Erbium zirconium phosphate Er<Subscript>0.33</Subscript>Zr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> of the NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> family. Structure contraction on heating

Erbium zirconium phosphate Er_0.33Zr₂(PO₄)₃, a member of the family of structural analogs of NaZr₂(PO₄)₃ (NZP), was prepared by the sol-gel process and studied by X-ray phase analysis, IR spectroscopy, and differential scanning calorimetry. The behavior of erbium zirconium phosphate on heating in the temperature interval from 25 to 625°C was studied by high-temperature X-ray diffraction. Expansion and contraction along different crystallographic directions and contraction of the structure as a whole were found. The overall contraction is due to higher contribution of the negative axial thermal expansion coefficients α _a and α _b to α_av and hence to the volume expansion of the phosphate. On heating to 900°C, the NZP structure is preserved.     

Phase transitions of the NASICON-type mixed phosphates LiM<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> (M = Ti,Zr) and LiInNb(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The structural phase transitions of LiTi₂(PO₄)₃, LiInNb(PO₄)₃, and LiZr₂(PO₄)₃ have been studied by X-ray diffraction, impedance spectroscopy, ⁷Li NMR spectroscopy, and calorimetry. The results indicate that, as the temperature is raised, the lithium ions in the structure of LiTi₂(PO₄)₃ and LiInNb(PO₄)₃ redistribute between the M1 and M2 sites. The thermal expansion coefficients along the crystallographic axes of LiTi₂(PO₄)₃ and LiInNb(PO₄)₃ are estimated.     

Mo-doped Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>@C composites for high stable sodium ion battery cathode

NASICON-type Na₃V₂(PO₄)₃ (NVP) with superior electrochemical performance has attracted enormous attention with the development of sodium ion batteries. The structural aggregation as well as poor conductivity of NVP hinder its application in high rate perforamance cathode with long stablity. In this paper, Na₃V_2-xMo _x (PO₄)₃@C was successfully prepared through two steps method, including sol-gel and solid state thermal reduction. The optimal doping amount of Mo was defined by experiment. When x was 0.15, the Na₃V_1.85Mo_0.15(PO₄)₃@C sample has the best cycle performance and rate performance. The discharge capacity of Na₃V_1.85Mo_0.15(PO₄)₃@C could reach 117.26 mA·h·g-1 at 0.1 C. The discharge capacity retention was found to be 94.5% after 600 cycles at 5 C.     

Liquid-phase epitaxy of NdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb-doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Epitaxial layers of NaAl₃(BO₃)₄ (NAB) and YAl₃(BO₃)₄〈Yb〉 (YAB〈Yb〉) containing up to 10 at % Yb have been grown by liquid-phase epitaxy on YAB substrates. Their growth kinetics have been studied at relative supersaturations of the high-temperature solution from 2 × 10^?2 to 16 × 10^?2. The ytterbium concentration in YAB〈Yb〉 has been shown to vary little during the epitaxial process. Near the edges of the substrate, the surface morphology of the layers is complicated by vicinals, which have a spiral form in the case of YAB〈Yb〉. On \(\{ 10\overline 1 1\} \) YAB substrates, homogeneous single-crystal NAB films have been grown.     

Fabrication of NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-type ceramic materials by spark plasma sintering

Ceramic materials based on Ca_0.5Zr₂(PO₄)₃ and NaFeNb(PO₄)₃, structural analogs of NaZr₂(PO₄)₃ (NZP), were prepared by spark plasma sintering. At sintering temperatures of 1100–1200 and 880°C and sintering times of 12 and 3 min, the relative densities reached were 99.1 and 99.9%, respectively. According to X-ray diffraction data, the sintering process caused no changes in phase composition. The ceramics had a dense, homogeneous microstructure and ranged in grain size from 0.5 to 2.5 μm.     

Electrical Conductivity and Electrochemical Characteristics of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-Based NASICON-Type Materials

NASICON-type materials with the compositions Na₃V_2–xAl_x(PO₄)₃, Na₃V_{2 - x}Fe_x(PO₄)₃, Na_{3 + x}V_2–xNi_x(PO₄)₃, and Na₃V_{2 - x}Cr_x(PO₄)₃ (x = 0, 0.03, 0.05, and 0.1) have been prepared and characterized by X-ray diffraction analysis, electron microscopy, and impedance spectroscopy. The results demonstrate that the highest electrical conductivity among the samples studied is offered by the material doped with 5% Fe: Na₃V_1.9Fe_0.1(PO₄)₃. The activation energy for low-temperature conduction in the doped materials decreases from 84 ± 2 to 54 ± 1 kJ/mol and that for high-temperature conduction is ~33 kJ/mol. The discharge capacity of Na₃V_1.9Fe_0.1(PO₄)₃/C under typical working conditions of cathodes of sodium ion batteries has been shown to exceed that of Na₃V₂(PO₄)₃/C. The capacity of the more porous material prepared by the Pechini process (Na₃V_1.9Fe_0.1(PO₄)₃/C-{II}) approaches the theoretical one at a low charge–discharge rate and retains its high level as the charge rate is raised (its discharge capacity was 117.6, 108.8, and 82.6 mAh/g at a discharge rate of 0.1C, 2C, and 8C, respectively).     

Mn-doped Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> nanocrystal with enhanced electrochemical properties based on aerosol synthesis method

Mn-doped Li₃V_2?x Mn _x (PO₄)₃ nanocrystals with enhanced electrochemical properties for lithium-ion batteries were synthesized by aerosol process successfully. The nanocrystals synthesized from aerosol-assisted spray process have an average particle size smaller than 500 nm, with some initial particle size of about 100 nm. The Mn-doped Li₃V₂(PO₄)₃ cathode materials show higher capacity and coulombic efficiency than pure Li₃V₂(PO₄)₃ materials. Especially, the Mn-doped Li₃V_1.94Mn_0.06(PO₄)₃ shows a capacity of 130 mAh/g in the voltage range of 3.0–4.4 V and a coulombic efficiency of 99.5 % at 1C. The results from XRD, SEM, HRTEM, and EIS suggested that lattice changes of Li₃V₂(PO₄)₃ due to Mn doping and the fine particles enabled by aerosol-assisted spray process can significantly reduce the charge-transfer resistance and improve the apparent Li⁺ diffusion coefficient of insertion/desertion in the electrodes, which were the critical reason of better electrochemical performance of Mn-doped Li₃V₂(PO₄)₃ cathode materials.     

Visible-light activities of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>/BiVO<Subscript>4</Subscript> composite photocatalysts

Gd₂O₃/BiVO₄ composite photocatalysts were hydrothermal synthesized and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and UV–vis diffusion reflectance spectra; all the composite photocatalysts exhibited enhanced photocatalytic activities than the pure BiVO₄ for degradation of methyl orange under visible-light irradiation. The improved activity of composites was discussed and ascribed to the electron-scavenging effect of dopants.     

Synthesis and luminescent characterization of YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript> phosphors

YAl₃(BO₃)₄:Tb³⁺ phosphors were fabricated by the sol–gel method. The phosphor showed prominent luminescence in green due to the magnetic dipole transition of ⁵D₄–⁷F₅. Structural characterization of the luminescent material was carried out with X-ray powder diffraction (XRD) analysis. Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. Photoluminescence measurements indicated that the phosphor exhibited bright green emission at about 541 nm under UV excitation. It is shown that the 11% of doping concentration of Tb³⁺ ions in YAl₃(BO₃)₄:Tb³⁺ phosphors is optimum.     

Ce and Eu activated Na<Subscript>2</Subscript>Zn<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>4</Subscript>, a new promising novel phosphor

A new efficient phosphor, Eu²⁺/Eu³⁺ and Ce³⁺ activated Na₂Zn₅(PO₄)₄ has been synthesized by solid-state reaction technique at high temperature. X-ray powder diffraction analysis confirmed the formation of Na₂Zn₅(PO₄)₄ host lattice. Scanning electron microscopy indicated that the microstructure of the phosphor consisted of irregular fine grains with a size of about 0·5–2 μm. Photoluminescence excitation spectrum measurements of Ce³⁺ activated Na₂Zn₅(PO₄)₄ show that the phosphor can be efficiently excited by UV-Vis light from 280 to 310 nm to realize emission in the visible (blue) range due to the 5d-4f transition of Ce³⁺ ions which is applicable for scintillation purpose, whereas Eu²⁺/Eu³⁺ activated Na₂Zn₅(PO₄)₄ phosphor emits blue, green and red emission spectrum shows at 487 nm, 546 nm with a dominant peak at 611 nm respectively, due to Eu²⁺/Eu³⁺ ions which is promising candidate for solid state lighting. Therefore, newly synthesised, by low cost and easy technique prepared, novel phosphors may be useful as RGB phosphor for solid state lighting application.     

Preparation and Thermal Expansion of Calcium Iron Zirconium Phosphates with the NaZr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> Structure

Ca_{0.5(1 + x)}Zr_2–xFe _x (PO₄)₃ phosphates have been synthesized by a sol–gel process. The individual compounds and solid solutions obtained crystallize in the NaZr₂(PO₄)₃ structure (trigonal symmetry, sp. gr. R\(\bar 3\)). Using high-temperature X-ray diffraction, we have determined their thermal expansion parameters in the temperature range from 25 to 800°C. With increasing x, the magnitudes of their linear thermal expansion coefficients and thermal expansion anisotropy decrease. Most of the synthesized phosphates can be rated as low-thermal-expansion compounds and can be regarded as materials capable of withstanding thermal “stress.”     

Crystal structure of KNa<Subscript>3</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>5</Subscript>O<Subscript>6</Subscript>(SO<Subscript>4</Subscript>)]

The crystal structure of a previously unknown compound KNa₃[(UO₂)₅O₆(SO₄)] [space group Pbca, a = 13.2855(15), b = 13.7258(18), c = 19.712(2) Å, V = 3594.6(7) ų] was solved by direct methods and refined to R ₁ = 0.055 for 3022 reflections with |F _hkl | ≥ 4σ |F _hkl |. In the structure there are five sym-metrically nonequivalent uranyl cations. They are linked by cationcation (CC) interactions to form a pentamer whose central cation is U(2)O ₂ ²⁺ forming two three-centered CC bonds. All the uranyl ions are coordinated in the equatorial plane by five O atoms, which leads to the formation of pentagonal bipyramids sharing common edges to form layers parallel to the (100) plane. The sulfate tetrahedron links the uranyl layers into a 3D framework. The K⁺ and Na⁺ cations are arranged in framework voids. A brief review of CC interactions in U(VI) compounds is presented.     

Synthesis and conductivity studies of Li<Subscript>1.5</Subscript>Al<Subscript>0.5</Subscript>Ge<Subscript>1.5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> solid electrolyte

This paper describes the preparation of a lithium ion conducting solid electrolyte with the composition Li_1.5Al_0.5Ge_1.5(PO₄)₃ by a new liquid-phase method with the use of the water-soluble salts Al(NO₃)₃ · 9H₂O, LiNO₃ · 3H₂O, and (NH₄)₂HPO₄ and the germano-oxalic acid H₂[Ge(C₂O₄)₃]. The synthesized materials have been characterized by X-ray diffraction, differential scanning calorimetry, thermogravimetry, and impedance spectroscopy. The results demonstrate that sintering of the synthesized amorphous powders at a temperature of 650°C leads to the formation of phase-pure Li_1.5Al_0.5Ge_1.5(PO₄)₃. The ionic conductivity of the electrolyte measured at frequencies from 10 Hz to 2 MHz using pellets with an 86% relative density was 4.2 × 10^–4 S/cm.     

Synthesis and properties of AgTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based NASICON-type phosphates doped with Nb<Superscript>5+</Superscript>, Zr<Superscript>4+</Superscript>, and Ga<Superscript>3+</Superscript>

We have synthesized materials based on a silver titanium phosphate with partial substitution of tri-, tetra-, or pentavalent cations for titanium: Ag_1±x Ti_2−x M _x (PO₄)₃ (M = Nb⁵⁺, Ga³⁺) and AgTi_2−x Zr _x (PO₄)₃. The materials have been characterized by X-ray diffraction and impedance spectroscopy and have been shown to have small thermal expansion coefficients. Their ionic conductivity has been determined. Silver ions in these materials are difficult to replace with protons.     

Effect of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> concentration in Bi-containing high-temperature solutions on the luminescence of epitaxial Gd<Subscript>3</Subscript>Ga<Subscript>5</Subscript>O<Subscript>12</Subscript> films

Single-crystal gadolinium gallium garnet films have been grown by liquid-phase epitaxy on (111) Gd₃Ga₅O₁₂ substrates from supercooled Bi₂O₃-B₂O₃ fluxed melts at different Gd₂O₃ concentrations. The luminescence spectra of the films have been measured at 10 and 300 K under unmonochromatized synchrotron X-ray excitation and selective UV synchrotron excitation. The Bi³⁺ luminescence is discussed.     

Electric-field effect on crystal growth in the Li<Subscript>3</Subscript>PO<Subscript>4</Subscript>-Li<Subscript>4</Subscript>GeO<Subscript>4</Subscript>-Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-LiF system

We have studied the electric-field effect on crystallization processes in the Li₃PO₄-Li₄GeO₄-Li₂MoO₄-LiF system. In zero field, Li_3+x P_1?x Ge _x O₄ (x = 0.31) crystals were grown on the cathode under the conditions of this study. At low applied voltages (≤ 0.5 V), we obtained Li₂MoO₄, Li₂GeO₃, and Li_1.3Mo₃O₈. In the range V = 0.5–1 V, crystals of Li_3+x P_1?x Ge _x O₄ solid solutions with x = 0.17, 0.25, 0.28, 0.29, and 0.36 were obtained. An applied electric field was shown to reduce the melting temperature of the starting mixtures and the crystallization onset temperature.     

Thermodynamic properties of NaZr<Subscript>2</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The heat capacity C _p ⁰ of crystalline NaZr₂(AsO₄)₃ has been measured in the range 7–650 K using precision adiabatic calorimetry and differential scanning calorimetry. The experimental data have been used to calculate the standard thermodynamic functions of the arsenate: C _p ⁰, enthalpy H ⁰(T) − H ⁰(0), entropy S ⁰(T), and Gibbs function G ⁰(T) − H ⁰(0) from T → 0 to 650 K. The standard entropy of its formation from elements is Δ_f S ⁰(NaZr₂(AsO₄)₃, cr, 298.15 K) = −1087 ± 1 J/(mol K).     

Tunable luminescence properties and energy transfer of single-phase Ca<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>O: Dy<Superscript>3+</Superscript>, Eu<Superscript>2+</Superscript> multi-color phosphors for warm white light

The novel Ca_4?x(PO₄)₂O: xDy³⁺ and Ca_4?x?y(PO₄)₂O: xDy³⁺, yEu²⁺ multi-color phosphors were synthesized by traditional solid-state reaction. The crystal structure, particle morphology, photoluminescence properties and energy transfer process were investigated in detail. The X-ray diffraction (XRD) results demonstrate that the products showed pure monoclinic phase of Ca₄(PO₄)₂O when x < 0.1. The scanning electron microscopy (SEM) indicated that the phosphors were grain-like morphologies with diameters of ~ 3.7–7.0 μm. Under excitation of 345 nm, Dy³⁺-doped Ca₄(PO₄)₂O phosphors showed multi-color emission bands at 410, 481 and 580 nm originated from oxygen vacancies and Dy³⁺. Interestingly, Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors exhibited blue emission band at 481 nm and broad emission band from 530 to 670 nm covering green to red regions. The energy transfer process from Dy³⁺ to Eu²⁺ was observed for the co-doped samples, and the energy transfer efficiency reached to 60% when Eu²⁺ molar concentration was 8%. In particular, warm/cool/day white light with adjustable CCT (2800–6700 K) and high CRI (R_a > 85) can be obtained by changing the Eu²⁺ co-doping contents in Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors. The optimized Ca_3.952(PO₄)₂O: 0.04Dy³⁺, 0.008Eu²⁺ phosphor can achieve the typical white light with CCT of 4735 K and CRI of 87.     

Photoluminescence and raman spectra of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> crystals

We have measured the photoluminescence and Raman spectra of (Ga₂S₃)_0.95(Sm₂O₃)_0.05 crystals and identified the mechanism of the energy transfer from the host to the rare-earth ion and the vibrational modes of the constituent atoms.