Synthesis and electrochemical behavior of nanosized LiNi1−xCaxO2 cathode materials for high voltage secondary lithium-ion cells

A new class of LiNi_1−xCa_xO₂ (x = 0.0, 0.1, 0.2, 0.3 and 0.5) layered oxide materials has been synthesized by a simple low temperature solid-state route with mixed nitrates/urea with glycerol as the starting materials. First we have taken TG/DTA for observing the phase transformations of LiNi_0.9Ca_0.1O₂. The structure of the synthesized oxides was analyzed using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) to identify the crystal structure and cation environment, respectively. The synthesized ceramic oxide battery materials were examined by using transmission electron microscope (TEM), scanning electron microscope (SEM) analysis to determine the particle size, nature and morphological structure. SEM with energy dispersive X-ray spectroscopic analysis (EDAX) analysis was carried out to explore the composition of the prepared materials. The electrochemical performance of LiNi_1−xCa_xO₂ electrodes was analyzed using cyclic voltammetry (CV) and galvanostatic charge-discharge cycling studies in the voltage range 3.0-4.5 V. Electrode made with cathode active material, acetylene black and poly(vinylidene difluoride) yield a discharge capacity of 178.1 mAh g⁻¹ (x = 0.2) with good specific capacity over several charge-discharge cycles. These results have been also supported by cyclic voltammograms.     

Annealing effect on structural and electrical properties of thermally evaporated Cd1−xMnxS nanocrystalline films

Thin films of Cd_1−xMn_xS (0 ≤ x ≤ 0.5) were deposited on glass substrates by thermal evaporation. All the films were deposited at 300 K and annealed at 573 K. The as-deposited and the annealed films were characterized for composition, structure and microstructure by using energy-dispersive analysis for X-rays, X-ray diffraction, scanning electron microscopy and atomic force microscopy. Electrical conductivity was studied in the temperature range 190-450 K. All the films exhibited wurtzite structure of the host material with the grain size varying in the range between 36 and 82 nm. Resistivity of all the films is strongly dependent on Mn content and annealing temperature and lies in the range 13-160 Ω cm.     

Lead substitutions for promoted critical current density Jc and mechanical properties of Mg1−xPbxB2 regime

Lead was used as softener dopant element to replace on magnesium sites in Mg_1−xPb_xB₂ regime (where x = 0.0, 0.05, 0.1 and 0.2 mole). Samples were prepared via high temperature solid-state reaction technique depending upon diffusion mechanism of Mg/Pb-vapour ions through boron-matrix. The maximum solubility limit of lead n was found to be ∼0.2 mole, which emphasises that substitution on MgB₂ system is stilling too limited and needs many precautions to be successful.The crystalline lattice constants were evaluated and exhibit noticeable length elongation in case of c-axis as x increases while a, b-axes were nearly constant. Furthermore, effect of Pb-doping was investigated carefully on microstructure and superconducting properties of MgB₂ system. SE-microscopic analysis indicated that lead ions diffuse regularly through surface and bulk in case of (x = 0.05 and 0.1 mole) and grain size was estimated and found in between 0.43 and 1.6 μm. Critical current densities (J_c's values) recorded an reasonable increase as Pb-content increase (from x = 0 to 0.1 mole) while recorded a slight decrease for sample with maximum lead content (x = 0.2 mole). The mechanical tensile strength of the samples was clearly improved linearly as Pb-content increase recording maximum tensile 31.7 MPa for sample with x = 0.2 mole.     

MOVPE growth of AlxIn1−xP using tertiarybutylphosphine in pure N2 ambient

We have investigated metalorganic vapor phase epitaxy (MOVPE) growth of Al_xIn_1−xP alloy using tertiarybutylphosphine (TBP) as the phosphorus source in pure N₂ ambient. The effect of the substrate temperature on the aluminum composition of Al_xIn_1−xP epilayers during the MOVPE growth has been studied. When the source flow rates were kept unchanged, the aluminum composition of the Al_xIn_1−xP epilayer increased monotonically when the substrate temperature, T_g, was raised from 580 °C to 660 °C during the growth. It became saturated when T_g reached 660 °C and above. The crystalline quality of the grown Al_xIn_1−xP epilayers has been investigated by X-ray diffraction and photoluminescence measurements. A linear relationship between the aluminum composition of the Al_xIn_1−xP epilayer and TMAl/(TMAl + TMIn) source flow ratio has been obtained when grown at the optimized growth temperature of T_g = 630 °C. It has also been observed that the aluminum incorporation coefficient of Al_xIn_1−xP epilayers decreased when the V/III source flow ratio was increased during the MOVPE growth.     

Effect of the Mn ion on electrical and magnetic properties of orthorhombic perovskite-type Ca(Mn1−xTix)O3−δ

Orthorhombic perovskite-type Ca(Mn_1−xTi_x)O_3−δ (0 ≤ x ≤ 0.7) was synthesized at 1173 K for 12 h in a flow of oxygen from a precursor gel prepared using citric acid and ethylene glycol. The Mn³⁺ ion was generated by substituting a Ti⁴⁺ ion in CaMnO₃. The average particle size was 100-300 nm and did not depend on x. The lattice constants and the (Mn, Ti)-O distance increased linearly with increasing x. The variation in global instability index (GII) indicated that the instability of the structure increases monotonically with increasing x. Ca(Mn_1−xTi_x)O_3−δ was an n-type semiconductor that had its minimum values of electrical resistivity (ρ) and activation energy (E_a) at x = 0.1. Ca(Mn_1−xTi_x)O_3−δ (x = 0 and 0.1) exhibited a weak ferromagnetic behavior. The variation in μ_eff indicated that the spin state of the Mn³⁺ ion changes from low to high at x = 0.1, then reverts to low in the range of 0.2 ≤ x ≤ 0.7. The variations in ρ and E_a are explained by the number of electrons according to the change in the spin state of the Mn³⁺ ion.     

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.     

Synthesis and characterization of Ni1−xZnxFe2O4 spinel ferrites from tailored layered double hydroxide precursors

In this paper, a series of pure Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrites have been synthesized successfully using a novel route through calcination of tailored hydrotalcite-like layered double hydroxide molecular precursors of the type [(Ni + Zn)_{1 − x − y}Fe_y²⁺Fe_x³⁺(OH)₂]^x+(SO₄²⁻)_x/2·mH₂O at 900 °C for 2 h, in which the molar ratio of (Ni²⁺ + Zn²⁺)/(Fe²⁺ + Fe³⁺) was adjusted to the same value as that in single spinel ferrite itself. The physico-chemical characteristics of the LDHs and their resulting calcined products were investigated by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS) and Mössbauer spectroscopy. The results indicate that calcination of the as-synthesized LDH precursor affords a pure single Ni_1 − xZn_xFe₂O₄ (0 ≤ x ≤ 1) spinel ferrite phase. Moreover, formation of pure ferrites starting from LDHs precursors requires a much lower temperature and shorter time, leading to a lower chance of side-reactions occurring, because all metal cations on the brucite-like layers of LDHs can be uniformly distributed at an atomic level.     

The effect of strain on nonlinear temperature dependence of resistivity in SrMoO3 and SrMoO3−xNx films

Highly oriented SrMoO₃ thin films have been fabricated by pulsed laser deposition of SrMoO₄ in hydrogen. The films are found to grow along the (1 0 0) direction on LaAlO₃ (1 0 0) and SrTiO₃ (1 0 0) substrates. The method has been extended for the fabrication of oxynitride thin films, using ammonia as the reducing medium. The resistivity measurements show nonlinear temperature dependent (Tⁿ) behaviour in the temperature interval of 10-300 K. The conduction mechanism is largely affected by the strain due to the substrate lattice. A combination of T and T² dependence of resistivity on temperature is observed for films having lesser lattice mismatch with the substrate. The X-ray photoelectron spectroscopic studies confirm the formation of SrMoO₃ and SrMoO_3−xN_x films.     

Re-examination of the structural properties of solid solutions SrxCa1−xCO3

We have re-examined the evolution of orthorhombic cell parameters as a function of the substitution parameter x in solid solutions Sr_xCa_1−xCO₃ in order to clarify contradictory results found in the literature. Calcium carbonate has been synthesized in the presence of Sr²⁺ ions (Sr/Ca molar ratio ranging from 10⁻² to 1), using experimental conditions that previously allowed us to obtain monophasic aragonite. The precipitates obtained have been analysed using powder X-ray diffractometry (XRD) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The powder XRD data confirm the occurrence of purely monophasic strontian-aragonites. Moreover, the cell parameters as well as the substitution parameter x have been refined for 0 < x < 0.5 against powder XRD data through Rietveld refinement. On the other hand, x was deduced from chemical analysis by ICP-AES. The agreement between both techniques is very satisfactory. The evolution of the cell parameters as a function of x is found to be linear within the studied range, this feature being confirmed for the overall domain (0 ≤ x ≤ 1) if one takes into account the cell parameters of aragonite CaCO₃ and strontionite SrCO₃. This result, that is consistent with the existence of continuous solid solutions obeying the Vegard's law in the Sr_xCa_1−xCO₃ system, contradicts previously published assertions.     

Structural and transport properties of stoichiometric Mn-doped magnetite: Fe3−xMnxO4

The polycrystalline samples of Fe_3−xMn_xO₄ (0.10 ≤ x ≤ 0.50) were prepared by a solid-state route reaction method. X-ray diffraction pattern shows that Mn²⁺ doped magnetites are in single phase and possess cubic inverse spinel structure. The resistivity measurements (10 < T < 300 K) for x = 0.0 and 0.01 confirms the first order phase transition at the Verwey transition T_V = 123 K and 117 K, respectively. No first order phase transition was evidenced for Fe_3−xMn_xO₄ (0.10 ≤ x ≤ 0.50). Small polaron model has been used to fit the semiconducting resistivity behavior and the activation energy ?_a, for samples x = 0.10 and 0.50 is about 72.41 meV and 77.39 meV, respectively. The Raman spectra of Fe_3−xMn_xO₄ at room temperature reveal five phonons modes for Fe_3−xMn_xO₄ (0.01 ≤ x ≤ 0.50) as expected for the magnetite (Fe₃O₄). Increased Mn²⁺ doping at Fe site leads to a gradual changes in phonon modes. The Raman active mode for Fe_3−xMn_xO₄ (x = 0.50) at ≅641.5 cm⁻¹ is shifted as compared to parent Fe₃O₄ at ≅669.7 cm⁻¹, inferring that Mn⁺² ions are located mostly on the octahedral sites. The laser power is fixed to 5 mW causes the bands to broaden and to undergo a small shift to lower wave numbers as well as increase in the full width half maxima for A_1g phonon mode with the enhancement of Mn²⁺ doping. Mössbauer spectroscopy probes the site preference of the substitutions and their effect on the hyperfine magnetic fields confirms that Mn⁺² ions are located mostly on the octahedral sites of the Fe_3−xMn_xO₄ spinel structure.     

Different microstructure and dielectric properties of Ba1−xCaxTiO3 ceramics and pulsed-laser-ablated films

A comparative study of the microstructure and dielectric properties between Ba_1−xCa_xTiO₃ (BCT) ceramics and films were performed in the whole Ca concentration range of x = 0-1. The ceramics were prepared by conventional solid-state reaction technique and the films by the method of pulsed-laser deposition. X-ray diffraction (XRD) study of the BCT ceramics exhibited a pure tetragonal phase for x = 0-0.25, a tetragonal-orthorhombic diphase for x = 0.25-0.85 and a pure orthorhombic phase for x = 0.90-1.00. And the dielectric phase transition temperature from tetragonal to cubic was marginally affected by the Ca doping into BaTiO₃. However, BCT films deposited on Pt/Si/SiO₂/Si substrates showed a different microstructure and dielectric properties. Tetragonal-orthorhombic diphase was not found in the BCT films for x = 0.25-0.85, and a large decrease of the Curie point and diffuse phase transition were observed in the BCT films. Based on the compositional analysis, such phenomena were ascribed to the occupancy of some Ca²⁺ to the Ti⁴⁺ sites in the BCT films.     

The effect of Cu content on the structure of Ni1−xCuxFe2O4 spinels

A series of Ni_1−xCu_xFe₂O₄ (0 ≤ x ≤ 0.5) spinels were synthesized employing sol-gel combustion method at 400 °C. The decomposition process was monitored by thermal analysis, and the synthesized nanocrystallites were characterized by X-ray diffraction, transmission electron microscopy, infra-red and X-ray photoelectron spectroscopy. The decomposition process and ferritization occur simultaneously over the temperature range from 280 °C to 350 °C. TEM indicates the increase of lattice parameter and particle size with the increase of copper content in accordance with the XRD analysis. Cu²⁺ can enter the cubic spinel phase and occupy preferentially the B-sites within x = 0.3, and redundant copper forms CuO phase separately. A broadening of the O 1s region increases with the increment of copper content compared to pure NiFe₂O₄, showing different surface oxygen species from the spinel and CuO. Cu²⁺ substitution favors the occupancy of A-sites by Fe³⁺.     

Electrical properties of MgAl2-2xZrxMxO4 (M = Co, Ni and x = 0.00-0.20) synthesized by coprecipitation technique using urea

This paper presents the results of a study concerning the structural and electrical properties of MgAl_2-2xZr_xM_xO₄ (x = 0.00-0.20 and M = Co²⁺ and Ni²⁺) prepared by a coprecipitation technique using urea as a precipitating agent. The X-ray diffraction data for the pure and its doped samples are consistent with the single-phase spinel and their crystallite sizes are in the range 7-20 ± 4 nm. The DC resistivity increases from 3.09 × 10⁹ Ω cm to 6.73 × 10⁹ and 8.06 × 10⁹ Ω cm whereas dielectric constant decreases from 5.80 to 5.11 and 4.95 on doping with Zr-Co and Zr-Ni, respectively. The electrical resistivity variations with increase in the dopant contents indicate two types of conduction mechanisms in operation. Several parameters such as, hopping energy (W), metal-semiconductor transition temperature (T_MS) and Debye temperature (θ_D) have also been determined. The increase in DC resistivity and decrease in dielectric constant suggest that the synthesized materials can be considered for application as an insulating and structural material in fusion reactors.     

Tantalum influence on physical properties of (K0.5Na0.5)(Nb1−xTax)O3 ceramics

Lead-free (K_0.5Na_0.5)(Nb_1−xTa_x)O₃ ceramics with x = 0.00-0.30 were prepared by the solid-state reaction technique. The effects of Ta on microstructure, crystallographic structure, phase transition and piezoelectric properties have been investigated. It has been shown that the substitution of Ta decreases Curie temperature T_C and orthorhombic-tetragonal phase transition temperature T_O-T, while increasing the rhombohedral-orthorhombic phase transition temperature T_R-O. In addition, piezoelectric activity is enhanced with the increase of Ta content. The ceramics with x = 0.30 have the high value of piezoelectric coefficient d₃₃ = 205 pC/N. Moreover, k_p shows little temperature dependence between −75° C and 75 °C, and d₃₃ exhibits very good thermal stability over the range from −196 °C to 75 °C in the aging test.     

Structure, dielectric and ferroelectric anisotropy of Sr2−xCaxBi4Ti5O18 ceramics

Sr_2−xCa_xBi₄Ti₅O₁₈(x = 0, 0.05) powders synthesized by solid state route were uniaxially pressed and sintered at 1225 °C for 2 h. The obtained dense ceramics exhibited crystallographic anisotropy with a dominant c axis parallel to the uniaxial pressing direction which was quantified in terms of the Lotgering factor. Microstructure anisotropy of both compositions (x = 0, 0.05) consisted of plate like grains exhibiting their larger surfaces mostly perpendicular to the uniaxial pressing direction. Dielectric and ferroelectric properties of Sr_2−xCa_xBi₄Ti₅O₁₈ ceramics were measured under an electric field (E) applied parallel and perpendicularly to uniaxial pressing direction. The obtained dielectric ?_R(T) and polarization (P-E) curves depended strongly on E direction thus denoting a significant effect from microstructure and crystallographic texture. Sr_2−xCa_xBi₄Ti₅O₁₈ properties were also significantly affected by Ca content (x): Curie temperature increased from 280 °C (x = 0) to 310 °C (x = 0.05) while ?_R and remnant polarization decreased for x = 0.05. The present results are discussed within the framework of the processing and crystal structure-properties relationships of Aurivillius oxides ceramics.     

Electron paramagnetic resonance (EPR) of antiferromagnetic nanoparticles of La1−xSrxCrO3 (0.000 ≤ x ≤ 0.020) synthesized by combustion reaction

Nanocrystalline particles of La_1−xSr_xCrO₃ (0.000 ≤ x ≤ 0.020) compounds were synthesized in order to investigate the antiferromagnetic (AFM) to paramagnetic (PM) phase transition temperature, g-factor, line width and intensity by electron paramagnetic resonance (EPR). All samples were synthesized by combustion reaction method using strontium nitrate, lanthanum nitrate, chromium nitrate and urea as fuel without subsequent heat treatment. X-ray diffraction patterns of all systems showed broad peaks consistent with orthorhombic structure of LaCrO₃. The absence of extra reflections in the diffraction patterns of as-prepared materials ensures the phase purity. The average crystallite sizes determined from the prominent (1 1 2) peak of the diffraction using Scherrer's equation was independent of the addition of Sr²⁺ ions; being ca. 31–29 nm for x = 0.000 and 0.020, respectively. The EPR line width and intensity were found to be dependent on Sr²⁺ addition and temperature. However, the AFM–PM transition temperature was found to be independent of strontium concentration, being ca. 296 K. In the PM phase, g-factor was nearly temperature independent with increasing of x. The EPR results indicated that the addition of Sr²⁺ ions may induce creation of Cr³⁺–Cr⁴⁺ clusters.     

Rietveld refinement of the semiconducting system Bi2−xFexTe3 from X-ray powder diffraction

The semiconducting system Bi_2−xFe_xTe₃ (x = 0.0, 0.02, 0.04 and 0.08) was synthesized at 1000 °C for 30 h. The scanning electron microscope (SEM) image reveals the tendency of the Bi_2−xFe_xTe₃ system to form a sheet structure with more pronounced alignment and to enhance the formation of some microstructure tubes. The structure of the system under study was refined on the basis of X-ray powder diffraction data using the Rietveld method. The analysis revealed the complete miscibility of Fe in the Bi₂Te₃ matrix and hence the formation of single phase. The system crystallizes in the space group R-3m [1 6 6]. The lattice parameters and the unit cell size slightly change by the incorporation of Fe. The refinement of instrumental and structural parameters led to reliable values for the R_B, R_F and Chi².     

Crystal structure and electrical properties of new tungsten bronzes: BxWO3 (0.01 ≤ x ≤ 0.08)

Boron tungsten bronzes B_xWO₃ (0.01 ≤ x ≤ 0.08) were synthesized by hybrid microwave method from mixtures of WO₃ and amorphous boron powder. With the increase of boron content, the crystal structure of B_xWO₃ transforms from orthorhombic (x = 0.01) to tetragonal α (x = 0.048) and then to tetragonal β (0.07 ≤ x ≤ 0.08). The average size of crystallites is in the range of 1-10 μm. All samples show semiconducting behaviour in their temperature dependence of resistivity. The conduction behaviour above 80 K for samples with x = 0.01 and 0.08 can be explained using the variable-range hopping and thermally activated mechanism, respectively. Comparative experiments showed that boron bronze phases cannot be obtained by the microwave heating of pure WO₃ powder or a mixture of B₂O₃ and WO₃ under the same conditions.     

Structural, spectroscopic and dielectric investigations on Ba8Zn(Nb6−xSbx)O24 microwave ceramics

Ba₈Zn(Nb_6−xSb_x)O₂₄ (x = 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8 and 2.4) ceramics were prepared through the conventional solid-state route. The materials were calcined at 1250 °C and sintered in the range 1400-1425 °C. The structure of the system was analyzed by X-ray diffraction, Fourier transform infrared and Raman spectroscopic methods. The theoretical and experimental densities were calculated. The microstructure of the sintered pellets was analyzed using scanning electron microscopy. The low frequency dielectric properties were studied in the frequency range 50 Hz-2 MHz. The dielectric constant (?_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q_u) are measured in the microwave frequency region using cavity resonator method. The τ_f values of the samples reduced considerably with the increase in Sb concentration. The materials have intense emission lines in the visible region. The compositions have good microwave dielectric properties and photoluminescence and hence are suitable for dielectric resonator and ceramic laser applications.     

Order-disorder phase transitions and high-temperature oxide ion conductivity of Er2+xTi2−xO7−δ (x = 0, 0.096)

The Er_2+xTi_2−xO_7−δ (x = 0.096; 35.5 mol% Er₂O₃) solid solution and the stoichiometric pyrochlore-structured compound Er₂Ti₂O₇ (x = 0; 33.3 mol% Er₂O₃) are characterized by X-ray diffraction (phase analysis and Rietveld method), thermal analysis and optical spectroscopy. Both oxides were synthesized by thermal sintering of co-precipitated powders. The synthesis study was performed in the temperature range 650-1690 °C. The amorphous phase exists below 700 °C. The crystallization of the ordered pyrochlore phase (P) in the range 800-1000 °C is accompanied by oxygen release. The ordered pyrochlore phase (P) exists in the range 1000−1200 °C. Heat-treatment at T ≥ 1600 °C leads to the formation of an oxide ion-conducting phase with a distorted pyrochlore structure (P2) and an ionic conductivity of about 10⁻³ S/cm at 740 °C. Complex impedance spectra are used to separately assess the bulk and grain-boundary conductivity of the samples. At 700 °C and oxygen pressures above 10⁻¹⁰ Pa, the Er_2+xTi_2−xO_7−δ (x = 0, 0.096) samples are purely ionic conductors.