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.     

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.     

Dielectric response of SrTiO<Subscript>3</Subscript>–SrMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> solid solutions in the terahertz–infrared range

The reflection and transmission spectra of ceramic samples of SrTiO₃–SrMg_1/3Nb_2/3O₃ solid solutions have been measured in the frequency range of 5–5000 cm^–1 and in the temperature range of 5–370 K. Based on these spectra, the spectra of the real ε'(ν) and imaginary ε''(ν) parts of the complex permittivity ε*(ν) have been simulated by the method of dispersion analysis. It has been found that the temperature evolution of the dielectric constant is entirely determined by the behavior of the soft mode.     

Current-induced voltage oscillations in superconducting Y<Subscript>1</Subscript>Ba<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript>

We investigated influence of bidirectional square wave current with long periods and dc current on the evolution of the voltage-time (V - t) curves in superconducting polycrystalline bulk Y₁Ba₂Cu₃O_7-δ (YBCO) material at the temperatures near the critical temperature. In a well-defined range of amplitudes and periods of driving current, and temperatures, novel type of non-linear dynamic responses was observed by means of the V-t curves. It was seen that such a non-linear response to bidirectional square wave current sometimes reflects itself as regular sinusoidal-like voltage oscillations. The sinusoidal-like and non-sinusoidal oscillations were discussed mainly in terms of the dynamic competition between pinning and depinning and significant relaxation effects which appear in this competing process. The density fluctuations associated with the current induced self-magnetic flux (SMF) lines and semi-elastic coupling of SMF lines with the pinning centers were also considered as possible physical mechanisms in the interpretation of the experimental results.     

Intermediate phases in [111]- and [001]-oriented PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>–29PbTiO<Subscript>3</Subscript> single crystals

Phase transformations in [111]- and [001]-oriented PbMg_1/3Nb_2/3O₃–29PbTiO₃ single crystals have been studied using dielectric and optical measurements before and after applying an electric field. It is shown that the subsequence of phase transitions rhombohedral (R)—tetragonal (T)—cubic (C) phases is observed in nonpolarized samples of both orientations as temperature increases. In the [111]-oriented crystal, an additional intermediate monoclinic phase (it is possible, M _a ) is induced after preliminary polarization at room temperature and the R–M _a –T–C phase transitions are observed on heating. In the [001]-oriented crystal, after its polarization, the monoclinic phase forms instead of the rhombohedral phase even at room temperature and the M _a –T–C transitions occur on heating. The results are discussed from the point of view of the existence polar nanoregions with different local symmetries in a glasslike matrix.     

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.     

Current dependent reorganization in superconducting Y<Subscript>1</Subscript>Ba<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript>

We present strong non-linear dynamic responses developing due to magnitude and type of driving current in bulk polycrystalline superconducting Y₁Ba₂Cu₃O_7-δ sample at zero magnetic field. Several novel types of dynamic changes induced by the transport current were observed via the time evolution of the voltage (V - t curves). The physical observations appearing in V - t curves were interpreted mainly with the reorganization of driving current in a multiply connected network of weak-link structure. It was found that such a dynamic process could cause an enhancement or suppression in superconducting order parameter due to the magnitude of the driving current and coupling strength of weak link structure together with the chemical and anisotropic states of the sample. It was shown that the general behavior of decays evolving in V - t curves is consistent with an exponential relation which is analogous to the glassy state relaxation.     

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.     

Surface of underdoped YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-</Subscript><Subscript>δ</Subscript> as revealed by STM/STS

We performed scanning tunneling microscopy and spectroscopy on untwinned crystals of underdoped YBa₂Cu₃O_{7- δ} at δ = 0.4. A comprehensive statistical analysis of our topographic data indicates a doping dependent cleaving behavior of this material. We find in particular that at δ = 0.4 the material primarily cleaves in multiples of one unit cell along the c-axis with a high corrugation of the topmost layer. Our data suggest that the low temperature cleaving mainly results in a disruption of the CuO chain layers involving a redistribution of the layer atoms onto the two cleaving planes. In a few instances, fractional step heights (in terms of the c-axis lattice constant) are observed as well. Scanning tunneling spectroscopy reveals that such fractional steps connect surfaces which differ significantly in their tunneling conductance.     

Internal friction and magnetoelectric response in two-layer composites Tb<Subscript>0.12</Subscript>Dy<Subscript>0.2</Subscript>Fe<Subscript>0.68</Subscript>–PbZr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>O<Subscript>3</Subscript>

The inverse magnetoelectric effect and internal friction in two-layer composites based on ferromagnetic Tb_0.12Dy_0.2Fe_0.68 and piezoelectric PbZr_0.53Ti_0.47O₃ are studied in an ac electrical field in the frequency range of 52–213 kHz at temperatures of 293 to 400 K. A correlation is found between the internal friction and the efficiency of the inverse magnetoelectric transformation at resonant frequencies.     

Phase formation in the BaCO<Subscript>3</Subscript>–PbO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Features of the formation of lead-ferroniobate compounds in the xBaCO₃–(1 – x)PbO–Fe₂O₃–Nb₂O₅ system by solid-phase synthesis are investigated. For perovskite-type lead-ferroniobate solid solution, a single-phase concentration region is revealed at 1233 K. The crystalline structures of the synthesized compounds are refined using Rietveld analysis and the Pm3?m and R3m space groups. Ceramic samples of lead ferroniobate are studied by scanning electron microscopy.     

Optical activity of γ<Subscript>1</Subscript>-(Ga<Subscript>x</Subscript>In<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>2</Subscript>Se<Subscript>3</Subscript> crystals

The optical activity of uniaxial γ₁-(Ga_xIn_1?x )₂Se₃ crystals (x=0.1, 0.2, 0.3, 0.4) is studied at T=295 and 77 K in the spectral range 0.5–0.8 πm. It is found that the cationic substitution In → Ga leads to a nonlinear increase in the specific rotation of the plane of polarization ρ and the component g ₃₃ of the gyration tensor. It is shown that the gyrotropy of the crystals studied is determined by high-energy transitions whose energy exceeds the energy of the edge transitions and that the gyrotropy observed has a molecular origin.     

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.     

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.     

Synthesis of high performance Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C cathode material by ultrasonic-assisted sol–gel method

A novel ultrasonic-assisted sol–gel method is proposed to prepare Li₃V₂(PO₄)₃/C cathode material. X-ray diffraction analyses show that both Li₃V₂(PO₄)₃/C(A) synthesized by the ultrasonic-assisted sol–gel method and Li₃V₂(PO₄)₃/C(B) synthesized by a traditional sol–gel method have monoclinic structure. Scanning electron microscopy images indicate that the Li₃V₂(PO₄)₃/C(A) composite has a more uniform morphology than that of the Li₃V₂(PO₄)₃/C(B) composite. In the voltage range of 3.0–4.3 V (vs. Li/Li⁺), the initial specific discharge capacities of the Li₃V₂(PO₄)₃/C(A) and Li₃V₂(PO₄)₃/C(B) samples are 129.8 and 125.9 mAh g⁻¹ at 1C rate (1C = 133 mA g⁻¹), respectively. Furthermore, at 2-C charge/10-C discharge rate, the specific discharge capacity of the Li₃V₂(PO₄)₃/C(A) composite retains 113.2 mAh g⁻¹ after 50 cycles, but the Li₃V₂(PO₄)₃/C(B) composite only presents a capacity of 94.8 mAh g⁻¹.     

A PEG-assisted rheological phase reaction synthesis of 5LiFePO<Subscript>4</Subscript>⋅Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C as cathode material for lithium ion cells

5LiFePO₄⋅Li₃V₂(PO₄)₃/C composite cathode material is synthesized by a polyethylene glycol (PEG)-assisted rheological phase method. As a surfactant and dispersing agent, PEG can effectively inhabit the aggregation of colloidal particles during the formation of the gel. Meanwhile, PEG will coat on the particles to play the role of carbon source during the sintering. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy, and electrochemical methods. XRD results indicate that the 5LiFePO₄⋅Li₃V₂(PO₄)₃/C composites are well crystallized and contain olivine-type LiFePO₄ and monoclinic Li₃V₂(PO₄)₃ phases. The composite synthesized at 650 °C exhibits the initial discharge capacities of 134.8 and 129.9 mAh g⁻¹ and the capacity retentions of 96.2 and 97.1 % after 50 cycles at 1C and 2C rates, respectively.     

Kinetics of nucleation of thermodynamically ordered ferroelectric phases in PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>–<Emphasis Type="Italic">x</Emphasis>PbTiO<Subscript>3</Subscript> crystals with different compositions

The kinetics of electric field-induced nucleation of ordered ferroelectric phases from a mixed glassy relaxor state has been studied in a number of single-crystal (1–x)PbMg_1/3Nb_2/3O₃–xPbTiO₃ (PMN–xPT) solid solutions (x = 29, 33, 35%) lying in a morphotropic phase region. It is shown that the formation of these phases and fast establishment of a macroscopic polarization are preceded by some delay time, depending on the electric field strength and temperature. It is found that the monoclinic phase is thermodynamically stable at room temperature in all the compounds in the time (~3000 s) and electric field (~1 kV/cm) ranges under study, whereas the monoclinic phase of the compound with x = 35% transforms, at temperatures near the temperature of the morphotropic phase transition after insignificant time interval of ~100 s, to another stable ferroelectric tetragonal phase.     

Photoinduced phenomena in amorphous As<Subscript>4</Subscript>S<Subscript>3</Subscript>Se<Subscript>3</Subscript>–Sn films

We investigate the kinetics of photodarkening and recording of holographic diffraction gratings in amorphous As₄S₃Se₃ thin-film structures doped with tin (Sn) in concentrations of 0–10 at %. It is established that an increase in the Sn concentration leads to a decrease in the photodarkening rate and degree. The photodarkening kinetics is approximated by a stretched exponential function. It is found that an increase in the Sn concentration leads to a decrease in the transmission (photodarkening) variation in the investigated As₄S₃Se₃–Sn films. It is determined that, in the recording of holographic diffraction gratings at a Sn concentration of 3–8 at %, the As₄S₃Se₃–Sn films exhibit the maximum sensitivity and diffraction efficiency of the recorded gratings. It is shown that the dependence of diffraction efficiency on the As₄S₃Se₃ film thickness has the maximum at a film thickness of 4 µm.