Structural properties of composite cathode material LiFePO<Subscript>4</Subscript>–Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Composite cathode material LiFePO₄–Li₃V₂(PO₄)₃ is synthesized through a chemical reduction and lithiation using FeVO₄·xH₂O as both iron and vanadium sources. The structural properties of LiFePO₄–Li₃V₂(PO₄)₃ are investigated. X-ray diffraction results show the composite material containing olivine type LiFePO₄ and monoclinic Li₃V₂(PO₄)₃ phases. High-resolution transmission electron microscopy and energy-dispersive X-ray spectrometry results indicate that mutual doping effects take place between the LiFePO₄ and Li₃V₂(PO₄)₃ particles with V³⁺ doping the LiFePO₄ while Fe²⁺ dopes the Li₃V₂(PO₄)₃. LiFePO₄–Li₃V₂(PO₄)₃ nanocomposites are formed in the carbon webs. There is no structural compatibility between monoclinic (Li₃V₂(PO₄)₃) and olivine (LiFePO₄) domains in composite material LiFePO₄–Li₃V₂(PO₄)₃.     

Magnetic and magnetoresistive properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sr<Subscript>2</Subscript>FeMoO<Subscript>6–δ</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoheterostructures

A method has been developed for fabricating nanoporous matrices based on anodic aluminum oxide for the deposition of ferromagnetic nanoparticles in them. The modes of deposition of strontium ferromolybdate thin films prepared by the ion-plasma method have been worked out, and the magnetic and magnetoresistive properties, structure, and composition of the films have been investigated. It has been revealed that the microstructure and properties of the strontium ferromolybdate films deposited by ionplasma sputtering depend on the deposition rate and the temperature of the substrate. Based on the measurement of the electrical resistivity of nanoheterostructures in a magnetic field, it has been found that the magnetoresistance reaches 14% at T = 15 K and B = 8 T, which is due to the manifestation of tunneling magnetoresistance.     

Synthesis and characterization of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>·LiMn<Subscript>0.33</Subscript>Fe<Subscript>0.67</Subscript>PO<Subscript>4</Subscript>/C cathode materials

A new polyanionic cathode material, Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C for lithium-ion batteries, was synthesized using a sol-gel method and with N,N-dimethyl formamide as a dispersion agent. The analysis of electron transmission spectroscopy and X-ray diffraction revealed that the composite contained two phases. The material has high crystallinity with a grain size of 20–50 nm. The valence states of Mn, V, and Fe in the composite were analyzed by X-ray photoelectron spectroscopy. The electrochemical kinetics in Li₃V₂(PO₄)₃ is effectively enhanced by the incorporation of LiMnPO₄ and LiFePO₄, via structure modification and reduced Li diffusion length. The Li₃V₂(PO₄)₃·LiMn_0.33Fe_0.67PO₄/C materials displayed high rate capacity and steady cycle performance with discharge capacity remained 148 mAh g^?1 after 50 cycles at the rate of 0.2C. In particular, the composite exhibited excellent reversible capacities, with the values of 157, 134, 120, 102, and 94 mAh g^?1 at charge/discharge 0.2, 0.5, 1, 2, and 5C rates, respectively.     

Spectroscopic analysis of Pr<Superscript>3+</Superscript> crystal-field transitions in YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Yttrium aluminium borate single crystals, doped with 1 and 4 mol% of Pr³⁺, were analyzed in the wave number range 500–25000 cm⁻¹ and temperature range 9–300 K by means of high-resolution Fourier transform spectroscopy. In spite of the complex spectra, exhibiting broad and split lines, the energy level scheme was obtained for several excited manifolds. The careful analysis of the spectra as a function of the temperature allowed us to identify most of the sublevels of the ground manifold. The thermally induced line shift, well described by a single-phonon coupling model, could be exploited to provide information about the energy of the phonons involved. The orientation of the dielectric ellipsoid and of the dipole moments associated to a few transitions was also determined from linear dichroism measurements. The experimental data were fitted in the framework of the crystal-field theory, but the agreement was not satisfactory, as already reported for Pr³⁺ ion in other matrices. Additional discrepancies came from the dichroic spectra analysis and the line splitting, possibly associated to hyperfine interaction. Some causes which might be responsible for the difficulties encountered in the Pr³⁺ ion theoretical modelling are discussed.     

Mössbauer and magnetic studies of the phase state of SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/La<Subscript>0.9</Subscript>Ca<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript> composites

The formation of an intermediate phase in SrFe₁₂O₁₉/La_0.9Ca_0.1MnO₃ composites was demonstrated for the first time using only Mössbauer spectroscopy. The SrFe₁₂O₁₉/La_0.9Ca_0.1MnO₃ composite was prepared by the two-stage (sol–gel and hydrothermal) synthesis with varying initial conditions. The X-ray diffraction studies showed that the composite consisted of two phases: well-formed structures of manganite La_0.9Ca_0.1MnO₃ and hexagonal ferrite SrFe₁₂O₁₉. It was found that nanocrystalline La_0.9Ca_0.1MnO₃ particles with size d ? 150 nm formed in the composites at the surface of plate-like SrFe₁₂O₁₉ crystallites. The Mössbauer studies showed that the composite contained additional (intermediate) phase La_0.9Ca_0.1Mn(Fe)O₃ that formed at the interface between SrFe12O19 and La_0.9Ca_0.1MnO₃ phases. The intermediate phase concentration increased with the molar content of La_0.9Ca_0.1MnO₃; in this case, the fraction of the surface of SrFe₁₂O₁₉ crystallites coated with La_0.9Ca_0.1MnO₃ increased, which led to the increase in the total area of the interface surface and the intermediate phase concentration.     

Large electrostrictive strain in lead-free Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–KNbO<Subscript>3</Subscript> ceramics

In the present work, (1−x)(0.935Bi_0.5Na_0.5TiO₃–0.065BaTiO₃)–xKNbO₃ (BNT–BT–KN, BNT–BT–100xKN) ceramics with x ranging from 0 to 0.1 were prepared by the conventional ceramic fabrication process. A large electrostrictive coefficient of ∼10⁻² m⁴ C⁻² is obtained with the composition x ranging from 0.02 to 0.1, which is close to the well-known electrostrictive material Pb(Mg_1/3Nb_2/3)O₃. Under an electric field of 4 kV/mm, the electrostrictive strain can reach as high as 0.08%. Besides, the electric field induced strain behavior indicates a temperature independent behavior within the temperature range of 20 to 150°C. The large electrostrictive strain is suggested to be ascribed to the formation of non-polar (NP) phase developed by the KNbO₃ substitution, and the high electrostrictive coefficient of BNT–BT–KN ceramics makes them great candidates to be applied in the new solid-state actuators.     

Electrical switching in the MoO<Subscript>3</Subscript>–WO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> and MoO<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

High field electrical switching on blown films of MoO₃(60%)–P₂O₅(40%), MoO₃(50%)–WO₃(10%)–P₂O₅(40%), and MoO₃(45%)–WO₃(15%)–P₂O₅(40%) having different thicknesses was studied and compared. Switching was observed using two terminal samples. S-type current–voltage characteristic (current-controlled negative resistance—CCNR) with memory was observed in molybdenum–phosphate glasses, but N-type characteristic (voltage-controlled negative resistance—VCNR) with threshold in tungsten–molybdenum–phosphate glasses was observed. The important observation was that with the addition of WO₃ to binary MoO₃–P₂O5 led to a change of I–V characteristic from CCNR with memory to VCNR with threshold. The measurements of density and molar volume showed linear relation between MoO₃ content and density which decreased with the increase of MoO₃ content. The samples’ thickness had no significant effect on threshold voltage. The attained results also indicated that the electrode material had no effect on switching property of devices. The switching behavior of the devices did not show any dependence on the polarity of the applied voltage. In terms of the effect of heat on the switching behavior of molybdenum–phosphate glasses, it was found that threshold voltage decreases with increasing of temperature. Finally, the switching phenomenon was explained by thermal (formation of crystalline filaments) and electronic models.     

Elastic properties of TeO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Ag<Subscript>2</Subscript>O glasses

A series of glasses [(TeO₂) _x (B₂O₃)_1−x ]_1−y [Ag₂O] _y with x = 70 and y = 10, 15, 20, 25 and 30 mol% were synthesised by rapid quenching. Longitudinal and shear ultrasonic velocity were measured at room temperature and at 5 MHz frequency. Elastic properties, Poisson's ratio, microhardness, softening temperature and Debye temperature have been calculated from the measured density and ultrasonic velocity at room temperature. The experimental results indicate that the elastic constants depend upon the composition of the glasses and the role of the Ag₂O inside the glass network is discussed. Estimated parameters based on Makishima–Mackenzie theory and bond compression model were calculated in order to analyse the experimental elastic moduli. Comparison between the experimental elastic moduli data obtained in the study and the calculated theoretically by the mentioned above models has been discussed.     

XRD,impedance, and Mössbauer spectroscopy study of the Li<Subscript>3</Subscript>Fe<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> + Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> composite for Li ion batteries

The synthesis procedure of the Li₃Fe₂(PO₄)₃?+?Fe₂O₃ composite is presented. The monoclinic (A type) and hematite phases were detected by X-ray diffraction after the synthesis of the composite. The structural α–β (at a temperature of 460 K) and β–γ (at a temperature of 523 K) phase transitions in the composite were indicated by the anomalies of the electrical conductivity, dielectric permittivity, and changes of activation energies of conductivity. Two phase transitions have been detected in the Li₃Fe₂(PO₄)₃?+?Fe₂O₃ composite by ⁵⁷Fe Mössbauer spectroscopy: the phase transition in Li₃Fe₂(PO₄)₃ from the paramagnetic to antiferromagnetic phase at temperature T _N?=?29.5 K and the Morin phase transition in Fe₂O₃ at temperature T _M?=?235 K.     

<Superscript>151</Superscript>Eu Mössbauer study of multiferroic Eu<Subscript>0.75</Subscript>Y<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

We are herewith reporting the ¹⁵¹Eu Mössbauer spectra collected on a polycrystalline powder sample of Eu_0.75Y_0.25MnO₃ from 15 K to room temperature. All the spectra consist of a single line, whose shape and related sample thickness are dependent on the temperature T. The thermal trend of the mean square displacement of Eu ion, obtained from the spectra analysis, clearly reveals a large low-temperature anharmonicity and in concomitance with the onset of the magnetic ordering consists in a linear strong decrease interrupted by two narrow wells at 29.5 K and 40 K. This behavior is interpreted in connection with the transfer of spectral weight from the 120 cm^-1 optical phonon to the electromagnonic modes. The T-trend of the central shift shows that Eu³⁺ electronic ground state in the magnetically ordered phase differs from the one in the paramagnetic state. Finally, the temperature dependence of the hyperfine field under T _N gives a contribution to interpret some controversial features regarding the phase-diagram.     

Nanostructural inhomogeneity of EuBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6 + δ</Subscript> superconductors

Samples of high-temperature superconducting oxide EuBa₂Cu₃O_{6 + δ} (Eu-123) with total cationic composition Eu: Ba: Cu = 1: 2: 3 are investigated by means of local X-ray microanalysis and high-resolution transmission electron microscopy. The cationic nonstoichiometry of Eu-123 oxide is revealed. The particles of the studied samples are inhomogeneous in structure on the nanoscale, with two types of inhomogeneities: one with typical sizes of one to several nanometers, and one with typical sizes of 10 to 20 nm, respectively.     

Sol–gel synthesis and characterization of Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite solid electrolytes

Composite solid electrolytes in the system (1???x)Li₂CO₃–xAl₂O₃, with x?=?0.0–0.5 (mole), were synthesized by a sol–gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy-dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed an amorphous feature of Li₂CO₃ and traces of α-LiAlO₂, γ-LiAlO₂ and LiAl₅O₈. The prepared composite samples possess high ionic conductivities at 130–180 °C on account of the presence of lithium aluminates as well as the formation of a high concentration of an amorphous phase of Li₂CO₃ via this sol–gel preparative technique.     

Study of the KNO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system by differential scanning calorimetry

The structural and the thermodynamic properties of potassium nitrate KNO₃ and its composites with nanosized aluminum oxide Al₂O₃ have been studied by differential scanning calorimetry. It has been found that an amorphous phase forms in composites (1–x)KNO_3–xAl₂O₃. The thermal effect corresponding to this phase has been observed at 316°C. It has been found that the phase transition heats of potassium nitrate decreased as the aluminum oxide fraction increased.     

Calculation of refractive indices for the (NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>COOH)<Subscript>2</Subscript> · HNO<Subscript>3</Subscript> crystal

The refraction R of the diglycine nitrate (DGN) crystal, (NH₂CH₂COOH)₂ · HNO₃, in the para-and ferroelectric phases has been calculated in the model of noninteracting diatomic chemical bonds of the elementary unit cell of the crystal on the basis of the longitudinal and transversal polarizabilities of these bonds. The calculated magnitudes of the principal refractive indices n _p , n _m , and n _g and the orientations of the optical indicatrix of the crystal agree satisfactorily with experimentally observed values. Introducing the coefficient of Lorenz-Lorentz interaction x into the corresponding formula permits better agreement of the calculated and experimental refractive indices of DGN crystal to be obtained. The temperature changes of these x coefficients upon the ferroelectric phase transition in the DGN crystal have been analyzed.     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Specific heat of the [NH<Subscript>2</Subscript>(CH<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> crystal in the temperature region 80–300 K

The specific heat of [NH₂(CH₃)₂]₂ZnCl₄ was measured calorimetrically in the temperature region 80–300 K. As the temperature T decreases, the C _p (T) dependence indicates a phase transition sequence, with the phase transition at T₆=151 K observed for the first time. The thermodynamic characteristics of the crystal were refined. The transformation occurring at T₂=298.3 K is shown to be an incommensurate-commensurate phase transition.     

Synthesis of cubic Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript> by modified sol–gel process

Polycrystalline cubic Li₇La₃Zr₂O₁₂ (LLZ) with garnet-related type structure has been synthesized at 700 °C by modified sol–gel processes using citric acid as organic complexing agent and butan-1-ol or propan-2-ol as surface active agent. Thermal analysis (thermogravimetric/differential thermal analysis) indicated that the gel must be annealed at around 700 °C to completely remove the organic solvent. X-ray powder diffraction, X-ray fluorescence, and scanning electron microscopic investigations revealed that Al may not be essential to form cubic-phase LLZ; however, the addition of Al₂O₃ led to enhanced sintering of LLZ.     

“Negative” gap in the spectrum of localized states of (In<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.9</Subscript>(SrO)<Subscript>0.1</Subscript>

The reflection R(?ω), transmission t(?ω), absorption α(?ω), and refraction n(?ω) spectra of polycrystalline In₂O₃–SrO samples with low optical transparency, which contain In₂O₃ and In₂SrO₄ crystallites with In₄SrO_{6 + δ} interlayers, are examined. In the region of small ?ω values, the reflection coefficient decreases as the resistance of samples saturated with oxygen increases. Spectral dependences n(?ω) and α(?ω) are calculated using the classical electrodynamics relations. The results are compared to the data based on the t(?ω) spectra. The calculated absorption spectra are interpreted within the model with an overlap of tails of the density of states in the valence band and in the conduction band. A “negative” gap E _gn in the density of states with a width from–0.12 to–0.47 eV is formed in highly disordered samples in this model. It is demonstrated that the high density of defects and the band of deep acceptor states of strontium in the major matrix In₂O₃ phase are crucial to tailing of the absorption edge and its shift toward lower energies. The direct gap E _gd = 1.3 eV corresponding to the In₂SrO₄ phase is determined. The energy band diagram and the contribution of tunneling, which reduces the threshold energy for interband optical transitions, are discussed.     

Specific physical properties of nanocrystalline (La<Subscript>0.65</Subscript>Sr<Subscript>0.35</Subscript>)<Subscript>0.8</Subscript>Mn<Subscript>1.2</Subscript>O<Subscript>3 ± Δ</Subscript> samples obtained by cold isostatic pressing

Single-phase powders of manganites (La_0.65Sr_0.35)_0.8Mn_1.2O_{3 ± Δ} with average crystallite sizes of 30, 50, and 500 nm were produced by co-precipitation. The samples studied were obtained by cold isostatic pressing of powders at a pressure of 1 GPa without subsequent sintering. It is shown that the size of particles has a significant effect on the electromagnetic properties of the manganite samples. As the crystallite size decreases, the electrical resistance and coercive force increase and the tunneling magnetoresistance of the samples and the Curie temperature decrease.