Cathodic materials for lithium-ion batteries based on spinels Li x Mn2−y Me y O4: Synthesis, phase composition, and structure of Li x Mn2−y Cr y O4 at x = 1.0−1.2 and y = 0−0.5

Extralithiated chromium-doped finely divided lithium-manganese spinels are synthesized as a result of a two-step solid-phase process with use made of the fusion-saturation method. The spinels are intended for application as cathodic materials in lithium-ion batteries. The phase composition and structural characteristics of samples of cathodic materials of the type Li _x Mn_2?y Cr _y O₄ are studied. The samples with x = 1.0?1.2 and y = 0?0.5 are characterized by phase purity and cubic syngony with parameter a = 0.817?0.823 nm and a disperseness equal to 1–2 nm. The maximum content of chromium and lithium in Li _x Mn_2?y Cr _y O₄ that does not lead to violation of cubic syngony is determined. Lithium excess in the cathodic material that does not exceed 0.2 formula units may be used for compensating the irreversible capacity. Replacing some manganese atoms by chromium may facilitate retention of the structures’s integrity in the course of cycling.     

The formation of superconducting oxide phases in the (Bi,Pb)−Sr−Ca−Cu−O System

The crystallization mechanism of superconducting phases in the (Bi,Pb)?Sr?Ca?Cu?O system was determined on the basis of the results of DTA, DTG and TG studies, supplemented by X-ray examination of ceramic powders obtained by the sol-gel method. It has been demonstrated that the factor determining the formation of superconducting phases: Bi₂Sr₂CaCu₂O_x (low-T _c ) and Bi₂Sr₂Ca₂Cu₃O_x (high-T _c ) is the kinetics of reaction of calcium and strontium carbonates with molten CuBi₂O₄. As a result of the reaction of the bimetallic compound CuBi₂O₄ with SrCO₃ in the liquid phase the compound Bi₂Sr₂CuO₆ is formed. This compound, reacting with calcium and copper oxides, yields superconducting phases: the low-T _c and the high-T _c phase. It has been also observed that an increase in the volume fraction of high-T _c phase in powder subjected to thermal treatment takes place probably due to the repeated disproportionation of low-T _c phase and its repeated synthesis from Bi₂Sr₂CuO₆, CuO and CaO.     

Fabrication, characterization and magnetic behaviour of alumina-doped zinc ferrite nano-particles

Zinc ferrite nano-powders with a nominal composition of ZnFe₂O₄ were prepared by combustion synthesis using mixture of urea and ammonium nitrate as fuel. The influence of alumina-doping on the structural, morphological and magnetic properties of ZnFe₂O₄ nano-particles was investigated by means of X-ray powder diffraction (XRD), infrared (IR) spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and vibrating sample magnetometer (VSM). XRD and IR analyses confirm the cubic spinel phase of ZnFe₂O₄ nano-particles. The Zn ferrite presented a uniform microstructure with grain size in nano-scale. Alumina-doping brought about a change in the morphology of the as prepared ferrite from sphere-like to regular hexagon. Al₂O₃-treatment led to a decrease in the coercivity (H_c), magnetization (M_s) and magnetic moment (n_B) of the investigated system. The maximum decrease in the values of H_c, M_s and n_B due to the treatment with 1.5 wt% Al₂O₃ attained 13.5, 17.4 and 13.5%, respectively. The observed results can be explained on the basis of particle size and the Fe³⁺ concentration in the octahedral and tetrahedral sites involved in the cubic spinel structure.     

Tribochemistry and kinetics of Al2(SO4)3·xH2O decomposition

The thermal decomposition of tribochemically activated Al₂(SO₄)₃·xH₂O was studied by TG, DTA and EMF methods. For some of the intermediate solids, X-ray diffraction and IR-spectroscopy were applied to learn more about the reaction mechanism. Thermal and EMF studies confirmed that, even after mechanical activation of Al₂(SO₄)₃·xH₂O, Al₂O(SO₄)₂ is formed as an intermediate. Isothermal kinetic experiments demonstrated that the thermochemical sulphurization of inactivated Al₂(SO₄)₃·xH₂O has an activation energy of 102.2 kJ·mol^?1 in the temperature range 850–890 K. The activation energy for activated Al₂(SO₄)₃·xH₂O in the range 850–890 K is 55.0 kJ·mol^?1. The time of thermal decomposition is almost halved when Al₂(SO₄)₃·xH₂O is activated mechanically. The results permit conclusions concerning the efficiency of the tribochemical activation of Al₂(SO₄)₃·xH₂O and the chemical and kinetic mechanisms of the desulphurization process.     

Synthesis and properties of the Co7Se8−xSx and Ni7Se8−xSx solid solutions

We report the synthesis and elementary properties of the Co₇Se_8−xS_x (x=0-8) and Ni₇Se_8−xS_x (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni₇Se_8−xS_x system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co₇Se_8−xS_x system, as well as Ni₇Se₈ and Ni₇SeS₇, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/mol_CoK² and ∼7 mJ/mol_NiK² for Co₇Se_8−xS_x and Ni₇Se_8−xS_x, respectively.     

Analysis of the fine structure of XANES spectra over Ni<Emphasis Type="Italic">K</Emphasis> edge in Ni(EtOCS<Subscript>2</Subscript>)<Subscript>2</Subscript>

The NiK edge X-ray absorption near edge spectra (XANES) of the Ni(EtOCS₂)₂ complex were measured. The theoretical NiK edge XANES spectra were calculated by the total multiple scattering and finite difference methods; the potential was calculated with a muffin-tin approximation and without it. It is shown that inclusion of the non-muffin-tin effects is important for modeling the NiK XANES spectrum for the Ni(EtOCS₂)₂ complex; good agreement with experiment was achieved only in the calculations with the total potential (without the muffin-tin approximation for the shape of the potential).     

Covalence reduction factors of four-coordinated pseudo-tetrahedral paramagnetic compounds inD 2d symmetry

Theoretical expressions for the covalence reduction factors of orbital angular momentum and spin-orbit coupling in pseudo-tetrahedral four-coordinated paramagnetic complexes withD _2d symmetry, denoted ask's andR's respectively, have been derived. p ]The mixing coefficients in the antibonding MO's for the CuCl ₄ ^2- ion in three complexes are estimated using suitable approximations. It is shown thatk's must be less thanR's in Tinkham's approximation. Certain misconceptions existing in the literature regarding the value of the integral 〈p _u |???u|s〉 have been clarified.     

The crystal chemistry of Bi6TP2O15+x, T=Fe, Ni, Zn: Isomorphism and polymorphism, structural relationship to Bi6TiP2O16

The crystal structures of compounds with nominal compositions Bi₆FeP₂O_15+x (I), Bi₆NiP₂O_15+x (II) and Bi₆ZnP₂O_15+x (III) were determined from single-crystal X-ray diffraction data. They are monoclinic, space group I2, Z=2. The lattice parameters for (I) are a=11.2644(7), b=5.4380(3), c=11.1440(5) Å, β=96.154(4)°; for (II) a=11.259(7), b=5.461(4), c=11.109(7) Å, β=96.65(1)°; for (III) a=19.7271(5), b=5.4376(2), c=16.9730(6) Å, β=131.932(1)°. Least squares refinements on F² converged for (I) to R1=0.0554, wR₂=0.1408; for (II) R₁=0.0647, wR₂=0.1697; for (III) R₁=0.0385, wR₂=0.1023. The crystals are complexly twinned by 2-fold rotation about , by inversion and by mirror reflection. The structures consist of edge-sharing articulations of OBi₄ tetrahedra forming layers in the a-c plane that then continue by edge-sharing parallel to the b-axis. The three-dimensional networks are bridged by Fe and Ni octahedra in (I) and (II) and by Zn trigonal bipyramids in (III) as well as by oxygen atoms of the PO₄ moieties. Bi also randomly occupies the octahedral sites. Oxygen vacancies exist in the structures of the three compounds due to required charge balances and they occur in the octahedral coordination polyhedron of the transition metal. In compound (III), no positional disorder in atomic sites is present. The Bi-O coordination polyhedra are trigonal prisms with one, two or three faces capped. Magnetic susceptibility data for compound (I) were obtained between 4.2 and 350 K. Between 4.2 and 250 K it is paramagnetic, μ_eff=6.1 μ_B; a magnetic transition occurs above 250 K.     

Influence of electrospraying parameters on the microstructure of La0.6Sr0.4Co0.2F0.8O3−δ films for SOFCs

Ceramics can play a remarkable role in the engineering of intermediate temperature solid oxide fuel cells (IT-SOFCs) capable of meeting the ambitious targets of reduced cost and improved lifetime. While mixed ionic-electronic conductors such as La_xSr_1−xCo_yFe_1−yO_3−δ are being used as volumic cathodes to increase the catalytic performance of these components, adequate microstructures are also an important requirement for optimal performance, particularly at lower operating temperatures. This work is devoted to the fabrication of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ films on Ce_0.9Gd_0.1O_2−δ substrates by electrostatic spray deposition (ESD) and to the characterization of the microstructural dependence on the deposition conditions. A wide variety of microstructures ranging from dense to porous, with particular features such as reticulation and micro-porosity, were obtained by varying the ESD deposition parameters: nozzle-to-substrate distance (15, 30, 43, 45, and 58 mm), solution flow rate (0.34 and 1.5 mL/h), and substrate temperature (300, 350, 400 and 450 °C). The correlation between deposition parameters and resulting microstructures was systematically studied and put into evidence.     

Thermal induced phase separation of E7/PMMA PDLC system

The phase behaviour of thermoplastic polymer-dispersed liquid crystal system is studied with particular emphasis on the various transitions that occur within the system. The extent of plasticization of the polymer(polymethyl methacrylate) by the low molecular weight liquid crystal(E7) along with the several transitions of theLC(Liquid Crystal) are determined by modulated DSC. Optical microscopy was used to construct the temperature versus composition phase diagram. Our study indicates the existence of a limiting temperature of 40°C around which the PMMA matrix turns glassy irrespective of the initial composition within the phase separated region, suggesting the intersection of the glass transition curve with the coexistence curve. A slight depression of theN-I(Nematic to Isotropic) transition of theLC is observed with increasing composition of PMMA whereas theS-M(Smectic to Nematic) transition and theT _g (Glass transition temperature) of theLC remain unaffected. The one phase mixture remains isotropic until phase separation at a lower temperature where theLC rich domains become nematic. The growth ofLC rich domains is studied as a function of temperature and time.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Phase relations, crystal chemistry, and dielectric properties in sections of the La2O3-CaO-MgO-TiO2 system

Subsolidus phase equilibria and crystal chemistry were studied for the La₂O₃-MgO-TiO₂ system and for the ternary sections LaMg_1/2Ti_1/2O₃-CaTiO₃-La₂O₃ and LaMg_1/2Ti_1/2O₃-CaTiO₃-La_0.833Mg_0.25Ti_0.75O₃ in the quaternary La₂O₃-CaO-MgO-TiO₂ system. Dielectric properties (relative permittivity and temperature coefficient of resonant frequency, τ_f) were measured at 5-10 GHz and mapped onto the phase equilibria relations to reveal the compositions of temperature-stable (τ_f=0) compounds and mixtures. Phase equilibria relations were obtained by X-ray powder diffraction analysis of approximately 80 specimens prepared by solid-state reactions in air at ∼1450°C. Six ternary phases were found to form in the La₂O₃-MgO-TiO₂ system, including the three previously reported compounds LaMg_1/2Ti_1/2O₃, La₅Mg_0.5Ti_3.5O₁₅, and “La₆MgTi₄O₁₈”; and the new phases La₁₀MgTi₉O₃₄, La₉Mg_0.5Ti_8.5O₃₁, and a perovskite-type solid solution (1−x)LaMg_1/2Ti_1/2O₃-xLa_2/3TiO₃ (0?x?0.5). The phase previously reported as “La₆MgTi₄O₁₈” was found to form off-composition, apparently as a point compound, at La₆Mg_0.913Ti_4.04O₁₈. Indexed experimental X-ray powder diffraction patterns are given for LaMg_1/2Ti_1/2O₃, La₅Mg_0.5Ti_3.5O₁₅, La₆Mg_0.913Ti_4.04O₁₈, La₁₀MgTi₉O₃₄, and La₉Mg_0.5Ti_8.5O₃₁. LaMg_1/2Ti_1/2O₃ exhibits a slightly distorted perovskite structure with ordered B-cations (P2₁/n; a=5.5608(2) Å, b=5.5749(3) Å, c=7.8610(5) Å, β=90.034(4)°). La₅Mg_0.5Ti_3.5O₁₅ (Pm1; a=5.5639(1), c=10.9928(5) Å) and La₆Mg_0.913Ti_4.04O₁₈ (R3m; a=5.5665(1), c=39.7354(9) Å) are n=5 and n=6 members, respectively, of the (111) perovskite-slab series A_nB_n−1O_3n. The new phases La₁₀MgTi₉O₃₄ (a=5.5411(2), b=31.3039(9), c=3.9167(1) Å) and La₉Mg_0.5Ti_8.5O₃₁ (a=5.5431(2), b=57.055(1), c=3.9123(1) Å) are n=5 and n=4.5 members, respectively, of the (110) perovskite-slab series A_nB_nO_3n+2, which exhibit orthorhombic subcells; electron diffraction revealed monoclinic superlattices with doubled c-parameters for both compounds. Extensive perovskite-type solid solutions form in the ternary sections LaMg_1/2Ti_1/2O₃-CaTiO₃-La₂O₃ and LaMg_1/2Ti_1/2O₃-CaTiO₃-La_0.833Mg_0.25Ti_0.75O₃. The La₂O₃-MgO-TiO₂ system contains two regions of temperature-stable (τ_f=0) compositions. The quaternary La₂O₃-CaO-MgO-TiO₂ system contains an extensive single-phase perovskite-type volume through which passes a surface of temperature-stable compositions with permittivities projected to be in the 40-50 range. Traces of this surface occur as lines of τ_f=0 perovskite-type phases in the ternary sections LaMg_1/2Ti_1/2O₃-CaTiO₃-La₂O₃ and LaMg_1/2Ti_1/2O₃-CaTiO₃-La_0.833Mg_0.25Ti_0.75O₃.     

Crystal structure and magnetic properties of high-oxygen pressure annealed Sr1−xLaxCo0.5Fe0.5O3−δ (0?x?0.5)

Structural and magnetic studies are presented for the perovskite type Sr_1−xLa_xCo_0.5Fe_0.5O_3−δ (0?x?0.5) materials annealed under moderately high-oxygen pressures of ∼200 atm. A detailed analysis of the room temperature neutron time-of-flight diffraction data reveals that the crystal structure of the sample SrCo_0.5Fe_0.5O_2.89(1), previously described as vacancy-disordered cubic, is similar to the formerly reported, oxygen-vacancy ordered Sr₈Fe₈O₂₃ compound, i.e. Sr₈Co₄Fe₄O₂₃ is tetragonal with the I4/mmm symmetry. With an increase of the La content the studied materials become nearly oxygen stoichiometric and a lowering of the crystal symmetry is observed from cubic (x=0.1 and 0.2) to tetragonal I4/mcm (x=0.3 and 0.4), and finally to monoclinic I12/c1 (x=0.5). Low-temperature structural and magnetic measurements show a ferromagnetic ordering with the maximum Curie temperature near 290 K at x=0.2.     

Algorithms to generate the structures of molecular crystals using the method of discrete modeling of packings

A full potential FLAPW-GGA method is used for the first time to study the electronic structure of hexagonal solid solutions of tungsten carbonitrides WC_1?x N _x (0 ≤ x ≤ 0.5) and to calculate their equilibrium structural parameters, density, cohesion energy, and coefficients of low-temperature heat capacity and Pauli paramagnetic susceptibility. They are discussed in comparison with similar values for initial binary phases: WC and WN and also hypothetical solid solutions WB_0.5C_0.5 and WB_0.5N_0.5.     

Synthesis, structure and physical properties of the new Zintl phases Eu11Zn6Sb12 and Eu11Cd6Sb12

Reported are the syntheses, crystal structure determinations from single-crystal X-ray diffraction, and magnetic properties of two new ternary compounds, Eu₁₁Cd₆Sb₁₂ and Eu₁₁Zn₆Sb₁₂. Both crystallize with the complex Sr₁₁Cd₆Sb₁₂ structure type—monoclinic, space group C2/m (no. 12), Z=2, with unit cell parameters a=31.979(4) Å, b=4.5981(5) Å, c=12.3499(14) Å, β=109.675(1)° for Eu₁₁Zn₆Sb₁₂, and a=32.507(2) Å, b=4.7294(3) Å, c=12.4158(8) Å, β=109.972(1)° for Eu₁₁Cd₆Sb₁₂. Their crystal structures are best described as made up of polyanionic and ribbons of corner-shared ZnSb₄ and CdSb₄ tetrahedra and Eu²⁺ cations. A notable characteristic of these structures is the presence of Sb-Sb interactions, which exist between two tetrahedra from adjacent layers, giving rise to unique channels. Detailed structure analyses shows that similar bonding arrangements are seen in much simpler structure types, such as Ca₃AlAs₃ and Ca₅Ga₂As₆ and the structure can be rationalized as their intergrowth. Temperature-dependent magnetization measurements indicate that Eu₁₁Cd₆Sb₁₂ orders anti-ferromagnetically below 7.5 K, while Eu₁₁Zn₆Sb₁₂ does not order down to 5 K. Resistivity measurements confirm that Eu₁₁Cd₆Sb₁₂ is poorly metallic, as expected for a Zintl phase.     

Structure Study of Bi2.5Na0.5Ta2O9 and Bi2.5Nam−1.5NbmO3m+3 (m=2-4) by Neutron Powder Diffraction and Electron Microscopy

The crystal structures of Bi_2.5Na_0.5Ta₂O₉ and Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi₂O₂)²⁺ fluorite layers and (A_m-1B_mO_3m+1)^2- (m=2-4) pseudo-perovskite slabs. Bi_2.5Na_0.5Ta₂O₉ (m=2) and Bi_2.5Na_2.5Nb₄O₁₅ (m=4) crystallize in the orthorhombic space group A2₁am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi_2.5Na_1.5Nb₃O₁₂ (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi_2.5Na_0.5Ta₂O₉ is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.     

The effect of experimental methods and measurement conditions on values of the kinetic parameters of [Co(NH3)6]2(C2O4)3·4H2O

Using the thermal decomposition of [Co(NH₃)₆]₂(C₂O₄)₃·4H₂O as a basis, the paper presents results which show how computed values of kinetic parameters are influenced by experimental conditions (ambient atmosphere, sample mass, linear heating rate) when using the non-isothermal methods and the Coats-Redfern (CR) modified equation. It also illustrates the influence of the experimental methods i.e. non-isothermal and isothermal (conventional) methods and also a quasiisothermal-isobaric one which can be recognised as equivalent to Constant Rate Thermal Analysis (CRTA). The results obtained have confirmed the significant influence of the experimental parameters as well as that of the experimental method used on the estimated values of kinetic parameters. The correlation between activation energy (E) and sample mass (m) or heating rate (β) is generally of a linear nature:E=a+bx     

A novel germanate, Cu2Fe2Ge4O13, with a four tetrahedra oligomer

The structure of Cu₂Fe₂Ge₄O₁₃, previously thought to be CuFeGe₂O₆, has been determined from single-crystal X-ray diffraction data to be monoclinic, P2₁/m, a=12.1050(6), b=8.5073(4), c=4.8736(2) Å, β=96.145(1)°, Z=2, with R1=0.0231 and wR2=0.0605. The unique structure has an oligomer of four germanate tetrahedra, cross-linked laterally by square-planar copper ions, joined end-to-end by a zigzag chain of edge-sharing iron oxide octahedra. Running along the a-direction the metal oxide chain consists of alternating Cu-Cu and Fe-Fe dimers. A hypothetical series of homologous structures (Cu_n−2Fe₂Ge_nO_3n+1 with n=3,4,…,∞) with different length germanate oligomers is proposed, where as n increases, the infinite chain of the CuGeO₃ is approached. In this context, Cu₂Fe₂Ge₄O₁₃ is viewed as being built from blocks of CuGeO₃ and the Fe oxide chains. This material has significance to the study of low-dimensional mixed-spin systems.