Effect of calcination conditions on lithium conductivity in Li<Subscript>1.3</Subscript>Ti<Subscript>1.7</Subscript>Al<Subscript>0.3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> prepared by sol-gel route

In order to study the influence of powder calcination temperature on lithium ion conductivity, synthesized Li_1.3Ti_1.7Al_0.3(PO₄)₃ (LATP) was calcined at temperatures between 750 and 900 °C. The shape and size of the particles were characterized employing scanning electron microscopy (SEM), and specific surface area of the obtained powder was measured. The crystallinity grade of different heat-treated powders was calculated from XRD spectra. Posteriorly, all powders were sintered at 1100 °C employing field-assisted sintering (SPS), and the electrical properties were correlated to the calcination conditions. The highest ionic conductivity was observed for samples made out of powders calcined at 900 °C.     

Thermal properties and ionic conductivity of Li<Subscript>1,3</Subscript>Ti<Subscript>1,7</Subscript>Al<Subscript>0,3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> solid electrolytes sintered by field-assisted sintering

Li_1,3Ti_0,7Al_0,3(PO₄)₃ (LATP) powder was obtained by a conventional melt-quenching method and consolidated by field-assisted sintering technology (FAST) at different temperatures. Using this technique, the samples could be sintered to relative densities in the range of 93 to 99 % depending on the sintering conditions. Ionic and thermal conductivity were measured and the results are discussed under consideration of XRD and SEM analyses. Thermal conductivity values of 2 W/mK and ionic conductivities of 4?×?10^?4 Scm^?1 at room temperature were obtained using relatively large particles and a sintering temperature of 1000 °C at an applied uniaxial pressure of 50 MPa.     

Electrochemical properties of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C cathode materials synthesized via ethylene glycol-assisted solvothermal method

The Li₃V₂(PO₄)₃/C (LVP/C) cathode materials for lithium-ion batteries were synthesized via ethylene glycol-assisted solvothermal method. The phase composition, phase transition temperature, morphology, and fined microstructure were studied using X-ray diffraction (XRD), differential thermal analyzer (DTA), scanning electron microscope (SEM), and transmission electron microscope (TEM), respectively. The electrochemical properties, impedance, and electrical conductivity of LVP/C cathode materials were tested by channel battery analyzer, the electrochemical workstation, and the Hall test system, respectively. The results shown that the appropriate amount of water added to ethylene glycol solvent contributes to the synthesis of pure phase LVP. The LVP₁₀/C cathode material can exhibit discharge capacities of 128, 126, 126, 123, 124, and 114 mAh g^?1 at 0.1, 0.5, 2, 5, 10, and 20 C in the voltage range of 3.0–4.3 V, respectively. Meanwhile, it shows also a stable cycling performance with the capacity retention of 89.6% after 180 cycles at 20 C.     

Grain size effects on dynamics of Li-ions in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> glass-ceramic nanocomposites

Li₃V₂(PO₄)₃ glass-ceramic nanocomposites, based on 37.5Li₂O-25V₂O₅-37.5P₂O₅ mol% glass, were successfully prepared via heat treatment (HT) process. The structure and morphology were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). XRD patterns exhibit the formation of Li₃V₂(PO₄)₃ NASICON type with monoclinic structure. The grain sizes were found to be in the range 32–56 nm. The effect of grain size on the dynamics of Li⁺ ions in these glass-ceramic nanocomposites has been studied in the frequency range of 20 Hz–1 MHz and in the temperature range of 333–373 K and analyzed by using both the conductivity and modulus formalisms. The frequency exponent obtained from the power law decreases with the increase of temperature, suggesting a weaker correlation among the Li⁺ ions. Scaling of the conductivity spectra has also been performed in order to obtain insight into the relaxation mechanisms. The imaginary modulus spectra are broader than the Debye peak-width, but are asymmetric and distorted toward the high frequency region of the maxima. The electric modulus data have been fitted to the non-exponential Kohlrausch–Williams–Watts (KWW) function and the value of the stretched exponent β is fairly low, suggesting a higher ionic conductivity in the glass and its glass-ceramic nanocomposites. The advantages of these glass-ceramic nanocomposites as cathode materials in Li-ion batteries are shortened diffusion paths for Li⁺ ions/electrons and higher surface area of contact between cathode and electrolyte.     

Investigations on the synthesis and electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C by different methods

Li₃V₂(PO₄)₃/C samples were synthesized by two different synthesis methods. Their influence on electrochemical performances of Li₃V₂(PO₄)₃/C as cathode materials for lithium-ion batteries was investigated. The structure and morphology of Li₃V₂(PO₄)₃/C samples were characterized by X-ray diffraction and scanning electron microscopy. Electrochemical performance was characterized by charge/discharge, cyclic voltammetry, and alternating current (AC) impedance measurements. Li₃V₂(PO₄)₃/C with smaller grain size showed better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of the Li₃V₂(PO₄)₃/C were attributed to the decreasing grain size and enhanced electrical conductivity produced via low temperature route. AC impedance measurements also showed that the Li₃V₂(PO₄)₃/C synthesized by low temperature route significantly decreased the charge-transfer resistance and shortened the migration distance of lithium ion.     

Enhanced electrochemical performance of lithium ion battery cathode Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C

Li-ion battery cathode material lithium-vanadium-phosphate Li₃V₂(PO₄)₃ was synthesized by a carbon-thermal reduction method, using stearic acid, LiH₂PO₄, and V₂O₅ as raw materials. And stearic acid acted as reductant, carbon source, and surface active agent. The effect of its content on the crystal structure and electrochemical performance of Li₃V₂(PO₄)₃/C were characterized by XRD and electrochemical performance testing, respectively. The results showed that the content of carbon source has no significant effect on the crystal structure of lithium vanadium phosphate. Lihtium vanadium phosphate obtained with 12.3% stearic acid demonstrated the best electrochemical properties with a typical discharge capacity of 119.4 mAh/g at 0.1 C and capacity retention behavior of 98.5% after 50 cycles. And it has high reversible discharge capacity of 83 mAh/g at 5 C with the voltage window of 3 to 4.3 V.     

Synthesis and electrochemical performance of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C by organic solvent replacement drying method

A series of Li₃V₂(PO₄)₃/C composite cathodes have been prepared by the organic solvent replacement drying method. Five kinds of organic solvent including ethyl alcohol, butyl alcohol, 2-methoxyethanol, 1,2-propylene glycol, and ethylene glycol were used in the drying process to replace the water respectively. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge tests were employed to analyze the crystal structure, morphology, and electrochemical properties of the as-prepared materials. The results show that the organic solvent has a great influence on the secondary particle size of the as-synthesized materials. Special emphasis is placed on the sample prepared with 1,2-propylene glycol, which has the smallest average particle size and uniform distribution, thus leading to the best high rate performance and long-term cycling stability. The electrode exhibits average specific discharge capacities of 127.6, 128.3, 127.7, 126.7, 125.5, 124.4, 121.9, and 117.0 mAh g^?1 at 0.1, 0.2, 0.5, 1, 3, 5, 10, and 20C, respectively. More encouragingly, this sample delivers an outstanding cycle life with capacity retention of up to 94.68% even after 1000 cycles at 20C. Moreover, EIS results demonstrate that this sample has the minimum resistance and the largest apparent lithium ion diffusion coefficient (1.569 × 10^?7 cm² s^?1) which can facilitate to the Li⁺ diffusion during the charge/discharge process. Our results indicate that this preparation strategy can be facile and versatile for the synthesis of other high-rate and high-capacity intercalation materials.     

Characteristics of the Li<Superscript>+</Superscript>-Ion Conductivity of Li<Subscript>3</Subscript>R<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> Crystals (R = Fe,Sc) in the Superionic State

The characteristics of Li+-ion conductivity σdc of structural γ modifications of Li₃R₂(PO₄)₃ compounds (R = Fe, Sc) existing in the superionic state have been investigated by impedance spectroscopy. The type of structural framework [R₂P₃O₁₂]_∞^3- affects the σdc value and the σdc activation enthalpy in these compounds. The ion transport activation enthalpy in γ-Li₃R₂(PO₄)₃ (ΔH_σ = 0.31 ± 0.03 eV) is lower than in γ-Li₃Fe₂(PO₄)₃ (ΔH_σ = 0.36 ± 0.03 eV). The conductivity of γ-Li₃Fe₂(PO₄)₃ (σ_dc = 0.02 S/cm at 573 K) is twice as high as that of γ-Li₃R₂(PO₄)₃. A decrease in temperature causes a structural transformation of Li₃R₂(PO₄)₃ from the superionic γ modification (space group Pcan) through the intermediate metastable β modification (space group P2₁/n) into the “dielectric” α modification (space group P2₁/n). Upon cooling, σdc for both phosphates decreases by a factor of about 100 at the superionic TSIC transition. In Li₃Fe₂(PO₄)₃ σdc gradually decreases in the temperature range T_SIC = 430–540 K, whereas in Li₃R₂(PO₄)₃ σdc undergoes a jump at T_SIC = 540 ± 25 K. Possible crystallochemical factors responsible for the difference in the σdc and ΔH_σ values and the thermodynamics and kinetics of the superionic transition for Li₃R₂(PO₄)₃ are discussed.     

Magnetic properties of DyFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The magnetic properties of an easy-axis trigonal DyFe₃(BO₃)₄ antiferromagnetic crystal have been theoretically studied. On this basis, recent experimental data [1] on the field and temperature dependences of magnetization and the temperature dependence of the initial magnetic susceptibility for three crystallographic directions in this antiferromagnet have been interpreted. The characteristics of the trigonal crystal field for the rare earth ion and the parameters of the Fe-Fe and Fe-Dy exchange interactions are determined. Limitations imposed by features of the magnetic characteristics (anisotropic magnetization in the three crystallographic directions, Schottky-type anomalies in the magnetic susceptibility, etc.) on the possible splitting of the ground-state multiplet in the crystal field and the splitting of the lowest doublet due to the f-d interaction for Dy³⁺ ions are established.     

Synthesis,thermal and electrical behavior of the superprotonic conductor phase in Rb<Subscript>3</Subscript>(HSeO<Subscript>4</Subscript>)<Subscript>2.5</Subscript>(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>0.5</Subscript> compound

The Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound was prepared and its thermal behavior and electric properties were investigated. The thermogravimetry (TGA) analysis and the differential scanning calorimetric (DSC) show the presence of a structural phase transition of the title compounds at 374 K which is confirmed by the variation of fp and σ_dc as a function of temperature. The complex impedance of the Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound has been investigated in the temperature range of 295–453 K and in the frequency range 209 Hz–1 MHz. The impedance plots show semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance Rp and constant phase elements CPE₁ in series with fractal capacity CPE₂. The frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. The conductivity dc follows the Arrhenius relation. The near value of activation energies obtained from the analysis of modulus, conductivity data, and circuit equivalent confirm that the transport is through the ion hopping mechanism, dominated by the motion of the H⁺ proton in the structure of the investigated materials.     

Luminescence in Dy<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> Activated K<Subscript>3</Subscript>Al<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The Dy³⁺ and Eu³⁺ activated K₃Al₂ (PO₄)₃ phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K₃Al₂ (PO₄)₃ was confirmed. In the photoluminescence emission spectra, the K₃Al₂(PO₄)₃:Dy³⁺ phosphor emits two distinctive colors: blue and yellow whereas K₃Al₂(PO₄)₃:Eu³⁺ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).     

Comparative Study of the Magnetoelectric Effect in HoAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and HoGa<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Single Crystals

The comparative study of the magnetoelectric properties and magnetostriction of HoGa₃(BO₃)₄ and HoAl₃(BO₃)₄ single crystals has been carried out. The investigated compounds exhibit qualitatively similar magnetodielectric and inverse magnetoelectric ME _E effects with the close absolute values, which is indicative of the weak effect of a nonmagnetic metal ion. On the contrary, the magnetostriction of the galloborate has been found to be threefold higher than that of the alumoborate. In addition, the difference between the qualitative behaviors of magnetostriction has been established: the magnetic-field dependence of magnetostriction for the alumoborate has the maximum near 70 kOe at T = 4.2 K, while the galloborate magnetostriction has no maximum and does not saturate in a field of 140 kOe.     

Efficient blue emission of ytterbium-doped Sr<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F under quasi-three-level intracavity pumping

We report an Yb:Sr₅(PO₄)₃F (Yb:S-FAP) laser emitting at 985 nm intracavity pumped by a 912 nm diode-pumped Nd:GdVO₄ laser. A 808 nm diode laser is used to pump the Nd:GdVO₄ crystal emitting at 912 nm, and the Yb:S-FAP laser emitting at 985 nm intracavity pumped at 912 nm. With incident pump power of 17.5 W, intracavity second harmonic generation has been demonstrated with a power of 131 mW at 492.5 nm by using a LBO nonlinear crystal.     

Antisite defects and valence state of vanadium in Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Electron paramagnetic resonance (EPR) studies have been performed with the aim of determining the valence state and local crystal structure of the nearest environment of vanadium ions in the initial, charged, and discharged samples of the cathode material Na_xV₂(PO₄)₃ (1 ≤ x ≤ 3). It has been found that the charged sample (x = 1) is characterized by an intense signal corresponding to V⁴⁺ ions located in a highly distorted octahedral crystal field. An EPR signal with the g-factor close to the g-factor of the V⁴⁺ ion has also been observed in the initial sample (x = 3), where the intensity of the resonance signal is one order of magnitude lower than that in the charged sample. It has been revealed that the resonance signal under consideration is associated with the formation of antisite defects when a part of vanadium ions are located in sites of sodium ions. It has also been found that the intensity of this signal increases after a complete charge–discharge cycle (x = 3).     

Dipole ordering and ionic conductivity in NASICON-Type Na<Subscript>3</Subscript>Cr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> structures

The aspects of structure, dipole ordering, and ionic conductivity of the Na₃Cr₂(PO₄)₃ crystal with the four polymorphic phases (α, α', β, and γ) have been investigated. The features of the α-Na₃Cr₂(PO₄)₃ crystal structure and its dipole ordering and relaxation polarization in the low-temperature α and α' phases have been refined. The occurrence of Na₃Cr₂(PO₄)₃ dipole ordering in the α and α' phases and high ionic conductivity in the β and γ phases is attributed to the structural changes in the rhombohedral [Me₂(PO₄)₃]^–3_3∞ crystal frame upon phase transformations α → α', α' → β, and β → γ. A model for explaining the dipole ordering and ionic conductivity phenomena in Na₃Cr₂(PO₄)₃ is proposed.     

Magnetic and thermal properties of single-crystal NdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

The neodymium ferroborate NdFe₃(BO₃)₄ undergoes an antiferromagnetic transition at T _N = 30 K, which manifests itself as a λ-type anomaly in the temperature dependence of the specific heat C and as inflection points in the temperature dependences of the magnetic susceptibility χ measured at various directions of an applied magnetic field with respect to the crystallographic axes of the sample. Magnetic ordering occurs only in the subsystem of Fe³⁺ ions, whereas the subsystem of Nd³⁺ ions remains polarized by the magnetic field of the iron subsystem. A change in the population of the levels of the ground Kramers doublet of neodymium ions manifests itself as Schottky-type anomalies in the C(T) and χ(T) dependences at low temperatures. At low temperatures, the magnetic properties of single-crystal NdFe₃(BO₃)₄ are substantially anisotropic, which is determined by the anisotropic contribution of the rare-earth subsystem to the magnetization. The experimental data obtained are used to propose a model for the magnetic structure of NdFe₃(BO₃)₄.     

Determination of the lattice parameters near the first-order phase transition in the Pb<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> ferroelastic

A new method for determining the lattice parameters near the first-order phase transition is proposed. The method is based on the model of a thin phase boundary and a linear dependence between the lattice parameters within a phase.     

Lithium diffusion in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based electrodes: a joint analysis of electrochemical impedance,cyclic voltammetry,pulse chronoamperometry,and chronopotentiometry data

In order to establish the mechanism and to determine the parameters of lithium transport in electrodes based on lithium-vanadium phosphate (Li₃V₂(PO₄)₃), the kinetic model was designed and experimentally tested for joint analysis of electrochemical impedance (EIS), cyclic voltammetry (CV), pulse chronoamperometry (PITT), and chronopotentiometry (GITT) data. It comprises the stages of sequential lithium-ion transfer in the surface layer and the bulk of electrode material’s particles, including accumulation of lithium in the bulk. Transfer processes at both sites are of diffusion nature and differ significantly, both by temporal (characteristic time, τ) and kinetic (diffusion coefficient, D) constants. PITT data analysis provided the following D values for the predominantly lithiated and delithiated forms of the intercalation material: 10^?9 and 3 × 10^?10 cm² s^?1, respectively, for transfer in the bulk and 10^?12 cm² s^?1 for transfer in the thin surface layer of material’s particles. D values extracted from GITT data are in consistency with those obtained from PITT: 3.5–5.8 × 10^?10 and 0.9–5 × 10^?10 cm² s^?1 (for the current and currentless mode, respectively). The D values obtained from EIS data were 5.5 × 10^?10 cm² s^?1 for lithiated (at a potential of 3.5 V) and 2.3 × 10^?9 cm² s^?1 for delithiated (at a potential 4.1 V) forms. CV evaluation gave close results: 3 × 10^?11 cm² s^?1 for anodic and 3.4 × 10^?11 cm² s^?1 for cathodic processes, respectively. The use of complex experimental measurement procedure for combined application of the EIS, PITT, and GITT methods allowed to obtain thermodynamic E,c dependence of Li₃V₂(PO₄)₃ electrode, which is not affected by polarization and heterogeneity of lithium concentration in the intercalate.     

Magnetic properties of an easy-plane trigonal NdFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> antiferromagnet

The field and temperature dependences of magnetization and the temperature dependences of the initial magnetic susceptibility have been theoretically studied for three crystallographic directions in a trigonal NdFe₃(BO₃)₄ antiferromagnetic crystal. The calculations were performed using a molecular field approximation and a crystal field model for the rare-earth subsystem. The obtained theoretical expressions are applied to the interpretation of recent experimental data [1–4] on the magnetic properties of NdFe₃(BO₃)₄. The results of calculations show a good agreement with experiment. The proposed theory adequately describes (i) anomalies of the Schottky type in the temperature dependence of the magnetic susceptibility, (ii) nonlinear curves of magnetization in the basal plane in a magnetic field up to 1 T (showing evidence of the first-order phase transitions) and their evolution with the temperature, and (iii) the field and temperature dependences of magnetization in a magnetic field up to 9 T.     

Spectral properties of a Nd<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>Ba<Subscript>2</Subscript>Gd<Subscript>3</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>8</Subscript> crystal

The spectral properties of a promising laser material, ternary molybdate Li₃Ba₂Gd₃(MoO₄)₈:Nd³⁺, are studied (i.e., its optical absorption spectra, luminescence spectra, kinetic of luminescence decay, and temperature dependence of luminescence). Luminescence of the crystalline matrix is detected, and the temperature dependence of its intensity and reabsorption by neodymium are investigated.