2–3 spinels from component oxides with rock salt and corundum structures and cation distribution is presented. Based on the information obtained in this study and trends in the stability of aluminate and chromite spinels, it can be deduced that copper vanadite is unstable.

Composition-controlled metal-insulator transitions and minimum metallic conductivity in the oxide systems LaNi1-xMxO3 (M = Cr, Mn, Fe, or Co)

The composition-controlled metal-insulator transition in the perovskite systems LaNi1-xMxO3 (M = Cr, Mn, Fe, and Co) has been investigated by transport measurements over the temperature range 12-300 K. These systems, which have critical electron densities (nc) in the range (1-2) -1020 electrons cm-3, exhibit sharp metal-insulator transitions at the base temperature. The corresponding minimum metallic conductivity (Ï-min), separating the localized and itinerant electronic regimes, is of the order of 102 ohm-1 cm-1. Particular attention is paid to the idea of Ï-min scaling with nc, and our present results are compared with earlier studies of the metal-insulator transition in low (e.g., Ge:Sb) and high (e.g., metal-ammonia, supercritical Hg) electron-density systems. A link is established between the transport and magnetic properties of the title systems at the metal-insulator transition.

Magnetic-properties of quasi-2-dimensional la1-xsr1+xmno4 and the evolution of itinerant electron ferromagnetism in the sro.(la1-xsrxmno3)n system

Quasi-two-dimensional oxides of the La,+,Sr,+,Mn04 system, possessing the KZNiF4 structure, show no evidence for ferromagnetic ordering in contrast to the corresponding three-dimensional La,+.Sr,MnO~ perovskites. Instead, there is an increasing tendency toward antiferromagnetic ordering with mcreasmg x m La,+,Sr,,, MnOp. Furthermore, these oxides are relatively high-resistivity materials over the entire compositional range. Substitution of Ba for Sr in La&r,.5Mn04 decreases the ferromagnetic interaction. Increasing the number of perovskite layers in SrO (La,-,Sr,MnO& causes an increase in electrical conductivity as well as ferromagnetic interaction. The oxide becomes a highly conducting ferromagnet when n 2 2.

Preparation, structure, and magnetic properties of isostructural La3MAlS7 and La3MFeS7 (M = Mg, Mn, Fe, Co, Ni, or Zn)

A series of quaternary metal sulfides of the general formula La3MM′S7 (M = Mn, Fe, Co; M′ = Al and M = Mg, Mn, Fe, Co, Ni; M′ = Fe) consisting of linear chains of face shared MS6 octahedra and isolated M′S4 tetrahedra has been prepared and studied. The aluminium compounds La3MAlS7 (M = Mn, Fe, Co) exhibit linear chain antiferromagnetism. Magnetic behavior of other La3MFeS7 sulfides has been examined in detail. The magnetic susceptibility of La3MgFeS7 shows that tetrahedral site Fe3+ undergoes a transition from Image to S = 2 spin state around 150 K.

Magnetic properties of quasi-two-dimensional La2NiO4

Magnetic susceptibility studies on single crystals of nearly stoichiometric La2NiO4 with the applied field both parallel and perpendicular to the c axis show a transition at 204 K below which two-dimensional canted antiferromagnetic order seems to exist. This oxide also undergoes a transition from isotropic to anisotropic susceptibility near 100 and 250 K.

Temperature dependence of 35Cl NQR in 2,6-dichloropyridine

Chlorine NQR in 2,6-dichloropyridine has been investigated in the temperature range 77 K to room temperature and a single resonance line has been observed throughout. Using this data, torsional frequencies of the molecule have been evaluated on the basis of both the Bayer theory and the modified Bayer theory incorporating Tatsuzaki correction.

High-Tc superconductivity in the Er---Ba---Cu---O and related systems

ErBa2Cu3O7 and Er0.5Y0.5Ba2Cu3O7 are both high-Tc superconductors attaining zero resistance above 80 K. Preliminary studies indicate that Yb1−xYxBa2Cu3O7 also exhibits zero resistance above 77 K.