scholarly journals Structural and Spectroscopic Effects of Li+ Substitution for Na+ in LixNa1-xCaGd0.5Ho0.05Yb0.45(MoO4)3 Scheelite-Type Upconversion Phosphors

Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7357
Author(s):  
Chang-Sung Lim ◽  
Aleksandr Aleksandrovsky ◽  
Maxim Molokeev ◽  
Aleksandr Oreshonkov ◽  
Victor Atuchin

A set of new triple molybdates, LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45, was successfully manufactured by the microwave-accompanied sol–gel-based process (MAS). Yellow molybdate phosphors LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45 with variation of the LixNa1-x (x = 0, 0.05, 0.1, 0.2, 0.3) ratio under constant doping amounts of Ho3+ = 0.05 and Yb3+ = 0.45 were obtained, and the effect of Li+ on their spectroscopic features was investigated. The crystal structures of LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45 (x = 0, 0.05, 0.1, 0.2, 0.3) at room temperature were determined in space group I41/a by Rietveld analysis. Pure NaCaGd0.5Ho0.05Yb0.45(MoO4)3 has a scheelite-type structure with cell parameters a = 5.2077 (2) and c = 11.3657 (5) Å, V = 308.24 (3) Å3, Z = 4. In Li-doped samples, big cation sites are occupied by a mixture of (Li,Na,Gd,Ho,Yb) ions, and this provides a linear cell volume decrease with increasing Li doping level. The evaluated upconversion (UC) behavior and Raman spectroscopic results of the phosphors are discussed in detail. Under excitation at 980 nm, the phosphors provide yellow color emission based on the 5S2/5F4 → 5I8 green emission and the 5F5 → 5I8 red emission. The incorporated Li+ ions gave rise to local symmetry distortion (LSD) around the cations in the substituted crystalline structure by the Ho3+ and Yb3+ ions, and they further affected the UC transition probabilities in triple molybdates LixNa1-xCaGd0.5(MoO4)3:Ho3+0.05/Yb3+0.45. The complex UC intensity dependence on the Li content is explained by the specificity of unit cell distortion in a disordered large ion system within the scheelite crystal structure. The Raman spectra of LixNa1-xCaGd0.5(MoO4)3 doped with Ho3+ and Yb3+ ions were totally superimposed with the luminescence signal of Ho3+ ions in the range of Mo–O stretching vibrations, and increasing the Li+ content resulted in a change in the Ho3+ multiplet intensity. The individual chromaticity points (ICP) for the LiNaCaGd(MoO4)3:Ho3+,Yb3+ phosphors correspond to the equal-energy point in the standard CIE (Commission Internationale de L’Eclairage) coordinates.

Crystals ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 1000
Author(s):  
Chang Sung Lim ◽  
Aleksandr Aleksandrovsky ◽  
Victor Atuchin ◽  
Maxim Molokeev ◽  
Aleksandr Oreshonkov

AgGd(MoO4)2:Ho3+/Yb3+ double molybdates with five concentrations of Ho3+ and Yb3+ were synthesized by the microwave employed sol–gel based process (MES), and the crystal structure variation, concentration effects, and spectroscopic characteristics were investigated. The crystal structures of AgGd1−x−yHoxYby(MoO4)2 (x = 0, 0.05; y = 0, 0.35, 0.4, 0.45, 0.5)at room temperature were determined in space group I41/a by Rietveld analysis. Pure AgGd(MoO4)2 has a scheelite-type structure with mixed occupations of (Ag,Gd) sites and cell parameters a = 5.24782 (11) and c = 11.5107 (3) Å, V = 317.002 (17) Å3, Z = 4. In doped samples, the sites are occupied by a mixture of (Ag,Gd,Ho,Yb) ions, which provides a linear cell volume decrease with the doping level increase. Under the excitation at 980 nm, AGM:0.05Ho,yYb phosphors exhibited a yellowish green emission composed of red and green emission bands according to the strong transitions 5F5 → 5I8 and 5S2/5F4 → 5I8 of Ho3+ ions. The evaluated photoluminescence and Raman spectroscopic results were discussed in detail. The upconversion intensity behavior dependent on the Yb/Ho ratio is explained in terms of the optimal number of Yb3+ ions at the characteristic energy transfer distance around the Ho3+ ion.


2002 ◽  
Vol 718 ◽  
Author(s):  
Hongwu Xu ◽  
Alexandra Navrotsky ◽  
M. Lou Balmer ◽  
Yali Su

AbstractA suite of perovskite phases with the compositions NaTixNb1-xO3-0.5x, 0 ≤ x ≤ 0.2, has been synthesized for the first time using the sol-gel method. Rietveld analysis of powder XRD data reveals that with increasing Ti content, the orthorhombic perovskite structure becomes more cubic-like, as evidenced by the smaller differences among its three cell parameters. Enthalpies of formation of the synthesized phases from the constituent oxides and from the elements have been determined by drop solution calorimetry into molten 3Na2O·4MoO3 solvent at 974 K. As Ti4+ substitutes for Nb5+, the formation enthalpies become less exothermic in a nearly linear manner. This behavior suggests that the Ti→Nb substitution destabilizes the perovskite structure, presumably because of the concomitant occurrence of O2- vacancies, which compensate the charge imbalance between Ti4+ and Nb5+ in the structure.


Author(s):  
Atef Y. Shenouda ◽  
M. M. S. Sanad

Li2NixFe1−xSiO4 (x = 0, 0.2, 0.4, 0.6, 0.8, and 1) samples were prepared by sol–gel process. The crystal structure of prepared samples of Li2NixFe1−xSiO4 was characterized by XRD. The different crystallographic parameters such as crystallite size and lattice cell parameters have been calculated. Scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR) investigations were carried out explaining the morphology and function groups of the synthesized samples. Furthermore, electrochemical impedance spectra (EIS) measurements are applied. The obtained results indicated that the highest conductivity is achieved for Li2Ni0.4Fe0.6SiO4 electrode compound. It was observed that Li/Li2Ni0.4Fe0.6SiO4 battery has initial discharge capacity of 164 mAh g−1 at 0.1 C rate. The cycle life performance of all Li2NixFe1−xSiO4 batteries was ranged between 100 and 156 mAh g−1 with coulombic efficiency range between 70.9% and 93.9%.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
A-Young Kim ◽  
Florian Strauss ◽  
Timo Bartsch ◽  
Jun Hao Teo ◽  
Jürgen Janek ◽  
...  

AbstractWhile still premature as an energy storage technology, bulk solid-state batteries are attracting much attention in the academic and industrial communities lately. In particular, layered lithium metal oxides and lithium thiophosphates hold promise as cathode materials and superionic solid electrolytes, respectively. However, interfacial side reactions between the individual components during battery operation usually result in accelerated performance degradation. Hence, effective surface coatings are required to mitigate or ideally prevent detrimental reactions from occurring and having an impact on the cyclability. In the present work, we examine how surface carbonates incorporated into the sol–gel-derived LiNbO3 protective coating on NCM622 [Li1+x(Ni0.6Co0.2Mn0.2)1–xO2] cathode material affect the efficiency and rate capability of pellet-stack solid-state battery cells with β-Li3PS4 or argyrodite Li6PS5Cl solid electrolyte and a Li4Ti5O12 anode. Our research data indicate that a hybrid coating may in fact be beneficial to the kinetics and the cycling performance strongly depends on the solid electrolyte used.


2017 ◽  
Vol 32 (S2) ◽  
pp. S38-S42
Author(s):  
Matthew R. Rowles ◽  
Cheng-Cheng Wang ◽  
Kongfa Chen ◽  
Na Li ◽  
Shuai He ◽  
...  

The crystal structure and thermal expansion of the perovskite samarium cobalt oxide (SmCoO3) have been determined over the temperature range 295–1245 K by Rietveld analysis of X-ray powder diffraction data. Polycrystalline samples were prepared by a sol–gel synthesis route followed by high-temperature calcination in air. SmCoO3 is orthorhombic (Pnma) at all temperatures and is isostructural with GdFeO3. The structure was refined as a distortion mode of a parent $ Pm{\bar 3}m $ structure. The thermal expansion was found to be non-linear and anisotropic, with maximum average linear thermal expansion coefficients of 34.0(3) × 10−6, 24.05(17) × 10−6, and 24.10(18) × 10−6 K−1 along the a-, b-, and c-axes, respectively, between 814 and 875 K.


2012 ◽  
Vol 18 (3) ◽  
pp. 436-444 ◽  
Author(s):  
Esam T. Ahmed Mohamed ◽  
Albert E. Kamanyi ◽  
Mieczysław Pluta ◽  
Wolfgang Grill

AbstractVariations of the mechanical properties of red blood cells that occur during their life span have long been an intriguing task for investigations. The research presented is based on noninvasive monitoring of red blood cells of different ages performed by scanning acoustic microscopy with magnitude and phase contrast. The characteristic signature of fixed cells from groups of three different ages fractionated according to mass density is obtained from the acoustic microscope images, with the data represented in polar graphs. The analysis of these data enables the determination of averaged values for the velocities of ultrasound propagating in the cells from the different groups ranging from (1,681 ± 16) m s−1in the youngest to (1,986 ± 20) m s−1in the oldest group. The determined bulk modulus varies with age from (3.04 ± 0.05) GPa to (4.34 ± 0.08) GPa. An approach to determine for an age-mixed population of red blood cells, collected from a healthy person, the age of the individual cells and the age dependence of the cell parameters including density, velocity, and attenuation of longitudinal polarized ultrasonic waves traveling in the cells is demonstrated.


2019 ◽  
Vol 97 (4) ◽  
pp. 347-354 ◽  
Author(s):  
Rizwin Khanam ◽  
Dambarudhar Mohanta

We report on the effect of chromium doping on the band gap lowering of nano-titania (TiO2) and subsequent implications as regards coloration characteristics mediated via photochromism and thermochromism processes. As can be found in the X-ray diffractograms, the sol-gel derived, Cr3+-doped nano-TiO2 systems have exhibited an anatase phase with the evidence of peak shifting towards a lower diffraction angle. The average crystallite size decreases, whereas lattice unit cell parameters and, consequently, cell volume, tend to increase with the inclusion of Cr3+ into the titania host. To be specific, 1% Cr-doped titania system showed nearly 5.8% cell expansion as compared to its un-doped counterpart. As revealed from the optical absorption spectroscopy, a narrowing of band gap is observed for the Cr doped nano-titania system: 3.18 eV for the un-doped system, and 2.61 and 2.41 eV for 0.3% and 1% Cr doping cases, respectively, considering direct band-to-band transitions. Moreover, doping led noticeable lowering of the exponent (n value), from its normal value, which suggests inclusion of adequate non-parabolicity feature to the energy band scheme. The photochromic feature, for a given incident radiation, demonstrates a lowered transmission response with increasing Cr content. A reversible thermochromism response has also been demonstrated for doped nano-titania systems subjected to heating with temperature varying between 0–55 °C. The Cr3+ doped nano-titania and similar systems would find scope in smart windows, display components, photocatalysis, etc., when a select coloration is desired.


2004 ◽  
Vol 03 (06) ◽  
pp. 749-755 ◽  
Author(s):  
YING LI ◽  
SUO HON LIM ◽  
TIM WHITE

The properties influencing the photocatalytic activity of TiO 2 particles have been suggested to include the surface area, crystallinity, crystallite size and crystal structure. Therefore, manipulation of the microstructure of titania, especially of nanocrystalline powders, is very important in the preparative process. In this study, nanocrystalline TiO 2 powders with controlled particle size and phase composition were synthesized at low temperature (<80°C) by a modified sol–gel method. The effects of gelation temperature were systematically investigated. It was found that this parameter played a critical role in determining the crystallinity of single phase anatase. With increasing gelation temperature, the crystallinity of anatase improved initially and then decreased if the temperature was raised to 80°C. These nanomaterials were characterized comprehensively by powder X-ray diffraction (including Rietveld analysis), high-resolution transmission electron microscopy, DSC/TGA thermal analysis and UV–Vis spectrometry.


2006 ◽  
Vol 21 (1) ◽  
pp. 45-51 ◽  
Author(s):  
Abderrahim Aatiq ◽  
My Rachid Tigha ◽  
Rabia Hassine ◽  
Ismael Saadoune

Crystallographic structures of two new orthophosphates Ca0.50SbFe(PO4)3 and CaSb0.50Fe1.50(PO4)3 obtained by conventional solid state reaction techniques at 900 °C, were determined at room temperature from X-ray powder diffraction using Rietveld analysis. The two compounds belong to the Nasicon structural family. The space group is R3 for Ca0.50SbFe(PO4)3 and R3c for CaSb0.50Fe1.50(PO4)3. Hexagonal cell parameters for Ca0.50SbFe(PO4)3 and CaSb0.50Fe1.50(PO4)3 are: a=8.257(1) Å, c=22.276(2) Å, and a=8.514(1) Å, c=21.871(2) Å, respectively. Ca2+ and vacancies in {[Ca0.50]3a[◻0.50]3b}M1SbFe(PO4)3 are ordered within the two positions, 3a and 3b, of M1 sites. Structure refinements show also a quasi-ordered distribution of Sb5+ and Fe3+ ions within the Nasicon framework. Thus, in {[Ca0.50]3a[◻0.50]3b}M1SbFe(PO4)3, each Ca(3a)O6 octahedron shares two faces with two Fe3+O6 octahedra and each vacancy (◻(3b)O6) site is located between two Sb5+O6 octahedra. In [Ca]M1Sb0.50Fe1.50(PO4)3 compound (R3c space group), all M1 sites are occupied by Ca2+ and the Sb5+ and Fe3+ ions are randomly distributed within the Nasicon framework.


2019 ◽  
Vol 7 (1) ◽  
pp. 016402
Author(s):  
Suliman Eltayeb Elhadi ◽  
Yadong Lu ◽  
Chao Liu

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