Synthesis of layered Li1.2+x[Ni0.25Mn0.75]0.8−xO2 materials (0 ≤ x ≤ 4/55) via a new simple microwave heating method and their electrochemical properties

Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) was prepared by a new simple microwave heating method and the effect of extra Li⁺ content on electrochemistry of Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) was firstly revealed. X-ray diffraction identified that they had layered α-NaFeO₂ structure (space group R-3m). Linear variation of lattice constant as a function of x value supported the formation of solid solution, that is, extra Li⁺ is possibly incorporated in structure of layered Li_1.2Ni_0.2Mn_0.6O₂ (x = 0), accompanying oxidization of Ni²⁺ to Ni³⁺ to form Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55). This was confirmed by X-ray photoelectron spectroscopy that Ni³⁺ appeared and increased in content with increasing x value. Charge–discharge tests showed that Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) truly displayed different electrochemical properties (different initial charge–discharge plots, capacities and cycleability). Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) in this work delivered the highest discharge capacity of 219 mAh g⁻¹ between 4.8 and 2.0 V. Increasing Li content (x value in Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂) reduced charge–discharge capacities, but significantly enhancing cycleability.     

Fabrication of dense LaCrO3-based interconnect thin membrane on anode substrates by co-firing

In order to develop cost-effective method to prepare ceramic interconnect membrane for solid oxide fell cell stacks, the triple-phase composites of NiO/Sm_0.2Ce_0.8O_2−δ/La_0.7Ca_0.3Cr_0.97O_3−δ with the weight ratios of 6:4:x (x = 0, 2, 3, 4, 5) were, respectively prepared, and then examined as novel anode supports. The sintering character, microstructure, electrical conductivity, fracture strength, and thermal expansion coefficient of the anodes were, respectively investigated in detail as a function of La_0.7Ca_0.3Cr_0.97O_3−δ content. Results indicate the above-mentioned performances of NiO/Sm_0.2Ce_0.8O_2−δ/La_0.7Ca_0.3Cr_0.97O_3−δ anode at x ≤ 3 have no significant reduction, and are still acceptable for the practical requirements for solid oxide fell cells. Furthermore, by using a simple and cost-effective drop-coating/co-firing process, dense La_0.7Ca_0.3Cr_0.97O_3−δ interconnect membrane was successfully prepared on the anode support of NiO/Sm_0.2Ce_0.8O_2−δ/La_0.7Ca_0.3Cr_0.97O_3−δ at x = 3. This work presents a simple technical route for developing dense interconnect membranes for Sm_0.2Ce_0.8O_2−δ-based fuel cell stacks.     

High-temperature oxygen non-stoichiometry, conductivity and structure in strontium-rich nickelates La2−xSrxNiO4−δ (x = 1 and 1.4)

Oxygen non-stoichiometry, electrical conductivity and thermal expansion of La_2−xSr_xNiO_4−δ phases with high levels of strontium-substitution (1 ≤ x ≤ 1.4) have been investigated in air and oxygen atmosphere in the temperature range 20–1050 °C. These phases retain the K₂NiF₄-type structure of La₂NiO₄ (tetragonal, space group I4/mmm). The oxygen vacancy fraction was determined independently from thermogravimetric and neutron diffraction experiments, and is found to increase considerably on heating. The electrical resistivity, thermal expansion and cell parameters with temperature show peculiar variations with temperature, and differ notably from La₂NiO_4±δ in this respect. These variations are tentatively correlated with the evolution of nickel oxidation state, which crosses from a Ni³⁺/Ni⁴⁺ to a Ni²⁺/Ni³⁺ equilibrium on heating.     

The structural and electrical property of CuCr1 − xNixO2 delafossite compounds

A series of CuCr_1 − xNi_xO₂ (0 ≤ x ≤ 0.06) polycrystalline samples was prepared. The electrical conductivity was measured in the temperature range of 160–300 K. It was found that the electrical conductivity (σ) increases rapidly with the doping of Ni²⁺ ions. At room temperature, the σ is 0.047 S cm^− 1 for the sample with x = 0.06, which is two orders of magnitude larger than that of the CuCrO₂ sample (9.49E− 4 S cm^− 1). The Seebeck coefficients are positive for all samples, which indicate p-type conducting of the samples. The experimental results imply that it is possible to get higher electrical conductivity p-type transparent conducting oxides (TCO) from CuMO₂ by doping with divalent ions.     

Synthesis of solid solution Er2−xCexW3O12 and studies of their thermal expansion behavior

The syntheses and structures of Er_2−xCe_xW₃O₁₂ were studied. It was found that pure phases could form only for 0.0 ≦ x ≦ 0.4 and 1.5 ≦ x ≦ 2.0. Compounds with 0 ≦ x ≦ 0.4 have the hydrated orthorhombic structure at room temperature and transform to unhydrated orthorhombic one above 135 °C whereas samples with 1.5 ≦ x ≦ 2.0 crystallize in monoclinic structure. Thermal expansion properties of Er_2−xCe_xW₃O₁₂ were studied with high temperature X-ray powder diffraction. Samples with 0 ≦ x ≦ 0.4 exhibit negative thermal expansion in temperature range of 200-800 °C and higher cerium content leads to more negative thermal expansion coefficient. However, compounds with 1.5 ≦ x ≦ 2.0 show positive thermal expansion owing to the edge-sharing polyhedra.     

Structural, electrochemical and thermal properties of LiNi0.8−xCo0.2CexO2 as cathode materials for lithium ion batteries

A series of cathode materials for lithium ion batteries with the formula LiNi_0.8−xCo_0.2Ce_xO₂ (0 ≤ x ≤ 0.03) were synthesized by sol–gel method using citric acid as a chelating agent. The effects of cerium substitution on the structural, electrochemical and thermal properties of the cathode materials are investigated through X-ray diffraction (XRD), charge–discharge cycling, cyclic voltammogram (CV), electrochemical impedance spectroscopy (EIS) experiments and differential scanning calorimetry (DSC). Results show that the Ce substitution made the layered structure of materials more regular and less cation-ion mixing. An effective improved cycling performance is observed for cerium-doped cathode materials, which is interpreted to a significant suppression of phase transitions and charge-transfer impedance increasing during cycling. The thermal stability of cerium-doped materials is also improved, which can be attributed to its lower oxidation ability and enhanced structural stability at delithiated state.     

Synthesis and properties of β type Bi(III)2?2xDy(II)2xO3 ? xx solid solution

In the present work, tetragonal β type Bi(III)_{2 − 2x}Dy(II)_2xO_{3 − x}■_x (■:,empty oxygen site) solid solutions have been synthesized in the ranges 0.06 ≤ x ≤ 0.08 at 750°C and 0.05 ≤ x ≤ 0.09 at 800°C by doping small amounts of Dy₂O₃ into monoclinic α -Bi₂O₃. X-ray powder diffraction (XRD) has been used for characterisation of the doped Dy₂O₃ powders as well as for calculation of the unit cell parameters. The polymorphic phase transitions, crystallographic properties, particle sizes, the scanning electron microscope (SEM) microprobe analysis and Dy₂O₃ content dependence of the lattice parameters of the observed β-phase has been reported. The obtained solid solutions had nonstoichiometric character and nonstoichiometry increases with the increasing amount of Dy₂O₃ addition. The experimental results suggested that oxygen vacancies are present in the crystal structure of Dy₂O₃ doped β type solid solutions.     

Doping-induced microstructural, textural and optical properties of In2Ti1−xVxO5+δ semiconductors and their role in the photocatalytic splitting of water

The physicochemical properties of V-doped indium titanates (In₂Ti_1−xV_xO_5+δ, 0.0 ≤ x ≤ 0.2) were investigated by using XPS, powder XRD, UV–vis, SEM and luminescence spectroscopy techniques. The Rietveld refinement of XRD data revealed that even though the V-containing samples were isostructural with In₂TiO₅ (orthorhombic space group Pnma), a systematic x-dependent variation was noticeable in the Ti–O bond lengths in [TiO₆] octahedral units, cell parameters and in the value of δ. XPS results confirmed the coexistence of V⁵⁺ and V⁴⁺ states, leading thereby to an enhancement in oxygen non-stoichiometry in the doped samples. A loading-dependent progressive shift from 400 to 750 nm was also observed in the onset of the absorption edge, indicating a significant narrowing of the band gap. Furthermore, the samples with higher V-content were comprised of the grain clusters having larger size and an irregular shape. The UV–vis, photoluminescence and thermoluminescence studies indicate that the doping-induced lattice defects may give rise to certain closely spaced acceptor/donor energy levels in between the band gap of host matrix. The indium titanates are found to serve as stable photocatalysts for water splitting under visible light, where oxygen was the major reaction product. The role of microstructural and morphological properties in the photocatalytic activity is discussed.     

Thermal expansion studies of Gd2Mo3O12 and Gd2W3O12

Simultaneous thermogravimetric/differential thermal analysis of Gd₂Mo₃O₁₂ showed an irreversible phase transition at 1178 K where as Gd₂W₃O₁₂ showed reversible phase transition at 1433 K, which were confirmed by powder X-ray diffraction. The thermal expansion behavior of α-Gd₂Mo₃O₁₂ (room temperature phase), β-Gd₂Mo₃O₁₂ (phase obtained by heating Gd₂Mo₃O₁₂ at 1223 K) and Gd₂W₃O₁₂ have been investigated using high temperature X-ray diffractometer. The cell volume of α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂, fit into polynomial expression with respect to temperature, showed positive thermal expansion up to 1073, 1173 and 1173 K, respectively. The average volume expansion coefficients for α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂ are 39.52 × 10⁻⁶, 21.23 × 10⁻⁶ and 37.96 × 10⁻⁶ K⁻¹, respectively.     

Synthesis, structure and dielectric characterization of Ln2Ti2−2xM2xO7(Ln=Gd, Er; M=Zr, Sn, Si)

The progress in wireless communications and information access has demanded the use of electronic ceramics exhibiting desired properties. To further our understanding of these properties, compounds in the Ln₂Ti_2-2xM_2xO₇ (Ln=Gd, Er; M=Zr, Sn, Si) systems were synthesized by ceramic methods and characterized by powder X-ray diffraction. The ZrO₂-doped Gd₂Ti_2−2xZr_2xO₇ compounds adopt the pyrochlore structure type and form a complete solid solution. Er₂Ti_2−2xZr_2xO₇ forms a pyrochlore solid solution for x<0.1. However, stoichiometric Er₂Zr₂O₇ does not form; instead Er₄Zr₃O₁₂ forms a with defect fluorite structure. The Sn-doped Ln₂Ti_2−2xSn_2xO₇ (Ln=Gd, Er) compounds form complete solid solutions, and the Si compounds adopt the pyrochlore structure up to x=0.05. At ambient temperature, dielectric constants range from 10 to 61 for Er₂Ti_2−2xZr_2xO₇ and 16-31 for Gd₂Ti_2−2xZr_2xO₇ with low dielectric loss (1×10⁻³) at 1 GHz.     

Crystallographic and low frequency conductivity studies of the spinel systems CuFe2O4 and Cu1?xZnxGa0.1Fe1.9O4; (0.0 ≤ x ≤ 0.5)

Spinel solid solutions of CuFe₂O₄ and Cu_1−xZn_xGa_0.1Fe_1.9O₄ with (0.0 ≤ x ≤ 0.5) are synthesized. Crystallographic phase transformation from tetragonal-to-cubic occurred at x = 0.2. The derived structural parameters manifest that Zn occupies the tetrahedral A-site while Cu and Ga occupy the octahedral B-site and Fe distributes among A- and B-sites. Electrical conductivity measurements of these materials as a function of temperature and frequency revealed semiconducting behavior except CuFe₂O₄ sample, which has a metallic behavior at low frequency and at high frequency, semiconductor-to-metallic transition occurred as temperature increases. The metallic behavior in this sample is attributed to cation-cation interactions at B-site while, the semiconductor behavior in Cu_1−xZn_xGa_0.1Fe_1.9O₄ compounds is due to the cation–anion–cation interactions at the same site in the spinel lattice. All compositions exhibit transition with change in the slope of conductivity versus temperature curve. This transition temperature (T_c) decreases linearly with increasing Zn content x. The relation of the universal exponent s with temperature gives evidence that over large polaron OLP and correlated barrier hopping CBH conduction mechanisms are presented in CuFe₂O₄ and Cu_1−xZn_xGa_0.1Fe_1.9O₄ compounds respectively.     

Microstructures and thermoelectric properties of p-type pseudo-binary AgxBi0.5Sb1.5−xTe3 (x = 0.05–0.4) alloys prepared by cold pressing

The p-type pseudo-binary Ag_xBi_0.5Sb_1.5−xTe₃ (x = 0.05–0.4) alloys were prepared by cold pressing. The thermal conductivities (κ) were calculated from the values of heat capacities, densities and thermal diffusivities measured, and range approximately from 0.66 to 0.56 (W K^− 1 m^− 1) for the Ag_xBi_0.5Sb_1.5−xTe₃ alloy with molar fraction x being 0.4. Combining with the electrical properties obtained in the previous study, the maximum dimensionless figure of merit ZT of 1.1 was obtained at the temperature of 558 K.     

Ionic Conductivity of Ln<Subscript>2 + <Emphasis Type="Italic">x</Emphasis></Subscript>Zr<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>7 − <Emphasis Type="Italic">x</Emphasis>/2</Subscript> (Ln = Sm-Gd) Solid Solutions

The electrical conductivity of Ln_{2 + x} Zr_{2 − x} O_{7 − x/2} (Ln = Sm-Gd) solid solutions prepared from mechanically activated Ln₂O₃ and ZrO₂ is shown to correlate with their structural properties. In the three systems, the x-T regions are determined in which electrical transport is dominated by oxygen-ion conduction. In the Sm₂O₃-ZrO₂ system, ionic conductivities from 5 × 10⁻⁴ to 6 × 10⁻³ S/cm at 740°C are found in Sm_{2 + x} Zr_{2 − x} O_{7 − x/2} with 26.6, 33.3, 35.5, 37, and 40 mol % Sm₂O₃ prepared at 1450, 1530, and 1600°C. Eu_{2 + x} Zr_{2 − x} O_{7 − x/2} and Gd_{2 + x} Zr_{2 − x} O_{7 − x/2} containing 33.3 to 37 mol % Ln₂O₃ have 740°C ionic conductivities of 10⁻³ to ∼7.5 × 10⁻³ and 10⁻³ to 7 × 10⁻³ S/cm, respectively. The activation energy of conduction in Ln_{2 + x} Zr_{2 − x} O_{7 − x/2} (Ln = Sm-Gd), E _a = 0.84–1.04 eV, increases with the atomic number of Ln and x. The highest ionic conductivity is offered by the stoichiometric Ln₂Zr₂O₇ (Ln = Sm-Gd) pyrochlores prepared at 1600°C, owing to the optimal concentration of Ln_Zr + Zr_Ln antistructure pairs (∼5–22%). The grains in the ceramic samples studied range in size from 0.5 to 2 µm.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 975–984.Original Russian Text Copyright © 2005 by Shlyakhtina, Kolbanev, Knotko, Boguslavskii, Stefanovich, Karyagina, Shcherbakova.     

Crystal structure and negative thermal expansion of solid solution Y<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Y₂W_3−x Mo _x O₁₂ (0.5 ≤ x ≤ 2.5) were successfully synthesized by the solid state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare earth tungstates and molybdates were found to crystallize in the same orthorhombic structure with space group Pnca, and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Y₂W_3−x Mo _x O₁₂ were determined as −16.2 × 10⁻⁶ K⁻¹ for x = 0.5 and −16.5 × 10⁻⁶ K⁻¹ for x = 2.5 in the identical temperature range of 200–800 °C. High-temperature XRD data and bond length analysis suggest that the difference between W–O and Mo–O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

Ca4REO(BO3)3 crystals for green and blue microchip laser generation: from crystal growth to laser and nonlinear optical properties

We have taken advantage of congruent melting behavior of the nonlinear rare-earth oxoborate Ca₄REO(BO₃)₃ family to perfect a process of collective fabrication of self-frequency doubling microchip laser based on Nd:GdCOB (Ca₄Gd_1−xNd_xO(BO₃)₃) crystals. The process goes from Czochralski boule to 1 × 3 mm² chips perfectly oriented (better than 0.1°) to the phase matching direction (θ=90°, φ=46°) in the XY principal plane, with dielectric mirrors directly deposited on both faces of the chips. 20 mW of self-frequency doubling output power at 530 nm was performed under 800 mW of diode laser as incident pump power at 812 nm. In addition, new compositions from the solid solution Ca₄Gd_1−xY_xO(BO₃)₃ (Gd_1−xY_xCOB) (x=0.13, 0.16, 0.44) have been grown by the Czochralski pulling method, in order to achieve noncritical phase matching (NCPM) second harmonic generation of ⁴F_3/2 → ⁴I_9/2 Nd³⁺ doped laser hosts. Three types of laser wavelengths have been chosen: Nd:YAP (YAlO₃) at 930 nm, Nd:YAG (Y₃Al₅O₁₂) at 946 nm, and Nd:ASL (Nd_ySr_1−x La_x−yMg_x Al_12−xO₁₉) at 900 nm. Angular acceptance measurements of these three types of compositions present very large values, compared to pure GdCOB or YCOB oriented in critical phase matching configurations.     

Combinatorial synthesis and rapid characterization of Mo1−xSnx (0x1) thin films

Thin films of Mo_1−xSn_x, continuously and linearly mapped for 0<x<1, have been prepared by d.c. magnetron sputter deposition under various growth conditions. X-ray diffraction results indicate that as x in high-pressure deposited Mo_1−xSn_x increases from 0 to approximately 0.45, the bcc lattice expands and no new phases are formed. At low deposition pressures, Mo₃Sn, a β-tungsten structured phase, is formed along with the bcc Mo–Sn solid solution for 0.1<x<0.3. The variation of the lattice parameter for this intermetallic phase also indicates that solid solutions, possibly of the form Mo_3+ySn, are being formed. These materials are of special interest as anode candidates in lithium-ion batteries.     

New ionic conductors Ln2 + xTi2 ? xO7 ? x /2 (Ln = Dy?Lu, x = 0.132)

New oxygen-ion conductors Ln_{2 + x}Ti_{2 – x}O_{7 – x/2} (Ln = Dy–Lu, x = 0.132) with a disordered pyrochlore structure are obtained. Their ionic conductivity attains 10^-3 S/cm at 740°C, owing to the presence of defects in both the cation and anion sublattices. The materials contain ~5% Ln_Ti antisite defects. Ln_2.132Ti_1.868O_6.934 ceramics are shown to be stable in the temperature range 1600–1700°C.Translated from Neorganicheskie Materialy, Vol. 40, No. 12, 2004, pp. 1501–1504.Original Russian Text Copyright © 2004 by Shlyakhtina, Mosunov, Stefanovich, Karyagina, Shcherbakova.     

Structural and electrical properties of La2−xBaxMo2O9−x/2 (x = 0-0.18)

La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) have been prepared by solid state reaction method. The lattice parameter of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) determined by XRD data refinement shows a linear dependence on the dopant Ba content x. For the specimen with a La/Ba molar ratio of 0.18-0.2, additional reflection of secondary phase exists in the XRD pattern, so the value of solubility limit for Ba in La₂Mo₂O₉ is defined in range of 0.18 < x < 0.2. As the replacement degree of La³⁺ by Ba²⁺ increases, the bulk conductivity of La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) decreases initially and then increases, a minimum value at La_1.9Ba_0.1Mo₂O_8.95 exists. Hebb-Wagner studies in argon atmosphere, which use an oxide-ion blocking electrode, show that La_2−xBa_xMo₂O_9−x/2 (x ≤ 0.18) are predominantly oxide-ion conducting in the temperature ranging from 773 to 1173 K. The average thermal expansion coefficient of La_1.84Ba_0.16Mo₂O_8.92 determined by high-temperature XRD was deduced as great as 17.5 × 10⁻⁶ K⁻¹ between 298 and 1173 K.     

Synthesis and characterization of LiCo0.3−xGaxNi0.7O2 (x = 0, 0.05) as a cathode material for lithium ion battery

The single phase of LiCo_0.3−xGa_xNi_0.7O₂ (x = 0, 0.05) was synthesized by a sol–gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance. The powders are homogeneous and have a good-layered structure. The synthesized LiCo_0.25Ga_0.05Ni_0.7O₂ exhibits better electrochemical performance with an initial discharge capacity of 180.0 mAh g⁻¹ and a capacity retention of 95.2% after 50 cycles between 2.8 and 4.4 V at 0.2C rate. The study on the structural evolution of the material during the cycling shows that Ga-doping improves the structure stability of LiCo_0.3Ni_0.7O₂ at ambient temperature and 55 °C. Meanwhile, Ga-doping not only suppresses the alternating current (AC) impedance of LiCo_0.3Ni_0.7O₂ but also promotes the Li⁺ diffusion in LiCo_0.3Ni_0.7O₂. Furthermore, thermal stability of the charged LiCo_0.25Ga_0.05Ni_0.7O₂ is improved, which may be attributed to the retard of O₂ evolution in LiCo_0.3Ni_0.7O₂ and the suppression of electrolyte oxidation during cycling by Ga-doping_.     

Microwave dielectric and elastic properties of glass-added Ba6−3xR8+2xTi18O54 (x = 2/3)

Microwave dielectric properties of Ba_6−3xSm_8+2xTi₁₈O₅₄ (x = 2/3) [BST] ceramics with the addition of 0–3 wt.% of various glasses have been studied. It has been found that the addition of 0.5 wt.% of the glasses decreases the sintering temperature by about 150 °C. In general, addition of 0.5 wt.% of Zn, Mg and Pb-based glasses deteriorate the quality factor, whereas aluminum and barium borosilicates do not decrease it considerably. The quality factor and dielectric constant decrease with increasing amount of glass. The temperature coefficient of resonant frequency shifts towards positive or negative depending on the composition of the glass. A glass–ceramic composite with a dielectric constant 64, Q × f nearly 8500 GHz and near to zero τ_f could be obtained at a sintering temperature of 1175 °C when 3–4 wt.% Al₂O₃–B₂O₃–SiO₂ glass was added to BST ceramic. The Young's modulus decreases with increasing amount of glass, irrespective of the composition of glass.