Monoclinic superstructure V<Subscript>14</Subscript>O<Subscript>6</Subscript> of the tetragonal solid solution of oxygen in vanadium

The monoclinic (space group C2/m) superstructure of V₁₄O₆, which is formed in the atom-vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is studied by the methods of x-ray diffraction and symmetry analysis. It has been found that the channel of the order-disorder phase transition attributed to the formation of the monoclinic suboxide V₁₄O₆ includes six superstructure vectors belonging to three non-Lifshitz stars {k ₁₋₁}, {k ₁₋₂}, and {k _1–3} of one type {k ₁}. The distribution function of the O atoms in the V₁₄O₆ monoclinic superstructure has been calculated. It has been shown that the displacements of V atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the fcc sublattice and the transition from the suboxide V₁₄O₆ to the cubic vanadium monoxide with the B1 structure.     

A Theoretical Study of <Superscript>51</Superscript>V Electric Field Gradient Tensors in Pyrovanadates and Metavanadates

A computational study of the ⁵¹V electric field gradient (EFG) tensors in pyrovanadates, α-Zn₂V₂O₇, Cd₂V₂O₇, β-Mg₂V₂O₇ and BaCaV₂O₇, and the metavanadates, LiVO₃, α-NaVO₃, KVO₃, ZnV₂O₆ and MgV₂O₆, is presented. Restricted Hartree–Fock and hybrid density functional theory calculations have been used to investigate the effects of the size of vanadium-oxygen clusters, basis set size, proton-termination and embedded cluster techniques on the accuracy of the calculated EFG tensors. Good agreement between theory and experiment is obtained for most of the vanadates. A sound methodology is suggested for calculating the EFG tensor in pyrovanadates which contain isolated V₂O₇ ⁴⁻ clusters. For metavanadates, the charges of the bridging oxygen atoms can be differentiated from those of terminal oxygen atoms by terminating the former with hydrogen atoms, and embedded cluster molecular orbital calculations are useful in accounting for the long-range electrostatic interactions which influence the EFG tensor components. EFG tensor orientations vary for different pyrovanadate structural types, and individual components are confined by symmetry elements in the metavanadates. A preliminary comparison is made between ⁵¹V EFG tensors calculated with ab initio and plane wave methods. Theoretical EFG tensor components and orientations, in combination with experimental ⁵¹V solid-state nuclear magnetic resonance data, are demonstrated to be useful tools for prediction of molecular structure. Authors' address: Robert W. Schurko, Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada     

DO<Subscript>3</Subscript>-type cubic structure of nonstoichiometric vanadium monoxide

An X-ray diffraction study indicates that nonstoichiometric vanadium monoxide VO _y ≡ V _x O _z (y = z/x) has a cubic structure of the DO₃ type (space group Fm $ \bar 3 $ \bar 3 m), where vanadium atoms are not only at the 4(a) sites of the metal fcc sublattice, but also at the tetrahedral 8(c) sites. This circumstance fundamentally distinguishes monoxide VO _y from strongly nonstoichiometric MX _y compounds with the B1 structure and the same space group, where atoms M and X and structural vacancies ▪ and ▭ of the metal and nonmetal sublattices, respectively, are distributed over the 4(a) and 4(b) sites. The dependence of the filling factor q of the tetrahedral interstices by vanadium atoms on the relative content y of oxygen in VO _y has been obtained. It has been shown that the composition of cubic vanadium monoxide should be represented as VO _y ≡ V _x O _z ≡ V _{x − 2q} V_2q ^(t)▪_{1 − x + 2q} O _z ▭_{1 − z} , taking into account the structure.     

Low-temperature synthesis of Cu-doped Li<Subscript>1.2</Subscript>V<Subscript>3</Subscript>O<Subscript>8</Subscript> as cathode for reversible lithium storage

Li_{1 .2}V₃O₈ and Cu-doped Li_1.2V₃O₈ were prepared at a temperature as low as 300 °C by a sol-gel method. The structure, morphology, and electrochemical performance of the as-prepared samples were characterized by means of X-ray diffraction, scanning electron microscopy, electrochemical impedance spectroscopy, and the galvanostatic discharge–charge techniques. It is found that the Cu-doped Li_1.2V₃O₈ sample exhibits less capacity loss during repeated cycling than the undoped one. The Cu-doped Li_1.2V₃O₈ sample demonstrates the first discharge capacity of 275.9 mAh/g in the range of 3.8–1.7 V at a current rate of 30 mA/g and remains at a stable discharge capacity of 264 mAh/g within 30 cycles. Furthermore, the possible role that copper plays in enhancing the cycleability of Li_1.2V₃O₈ has also been elucidated.     

Lithiated c-V<Subscript>2</Subscript>O<Subscript>5</Subscript> thin-film as positive electrode for rocking-chair solid-state lithium microbattery

We report for the first time the use of lithiated crystalline V₂O₅ thin films as positive electrode in all-solid-state microbatteries. Crystalline Li_xV₂O₅ films (x ≈ 0.8 and 1.5) are obtained by vacuum evaporation of metallic lithium deposited on sputtered c-V₂O₅. An all-solid-state lithium microbattery of Li_1.5V₂O₅/LiPON/Li exhibited a typical reversible capacity of 50 μAh/cm² in the potential range 3.8/2.15 V which exceeds by far the results known on all-solid-state lithium batteries using amorphous V₂O₅ films and lithiated amorphous Li_xV₂O₅ thin films as positive electrode. Hence, the present work opens the possibility of using high performance crystalline lithiated V₂O₅ thin films in rocking-chair solid-state microbatteries.     

S<Subscript>3</Subscript> symmetry and neutrino masses and mixings

Based on the universal seesaw mass matrix model with the three scalars φ_i, and by assuming S₃ flavor symmetry for the Yukawa interactions, the lepton masses and mixings are investigated systematically. In order to understand the observed neutrino mixing, the charged leptons (e,μ,τ) are regarded as the three objects (e₁,e₂,e₃) of S₃, while the neutrino mass eigenstates are regarded as the irreducible representation (ν_η,ν_σ,ν_π) of S₃, where (ν_π,ν_η) and ν_σ are a doublet and a singlet, respectively, which are composed of the three objects (ν₁,ν₂,ν₃) of S₃.     

Atomic displacements in the V<Subscript>52</Subscript>O<Subscript>64</Subscript> superstructure and the short-range order in superstoichiometric cubic VO<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> vanadium monoxide with metal vacancies

Atomic displacements in the lattice of the tetragonal V₅₂O₆₄ superstructure have been experimentally determined. It has been found that atomic displacement waves, which are attributed to the formation of the short-range displacement order, appear in the vanadium and oxygen sublattices of this superstructure. It has been shown that the V₅₂O₆₄ superstructure is formed on the basis of disordered superstoichiometric cubic vanadium monoxide with the short-range order in the metallic sublattice. The character of the short-range order is such that vanadium atoms occupying tetrahedral positions are in the environment of four vacant sites of the vanadium sublattice. This means that the superstoichiometric VO_>1.0 vanadium monoxide has a cubic structure differing from the B1-type structure characteristic of most of the strongly nonstoichiometric cubic compounds MX _y (X = C, N, O) of transition metals.     

Effect of carbon vacancies on the electric resistivity of nonstoichiometric VC<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> vanadium carbide

The influence of the temperature, concentration, and distribution of structure vacancies of the carbon sublattice on the electric resistivity ρ of nonstoichiometric VC _y vanadium carbide (0.66 ≤ y ≤ 0.875) has been studied in the temperature range of 300–1200 K. The symmetry and structure characteristics of the ordered V₆C₅ and V₈C₇ phases formed owing to low-temperature annealing on various sections of the homogeneity region of the VC _y carbide. The dependence of the residual electric resistivity on the content of the disordered vanadium carbide is explained by the atom-vacancy interaction and the change in the carrier concentration in the homogeneity region of VC _y .     

Magnetic properties of the Gd<Subscript>2</Subscript>V<Subscript>0.67</Subscript>Mo<Subscript>1.33</Subscript>O<Subscript>7</Subscript> and Y<Subscript>2</Subscript>VMoO<Subscript>7</Subscript> pyrochlore compounds

It is demonstrated that 50% substitution of vanadium for molybdenum in the pyrochlore lattice of the complex oxide Y₂(V _x Mo_{1 ? x} )₂O₇ results in a transition from the spin-glass ground state (at x = 0) to the ferromagnetic state in Y₂VMoO₇ (a = 10.1645(2) Å, T _C = 55 K). The Gd₂V_0.67Mo_1.33O₇ compound (a = 10.2862(3) Å) is a ferromagnet with T _C (84 K) exceeding that of undoped Gd₂MnO₂O₇.     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

Extraction of the neutron charge form factor G<Superscript>n</Superscript><Subscript>E</Subscript>(Q<Superscript>2</Superscript>) from the charge form factor of deuteron G<Superscript>d</Superscript><Subscript>C</Subscript>(Q<Superscript>2</Superscript>)

We extract the neutron charge form factor G ⁿ _E(Q ²) from the charge form factor of deuteron G ^d _C(Q ²) obtained from T ₂₀(Q ²) data at 0≤Q ²≤ 1.717 (GeV/c)². The extraction is based on the relativistic impulse approximation in the instant form of the relativistic Hamiltonian dynamics. Our results (12 new points) are compatible with existing values of the neutron charge form factor of other authors. We propose a fit for the whole set (36 points) taking into account the data for the slope of the form factor at Q ² = 0. Received: 26 July 2002 / Accepted: 18 September 2002 / Published online: 4 February 2003 RID="a" ID="a"e-mail: krutov@ssu.samara.ru RID="b" ID="b"e-mail: troitsky@theory.sinp.msu.ru Communicated by V.V. Anisovich     

Cells studies on PEO/PEG/NaClO<Subscript>3</Subscript> thin-film electrolyte system based on composite V<Subscript>2</Subscript>O<Subscript>5</Subscript> electrode

The thin-film solid polymer electrolyte based on polyethylene oxide (PEO) with sodium chlorite (NaClO₃) has been prepared by a solution-cast technique. The electrolyte was characterized by X-ray diffraction (XRD), infrared (IR), cyclic voltammetry, alternating current conductivity, and Wagner’s polarization studies. The complexation of NaClO₃ with PEO was confirmed through the XRD and IR studies. The transference number measurement has shown that the ion transport is predominant over electrons in the polymer electrolytes (t _ions ≈ 0.94). The conductivity enhancement was observed in the case of the PEO/NaClO₃ system with the addition of plasticizers (low-molecular-weight polyethylene glycol, organic solvents propylene carbonate and dimethyl formamide. Cyclic voltammetry analysis showed the stability and redox character of the electrolyte and electrode. Finally, polymer electrolyte systems were examined by electrochemical cell studies using V₂O₅ and composite V₂O₅ cathode at temperature of 35 °C. Overall, the plasticized electrolyte shows a better electrochemical performance, and a higher discharge capacity was observed in composite V₂O₅-based cells over V₂O₅-based cells.     

Vibrational spectra of monoisotopic SiH<Subscript>4</Subscript> and GeH<Subscript>4</Subscript> in low-temperature matrices

IR absorption spectra of monoisotopic ²⁸SiH₄ and ⁷⁶GeH₄ are studied in Ar and N₂ matrices at 10 K. It is shown that the absorption spectra of silane and germane are similar in the regions of the stretching ν₃ and bending ν₄ vibrations. Four groups of bands can be separated out in the spectra of each molecule: (1) narrow bands characteristic of the matrix isolation studies, (2) broad bands, (3) diffuse absorption with a large value of the spectral moment M ₂^* the intensity of which increases upon annealing, and (4) bands of dimers the intensity of which increases quadratically with concentration. The spectra of ²⁸SiH₄ and ⁷⁶GeH₄ in nitrogen matrices contain a triplet in the stretching region and a doublet in the bending region, which is explained by the change in the molecular symmetry from T _d to C _3V on passage from the gas phase to solid nitrogen.     

Ordered monoclinic vanadium suboxide V<Subscript>14</Subscript>O<Subscript>6</Subscript>

The monoclinic (space group C2/m) superstructure of the suboxide V₁₄O₆, which is formed as a result of the atomic and vacancy ordering of the tetragonal solid solution of oxygen in vanadium, is investigated using X-ray diffraction and symmetry analysis. The monoclinic suboxide V₁₄O₆ is observed in the vanadium oxide samples VO_0.57, VO_0.81, and VO_0.86 synthesized at 1770 K and the samples VO _y (0.87 ≤ y ≤ 0.98) additionally annealed at 1470 K after the synthesis. It is established that the channel of the disorder-order phase transition associated with the formation of the monoclinic suboxide V₁₄O₆ includes six superstructure vectors belonging to three non-Lifshitz stars of one type {k ₁}. The distribution function of the oxygen atoms in the monoclinic superstructure of the suboxide V₁₄O₆ is calculated. It is demonstrated that the displacements of vanadium atoms distort the body-centered tetragonal metal sublattice, thus preparing the formation of the facecentered cubic sublattice and the transition from the suboxide V₁₄O₆ to the cubic vanadium monoxide with the B1 structure.     

Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).     

Magnetic susceptibility in quasi one-dimensional Ba<Subscript>a2</Subscript>V<Subscript>3</Subscript>O<Subscript>9</Subscript>: chain segmentation versus the staggered field effect

A pronounced Curie-like upturn of the magnetic susceptibility χ( T ) of the quasi one-dimensional spin chain compound Ba₂V₃O₉ has been found recently [#!kaul:02!#]. Frequently this is taken as a signature for a staggered field mechanism due to the presence of g-factor anisotropy and Dzyaloshinskii-Moriya interaction. We calculate this contribution within a realistic structure of vanadium 3 d- and oxygen 2 p-orbitals and conclude that this mechanism is far too small to explain experimental results. We propose that the Curie term is rather due to a segmentation of spin chains caused by broken magnetic bonds which leads to uncompensated S = ? spins of segments with odd numbers of spins. Using the finite-temperature Lanczos method we calculate their effective moment and show that ∼ 1% of broken magnetic bonds is sufficient to reproduce the anomalous low-T behavior of χ( T ) in Ba₂V₃O₉. Received 19 December 2002 / Received in final form 29 January 2003 Published online 14 March 2003     

Enhanced electrochemical performance of lithium ion battery cathode Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C

Li-ion battery cathode material lithium-vanadium-phosphate Li₃V₂(PO₄)₃ was synthesized by a carbon-thermal reduction method, using stearic acid, LiH₂PO₄, and V₂O₅ as raw materials. And stearic acid acted as reductant, carbon source, and surface active agent. The effect of its content on the crystal structure and electrochemical performance of Li₃V₂(PO₄)₃/C were characterized by XRD and electrochemical performance testing, respectively. The results showed that the content of carbon source has no significant effect on the crystal structure of lithium vanadium phosphate. Lihtium vanadium phosphate obtained with 12.3% stearic acid demonstrated the best electrochemical properties with a typical discharge capacity of 119.4 mAh/g at 0.1 C and capacity retention behavior of 98.5% after 50 cycles. And it has high reversible discharge capacity of 83 mAh/g at 5 C with the voltage window of 3 to 4.3 V.     

Structure,lattice dynamics,and exchange interaction in Lu<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>, Y<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>: an ab initio approach

Ab initio calculations of the crystal structure and fundamental vibrations of vanadium pyrochlores Lu₂V₂O₇ and Y₂V₂O₇ are performed. The calculations are performed in the framework of the density functional theory (DFT) with the use of hybrid functionals. The ions involved in the vibrations are determined by the isotope substitution method. Values of the isotropic exchange interaction constant were calculated. Theoretical results for the crystal structure parameters, the vibrational frequencies, and the isotropic exchange interaction parameter are compared with the experimental data.     

Effects of dopant on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials

The effects of dopant on the electrochemical properties of spinel-type Li_3.97M_0.1Ti_4.94O₁₂ (M = Mn, Ni, Co) and Li_(4-x/3)Cr_xTi_(5-2x/3)O₁₂(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm² between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr³⁺ dopant improved the reversible capacity and cycling stability over the pristine Li₄Ti₅O₁₂. The substitution of the Mn³⁺ and Ni³⁺ slightly decreased the capacity of the Li₄Ti₅O₁₂. Dopants such as Co³⁺ to some extent worsened the electrochemical performance of the Li₄Ti₅O₁₂.     

Soft X-ray resonant scattering study of single-crystal LaSr<Subscript>2</Subscript>Mn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Soft X-ray resonant scattering studies at the Mn L_{II, III}- and the La M_{IV, V}- edges of single-crystal LaSr₂Mn₂O₇ are reported. At low temperatures, below T_N ≈ 160 K, energy scans with a fixed momentum transfer at the A-type antiferromagnetic (0 0 1) reflection around the Mn L_{II, III}-edges with incident linear σ and π polarizations show strong resonant enhancements. The splitting of the energy spectra around the Mn L_{II, III}-edges may indicate the presence of a mixed valence state, e.g., Mn³⁺/Mn⁴⁺. The relative intensities of the resonance and the clear shoulder-feature as well as the strong incident σ and π polarization dependences strongly indicate its complex electronic origin. Unexpected enhancement of the charge Bragg (0 0 2) reflection at the La M_{IV, V}-edges with σ polarization has been observed up to 300 K, with an anomaly appearing around the orbital-ordering transition temperature, T_OO ≈ 220 K, suggesting a strong coupling (competition) between them.