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).     

Enhanced electrochemical performance of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>F<Subscript>3</Subscript> for Na-ion batteries with nanostructure and carbon coating

Carbon-coating Na₃V₂(PO₄)₂F₃ nanoparticles (NVPF@C NP) were prepared by a hydrothermal assisted sol–gel method and applied as cathode materials for Na-ion batteries. The as-prepared nanocomposites were composed of Na₃V₂(PO₄)₂F₃ nanoparticles with a typical size of ~?100 nm and an amorphous carbon layer with the thickness of ~?5 nm. Cyclic voltammetry, rate and cycling, and electrochemical impedance spectroscopy tests were used to discuss the effect of carbon coating and nanostructure. Results display that the as-prepared NVPF@C NP demonstrates a higher rate capability and better long cycling performance compared with bare Na₃V₂(PO₄)₂F₃ bulk (72 mA h g^?1 at 10 C vs 39 mA h g^?1 at 10 and 1 C capacity retention of 95% vs 88% after 50 cycles). The remarking electrode performance was attributed to the combination of nanostructure and carbon coating, which can provide short Na-ion diffusion distance and rapid electron migration.     

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.     

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.     

Single phased Sr<Subscript>3</Subscript>La(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>:Eu<Superscript>2+</Superscript>/Mn<Superscript>2+</Superscript> phosphors: solid state synthesis,tunable luminescence and potential applications in white light LEDs

A series of Sr₃La(PO₄)₃:Eu²⁺/Mn²⁺ phosphors were synthesized by a solid state reaction. The phase and the optical properties of the synthesized phosphors were investigated. The XRD results indicate that the doped Eu²⁺ and Mn²⁺ ions do not change the phase of Sr₃La(PO₄)₃. The peak wavelengths of Eu²⁺ single doped and Eu²⁺/Mn²⁺ codoped Sr₃La(PO₄)₃ phosphors shift to longer wavelength due to the larger crystal field splitting for Eu²⁺ and Mn²⁺. The increases of crystal field splitting for Eu²⁺ and Mn²⁺ are induced by the substitution of Sr²⁺ by Eu²⁺ and Mn²⁺ in Sr₃La(PO₄)₃ host. Due to energy transfer from Eu²⁺ to Mn²⁺ in Sr₃La(PO₄)₃:Eu²⁺/Mn²⁺ phosphors, tunable luminescence was obtained by changing the concentration of Mn²⁺. And the white light was emitted by Sr₃La(PO₄)₃:3.0 mol%Eu²⁺/4.0 mol%Mn²⁺ and Sr₃La(PO₄)₃:3.0 mol%Eu²⁺/5.0 mol%Mn²⁺ phosphors.     

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.     

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.     

Li-ion storage performance and electrochemically induced phase evolution of layer-structured Li[Li<Subscript>0.2</Subscript>Mn<Subscript>0.54</Subscript>Ni<Subscript>0.13</Subscript>Co<Subscript>0.13</Subscript>]O<Subscript>2</Subscript> cathode material

Li-rich Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂ (LMNC) powders were synthesized by a gel-combustion method. The related microstructure, electrochemical performance and electrochemically induced phase evolution were characterized. The 900°C calcined powders have a hexagonal layered structure with high ordered degree and low cationic mixing level. The calcined materials as cathode electrode for Li-ion battery deliver the high electrochemical properties with an initial discharge capacity of 243.5 mA?h?g^–1 at 25 mA?g^–1 and 249.2 mA?h?g^–1 even after 50 cycles. The electrochemically induced phase evolution investigated by a transmission electron microscopy indicates that Li⁺ ions deintercalated first from the LiMO₂ (M = Mn, Co, Ni) component and then from Li₂MnO₃ component in the LMNC during the charge process, while Li⁺ ions intercalated into Li_1–xMO₂ component followed by into MnO₂ component during the discharge process.     

Magnetization reversal and tunable exchange bias behavior in Mn-substituted NiCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single phase samples of Ni(Cr_1?xMn _x )₂O₄ (x = 0–0.50) were synthesized by using sol–gel route. Investigation of structural, magnetic, exchange bias and magnetization reversal properties was carried out in the bulk samples of Ni(Cr_1?xMn _x )₂O₄. Rietveld refinement of the X-ray diffraction patterns recorded at room temperature reveals the tetragonal structure for x = 0 sample with I4₁/amd space group and cubic structure for x ≥ 0.05 samples with \( {\text{Fd}\bar{3}\text{m}} \) space group. Magnetization measurements show that all samples exhibit ferrimagnetic behavior, and the transition temperature (T_C) is found to increase from 73 K for x = 0 to 138 K for x = 0.50. Mn substitution induces magnetization reversal behavior especially for 30 at% of Mn in NiCr₂O₄ system with a magnetic compensation temperature of 45 K. This magnetization reversal is explained in terms of different site occupation of Mn ions and the different temperature dependence of the magnetic moments of different sublattices. Study of exchange bias behavior in x = 0.10 and 0.30 samples reveals that they exhibit negative and tunable positive and negative exchange bias behavior, respectively. The magnitudes of maximum exchange bias field of these samples are found to be 640 and 5306 Oe, respectively. Exchange bias in x = 0.10 sample originates from the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. The tunable exchange bias behavior in x = 0.30 sample is explained in terms of change in domination of one sublattice moment over the other as the temperature is varied.     

Synthesis and electrochemical properties of Nb-doped Li3V2(PO4)3/C cathode materials for lithium-ion batteries

Li₃V_2−xNb_x(PO₄)₃/C cathode materials were synthesized by a sol-gel method. X-ray diffraction patterns demonstrated that the appropriate addition of Nb did not destroy the lattice structure of Li₃V₂(PO₄)₃, and enlarged the unit cell volume, which could provide more space for lithium intercalation/de-intercalation. Transmission electron microscopy and energy dispersive X-ray spectroscopy analysis illustrated that Nb could not only be doped into the crystal lattice, but also form an amorphous (Nb, C, V, P and O) layer around the particles. As the cathode materials of Li-ion batteries, Li₃V_2−xNb_x(PO₄)₃/C (x ≤ 0.15) exhibited higher discharge capacity and better cycle stability than the pure one. At a discharge rate of 0.5C, the initial discharge capacity of Li₃V_1.85Nb_0.15(PO₄)₃/C was 162.4 mAh/g. The low charge-transfer resistances and large lithium ion diffusion coefficients confirmed that Li₃V_2−xNb_x(PO₄)₃/C samples possessed better electronic conductivity and lithium ion mobility. These improved electrochemical performances can be attributed to the appropriate amount of Nb doping in Li₃V₂(PO₄)₃ system by enhancing structural stability and electrical conductivity.     

Nano-domain structure of Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript> spinel

XRD-pure Li₄Mn₅O₁₂ spinels are obtained below 600 °C from oxalate and acetate precursors. The morphology consists of nanometric particles (about 25 nm) with a narrow particle size distribution. HRTEM and electron paramagnetic resonance (EPR) spectroscopy of Mn⁴⁺ are employed for local structure analysis. The HRTEM images recorded on nano-domains in Li₄Mn₅O₁₂ reveal its complex structure. HRTEM shows one-dimensional structure images, which are compatible with the (111) plane of the cubic spinel structure and the (001) plane of monoclinic Li₂MnO₃. For Li₄Mn₅O₁₂ compositions annealed between 400 and 800 °C, EPR spectroscopy shows the appearance of two types of Mn⁴⁺ ions having different metal environments: (i) Mn⁴⁺ ions surrounded by Li⁺ and Mn⁴⁺ and (ii) Mn⁴⁺ ions in Mn⁴⁺-rich environment. The composition of the Li⁺, Mn⁴⁺-shell around Mn⁴⁺ mimics the local environment of Mn⁴⁺ in monoclinic Li₂MnO₃, while the Mn⁴⁺-rich environment is related with that of the spinel phase. The structure of XRD-pure Li₄Mn₅O₁₂ comprises nano-domains with a Li₂MnO₃-like and a Li_4/3−x Mn_5/3+x O₄ composition rather than a single spinel phase with Li in tetrahedral and Li_1/3Mn_5/3 in octahedral spinel sites. The annealing of Li₄Mn₅O₁₂ at temperature higher than 600 °C leads to its decomposition into monoclinic Li₂MnO₃ and spinel Li_4/3−x Mn_5/3+x O₄.     

Crystallization from high-temperature solutions in the K<Subscript>2</Subscript>O-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

We have studied general trends of crystallization from high-temperature solutions in the K₂O-P₂O₅-V₂O₅-Bi₂O₃ system at P/V = 0.5?2.0, K/(P + V) = 0.7?1.4, and Bi₂O₃ contents from 25 to 50 wt % and identified the stability regions of BiPO₄, K₃Bi₅(PO₄)₆, K₂Bi₃O(PO₄)₃, and K₃Bi₂(PO₄)_{3 ? x} (VO₄) _x (x = 0?3) solid solutions. The synthesized compounds have been characterized by X-ray powder diffraction and IR spectroscopy, and the structure of two solid solutions has been determined by single-crystal X-ray diffraction (sp. gr. C ₂/c): K₃Bi₂(PO₄)₂(VO₄), a = 13.8857(8), b = 13.5432(5), c = 6.8679(4) Å, β = 114.031(7)°; K₃Bi₂(PO₄)_1.25(VO₄)_1.75, a = 13.907(4), b = 13.615(2), c = 6.956(2) Å, β = 113.52(4)°.     

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.”     

The magnetic properties of BiY<Subscript>2</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles doped with Cr ions

BiY₂Cr _x Fe_5?x O₁₂ (x = 0, 0.05, 0.1, 0.2, 0.3) nanocrystals were synthesized by using a sol-gel method. Samples were characterized by the powder X-ray diffraction (XRD), the thermal gravity analysis (TGA) and the differential thermal analysis (DTA), the vibrating sample magnetometer(VSM) and Mössbauer spectrums. The average sizes of the particles were determined by the Scherrer’s formula. The special Ms and Mössbauer spectra of BiY₂Cr _x Fe_5?x O₁₂ nanocrystals are researched at room temperature. It is seen that the special Mss of samples are initially increased with increasing Cr³⁺ content (x < 0.1), and decreased with increasing content of Cr³⁺ ions (x > 0.1).     

Phase conversion and spectral properties of long lasting phosphor Zn<Subscript>3</Subscript> (PO<Subscript>4</Subscript>)<Subscript>2</Subscript>:Mn<Superscript>2+</Superscript>, Ga<Superscript>3+</Superscript>

A red long lasting phosphor Zn₃(PO₄)₂:Mn²⁺,Ga³⁺ (ZPMG) was prepared by ceramic method, and phase conversion and spectral properties were investigated. Results indicated that the phase conversion from α-Zn₃(PO₄)₂, β-Zn₃(PO₄)₂ toγ-Zn₃(PO₄)₂ occurs with different manganese concentration incorporated and sinter process. The structural change induced by the phase transformation results in a remarkable difference in the spectral properties. The possible luminescence mechanism for this red LLP with different forms has been illustrated.     

Sr<Subscript>3</Subscript>GdLi(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F: Sm<Superscript>3+</Superscript> phosphor: preparation and luminescence properties evaluation

A series of Sr₃Gd_1?xLi(PO₄)₃F: xSm³⁺ (x?=?0.02, 0.04, 0.06, 0.08) phosphors were synthesized by a high-temperature solid state method. The Sm³⁺ activated Sr₃GdLi(PO₄)₃F phosphors can be efficiently excited by the wavelengths in the range from 350 to 450 nm, which matches perfectly with that of the commercial near-UV LED chips. The optimal doping concentration of Sr₃Gd_1?xLi(PO₄)₃F: xSm³⁺ phosphors was determined to be x?=?0.04, corresponding to the quantum efficiency of 2.23%, and the CIE chromaticity coordinates (x?=?0.5172, y?=?0.4641). The concentration quenching mechanism of Sm³⁺ in Sr₃GdLi(PO₄)₃F host is mainly attributed to the dipole–dipole interaction, which was confirmed by the fluorescent lifetimes. The effect of temperature on the photoluminescence property of Sr₃GdLi(PO₄)₃F: Sm³⁺ was investigated. 90% of the intensity is preserved at 150 °C. In addition, a white light emitting diode (WLED) lamp was fabricated by a 405 nm n-UV LED chip coated with Sr₃Gd_0.96Li(PO₄)₃F:0.04Sm³⁺ phosphor and commercial yellow phosphor (YAG: Ce³⁺) of a certain mass ratio. The present work indicates that the Sr₃GdLi(PO₄)₃F: Sm³⁺ orange–red-emitting phosphors tend to be potential application in n-UV WLED.     

Influence of silver addition on microstructures and transport properties of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript>:Ag<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> composites

In order to obtain high temperature coefficient of resistance (TCR) value of La_0.67Ca_0.33MnO₃:Ag _x (LCMO:Ag _x ) composites, samples with different Ag contents (x?=?0, 0.1, 0.2, 0.25, 0.3, and 0.5) were prepared by sol–gel method. X-ray diffraction analyses indicated that all samples had orthorhombic perovskite structures. As x increased, lattice parameters (a, b, c) and cell volumes underwent slight expansions. Interestingly, the addition of Ag dramatically affected TCR and magneto-resistance (MR) values. Elevated TCR value up to 53.46%·K^?1 at 277 K was observed for LCMO:Ag _x composites with added Ag at the composition of x?=?0.1. Meanwhile, MR value at 263 K reached 71% at the magnetic field of 1 T for samples with Ag composition of x?=?0.25. The increase in Mn⁴⁺/Mn³⁺ ratio and improvement in crystallization caused by added Ag was found responsible for the elevated values of TCR, MR, and T_p. These findings may have practical use in high-performance magneto-resistive manganites.     

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.     

Solid-state reactions in the system Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>

The formation mechanisms of Li _x Na_{1 ?x} Ta _y Nb_{1 ? y} O₃ perovskite solid solutions in the Li₂CO₃-Na₂CO₃-Nb₂O₅-Ta₂O₅ system have been studied by x-ray diffraction, differential thermal analysis, thermogravimetry, IR spectroscopy, and mass spectrometry at temperatures from 300 to 1100°C. The results indicate that the synthesis of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions involves a complex sequence of consecutive and parallel solid-state reactions. An optimized synthesis procedure for Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions is proposed.