Evaluation of NaFeTiO<Subscript>4</Subscript> as an electrode for energy storage application

We report a polycrystalline NaFeTiO₄ prepared via conventional solid-state reaction route. X-ray diffraction (XRD) results and Rietveld refinement confirmed single-phase NaFeTiO₄ having an orthorhombic unit cell with lattice parameters a = 9.17051 Å, b = 2.96310 Å, and c = 10.73676 Å and Pnma space group (No. 62). Energy dispersive spectrum (EDS) yielded sample stoichiometry that agrees well with its molecular formula. The surface morphology indicated a cylindrical rod-like microstructure comprising well-defined grains having variable dimension, i.e., diameter ~?250 to 350 nm and length ~?1 to 5 μm. Vibrational spectroscopy (FTIR/Raman) results indicated presence of FeO₆ and TiO₆ octahedra in good agreement with crystallographic study. Brunner-Emmet-Teller (BET) surface area measurement yielded a specific surface area as high as ~?4.28 m² g^?1. Electrical impedance spectrum indicated presence of grains separated by well-defined grain boundaries in agreement with microstructural analysis. Electrical conductivity of the material was estimated to be ~?6.05 × 10^?6 S cm^?1. The structural model obtained using XRD and vibrational spectrum results suggest layered tunnel/cage structure of cage dimension ~?4.65 Å, along [010] direction in the xz plane, which is larger than the size of Na⁺ ion (0.98 Å). So, easier Na⁺ migration feasibility exists in NaFeTiO₄ crystal lattice making it a good candidate for electrode applications.     

Synthesis, crystal structure, and spectroscopic study of K0.92(2) Zn0.08(2) H1.92(2) (PO4) (Zn-KDP)

The structure of K0.92₍₂₎ Zn_0.08(2) H_1.92(2) (PO₄) was determined using single-crystal X-ray diffraction. The crystal structure of the Zn-KDP belonged to the tetragonal space group $ \mathrm{I}\overline{4}2\mathrm{d} $ , with cell parameters of a?=?b?=?7.4487(5)?Å and c?=?6.9703(5)?Å, 386.73(5) Å3, Z?=?4, and R?=?0.023. Zn²⁺ ions were used as substitutes for K⁺ ions with hydrogen vacancy. The Zn-KDP single crystals were submitted to further Raman, infrared, and ¹H NMR studies to investigate chemical group functionalisation, possible bonding between the organic and inorganic materials, and partial substitution of K⁺ by Zn²⁺. The latter partial substitution was confirmed by the deviation of IR frequencies for O–H stretching, the variation of IR and Raman frequencies for stretching and bending vibrations ν(PO₄) of H₂PO₄, and the appearance of additional Raman (147, 386 and 481 cm^?1) vibrational bands. Electrical conductivity measurements were performed on polycrystalline pellets of Zn-KDP and pure KDP at room temperatures (RT) of up to 473K. In both cases, a conductivity jump close to 453K was observed, and a stronger increase of conductivity was measured.     

A new one-dimensional hybrid material lattice: AC conductivity and structural characterization of [C<Subscript>7</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>][CdCl<Subscript>4</Subscript>]

The present paper reports the synthesis, crystal structure, ¹³C and ¹¹¹Cd cross-polarization magic-angle spinning nuclear magnetic resonance(CP-MAS-NMR) analysis and ac conductivity for a new organic–inorganic hybrid salt, [C₇H₁₂N₂][CdCl₄]. The compound crystallizes in the triclinic system, space group P\( \overline 1 \), with unit cell dimensions: a?=?7.1050(3) Å, b?=?8.9579(3) Å, c?=?9.4482(3) Å, α?=?81.415(1)°, β?=?89.710(2)°, γ?=?85.765(1)°, V?=?592.97(4) Å³, and Z?=?2. The asymmetric unit is composed of one-2,4-diammonium toluene cation and one [CdCl₄]^2? anion. The Cd atom is in a slightly distorted octahedra coordination environment. Its structure can be described by infinite chains of CdCl₆ octahedron linked to organic cations by a strong charge-assisted N–H???Cl interactions in order to build organic–inorganic layers staked along \( \left[ {0\overline 1 1} \right] \) direction. The solid state ¹³C CP-MAS-NMR spectra has shown seven isotropic resonances, confirming the existence of seven non-equivalent carbon atoms, which is consistent with crystal structure determined by X-ray diffraction. As for ¹¹¹Cd MAS-NMR, it has shown one cadmium site with isotropic chemical shift observed at 167.2 ppm. The complex impedance of the compound has been investigated in the temperature range of 403–460 K and in the frequency range of 200 Hz–5 MHz. The impedance plots have shown 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 R _p and constant phase elements.     

Synthesis,crystal structure,thermal analysis,and electrical properties of bis tetrapropylammonium hexachloro-dizincate compound

The present paper accounts for the synthesis, crystal structure, differential scanning calorimetry, vibrational study, and electrical properties of the [N(C₃H₇)₄]₂Zn₂Cl₆ compound. The latter is crystallized at room temperature in the triclinic system ( $ P\overline{1} $ space group) with the following unit cell parameters: a?=?13.736(2)Å, b?=?17.044(3)Å, c?=?17.334(2)Å, α?=?68.30(2)°, β?=?75.14(2)°, and γ?=?84.93(3). The atomic arrangement can be described by alternating organic and inorganic layers parallel to the (001) plan, made up of [N(C₃H₇)₄]⁺ groups and [Zn₂Cl₆]^2? dimers, respectively. In crystal structure, the inorganic layer, built up by Zn₂Cl₆ dimers, is connected to the organic ones through van der Waals interaction in order to build cation–anion–cation cohesion. The infrared and Raman studies confirm the presence of the organic group tetrapropylammonium and the Zn₂Cl₆ anion. Concerning the differential scanning calorimetry, it revealed two reversible solid–solid phase transitions of first order: at 327/324 K and 347/343 K (heating/cooling). Besides, the impedance spectroscopy study, reported in the sample, reveals that the conduction in the material is due to a hopping process. Regarding the temperature dependence of the dc conductivity, it suggests Arrhenius type: σ _dc T?=?B ?exp(?E _a /kT). The tetrapropylammonium cations appeared to be the most sensitive to the phase transition.     

Synthesis,Crystal Structure and Luminescent Properties of Some Zn(II) Schiff Base Complexes: Experimental and Computational Study

A series of Zn(II)-Schiff bases I, II and III complexes were synthesized by reaction of o-phenylenediamine with 3-methylsalicylaldehyde, 4-methylsalicylaldehyde and 5-methylsalicylaldehyde. These complexes were characterized using FT-IR, UV-Vis, Diffuse reflectance UV-Vis, elemental analysis and conductivity. Complex III was characterized by XRD single crystal, which crystallizes in the triclinic system, space group P-1, with lattice parameters a?=?9.5444(2) Å, b?=?11.9407(2) Å, c?=?21.1732(3) Å, V?=?2390.24(7) ų, D _c ?=?1.408 Mg m^?3, Z?=?4, F(000)?=?1050, GOF?=?0.981, R1?=?0.0502, wR2?=?0.1205. Luminescence property of these complexes was investigated in DMF solution and in the solid state. Computational study of the electronic properties of complex III showed good agreement with the experimental data.     

Rare earth ions (Eu3+ and Nd3+) doped BaSnF4: transport and photoluminescence characteristics

Investigation on the X-ray diffraction results of rare earth ions such as Eu³⁺ and Nd³⁺ doped BaSnF₄ materials indicates that the doped materials show a similar pattern of BaSnF₄ with the same tetragonal structure (P₄/nmm). The transport properties of the materials have been investigated by impedance spectroscopy, and the results show that the conductivity values are closely related to both concentration and type of the dopant ion. All of these doped materials show an increase in conductivity over un-doped BaSnF₄. The highest conductivity is observed in 3 mol% Nd³⁺ ion-doped BaSnF₄ system (9.01?×?10^?4 Scm^?1), which is about one order higher in comparison to BaSnF₄ conductivity (1.1?×?10^?4 Scm^?1). The room temperature emission spectrum of BaSnF₄:Eu³⁺ and BaSnF₄:Nd³⁺ shows the characteristic bands arising from ⁵D₀?→?⁷F _j (j?=?1, 2, 3, and 4) and ⁴F_3/2 to ⁴I _j (j?=?9/2 and 11/2) transitions of Eu³⁺ and Nd³⁺ ions, respectively.     

Preparation of Sm3+–Eu3+ coactivating red-emitting phosphors and improvement of their luminescent properties by charge compensation

By charge compensating, a series of red-emitting phosphors Ca_0.54Sr_0.16Ca_0.54Sr_0.31Eu_0.08Sm_0.02(MoO₄)_0.6(WO₄)_0.4 were synthesized. Two approaches to charge compensation were used: (a) 2Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+M ⁺, where M⁺ is a monovalent cation like Li⁺, Na⁺ or K⁺; (b) Ca²⁺/Sr²⁺→Eu ³⁺/Sm³⁺+N ^?, where N⁺ is a monovalent anion like F^?, Cl^?, Br^?, or I^?. One red LED was made by combining the phosphor and 390–405 nm emitting LED chip under 20 mA forward-bias current, the color purity, chromaticity coordinates and the luminous intensity of which were 99.5%, x=0.66, y=0.33, 5600 mcd, respectively.     

Effects of Al doping for Li[Li0.09Mn0.65*0.91Ni0.35*0.91]O2 cathode material

Li-rich Mn-based Li[Li_0.09Mn_{0.65*(0.91???x)} Ni_{0.35*(0.91???x)} Al _x ]O₂ cathode materials have been prepared by traditional solid-state reaction. The lattice parameters a, c, and V have decreased, but c/a increased with the increase of Al doping. All the samples show analogy morphology of a quasi-spherical shape. Li[Li_0.09Mn_0.591Ni_0.319]O₂ sample shows a higher initial discharge capacity of 239.4 mAh?g^?1 at 20 mA?g^?1, while Li[Li_0.09Mn_0.582Ni_0.314Al_0.015]O₂ sample presents a higher discharge capacity of 170.1 mAh?g^?1 and ratio of 72.0 % with 200 vs. 20 mA?g^?1. The solid electrolyte interface resistance (R _SEI) and charge transfer process resistance (R _ct ) values are relatively smaller for Al-doped samples than those of non-doped samples. Almost no reduction is observed after 24-time cycles in different discharge rates for the samples prepared.     

X-ray structure refinement,vibrational spectroscopy,and ionic conductivity of Na0.11Ca9.64Sm0.23(PO4)6F2

The present paper is interested in the study of compounds from the apatite family, which is an apatite structure of individual rare earth substituted fluorapatite. In fact, an Sm-Bearing fluorapatite Ca_10–2yNa_ySm_y(PO₄)₆A₂ with x?=?0.11 and y?=?0.23 has been synthesized by solid-state reaction and characterized by X-ray powder diffraction. The site occupancies of substituents are 0.01091 for Sm and 0.02601 for Na in the Ca(1) position and 0.05317 for Sm in the Ca(2) position. Besides, the observed frequencies in the Raman and infrared spectra were explained and discussed on the basis of unit cell group analyses and in comparison with fluorapatite and other fluorapatites. In addition to the proton conduction, the possibility of a Na⁺ contribution to the conductivity in the high-temperature phase is proposed. The highest overall conductivity values were found at σ_{475 °C}?=?2.03?×?10^?5 S cm^?1 and Ea?=?0.60 eV.     

Hopping conductivity of carbynes modified under high pressures and temperatures: Galvanomagnetic and thermoelectric properties

The conductivity, thermopower, and magnetoresistance of carbynes structurally modified by heating under a high pressure are investigated in the temperature range 1.8–300 K in a magnetic field up to 70 kOe. It is shown that an increase in the synthesis temperature under pressure leads to a transition from 1D hopping conductivity to 2D and then to 3D hopping conductivity. An analysis of transport data at T ≤ 40 K makes it possible to determine the localization radius a ～ (56?140) Å of the wave function and to estimate the density of localized states _g(E _F) for various dimensions d of space: _g(E _F) ≈ 5.8 × 10⁷ eV^?1 cm^?1 (d=1), _g(E _F) ≈5×10¹⁴ eV^?1 cm ^?2 (d=2), and _g(E _F)≈1.1×10²¹ eV^?1 cm_?3 (d=3). A model for hopping conductivity and structure of carbynes is proposed on the basis of clusterization of sp ² bonds in the carbyne matrix on the nanometer scale.     

Charge transfer in TlFeS2 and TlFeSe2

The temperature dependences of the conductivity and the thermoelectric coefficient in TlFeS₂ and TlFeSe₂ samples have been investigated in the temperature range 85–400 K. The variable-range hopping conduction has been established. It is found that the density of localized states N _F near the Fermi level is 1.7×10¹⁸ and 3.3×10¹⁸ eV^?1 cm^?3, and the average hopping length R is 109 and 104 Å for TlFeS₂ and TlFeSe₂, respectively. The non-Arrhenius (activationless) behavior of the hopping conductivity is established in the temperature region T<200 K for TlFeS₂ and T<250 K for TlFeSe₂.     

Spectral and surface investigations of Ca2V2O7:Eu3+ nanophosphors prepared by citrate-gel combustion method: a potential red-emitting phosphor for near-UV light-emitting diodes

In the present work, red-emitting Ca₂V₂O₇:xEu³⁺ (x = 0.5–6.0 mol%) nanophosphors, in the form of powders, were synthesized by the citrate-gel combustion method using metal nitrates as precursors and citric acid as fuel. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy, photoluminescence (PL) and cathodoluminescence (CL) spectroscopy were used to study the structure, morphology and spectral properties of the samples. The chemical compositions and electronic states of the powders were analyzed with X-ray photoelectron spectroscopy. The average crystallite sizes estimated using the XRD data were found to be in the range of 30–45 nm, and were cross verified by TEM. The lattice parameters determined by the POWD program were approximated as a = 7.242 Å, b = 6.674 Å, c = 6.932 Å and V = 291.24 Å³, respectively. Under UV (395 nm) (PL) and electron (CL) excitation, the nanophosphors show characteristic emission from the Eu³⁺ ion (⁵D₀ → ⁷F_j, j = 1–5) with the main peaks at 612 and 616 nm. The maximum emission intensity was recorded from the sample with an Eu³⁺ concentration of 4 mol% and a critical energy distance of 19.084 Å between the donor and the acceptor. Above this concentration, there was a reduction in the intensity due to dipole–dipole induced concentration quenching effects. The potential applications of this phosphor as a high color-purity phosphor in light-emitting diodes are evaluated.     

Anionic conductivity and thermal stability of single crystals of solid solutions based on calcium fluoride

The temperature and composition dependencies of the anionic conductivity in the temperature range from ambient to 1073 K were studied for single crystals of Ca_1−xGd_xF_2+x (x=1×10⁻⁴, 1×10⁻³, 1×10⁻² and 1×10⁻¹) and of Ca_0.8R_0.2F_2.2 (R=La, Ce, Pr, Nd, Gd, Dy, Er, Tm, Yb, Lu and Y), having the fluorite structure. The conductivity plots for the concentrated Ca_0.8R_0.2F_2.2 solid solutions display the low-temperature and high-temperature linear (Arrhenius) regions with the knee temperature T_k∼770 K. The values of the conductivity activation enthalpy obey the relation ΔH_HT(T>T_k)>ΔH_LT(T<T_k). The conductivity mechanism in heavily doped Ca_1−xR_xF_2+x crystals is associated with the clusters of the point defects which decrease the potential barriers for fluoride anions moving by hops over the structural sites of the anion sub-lattice. We studied the effect of the dimensional factor (doped cation radii) on the anionic transport in these crystals. A correlation between anionic transport and atomic structure of the studied crystals is discussed.     

UV and VUV spectroscopic study of Na0.4Y0.6F2.2 crystals doped with rare-earth ions

The short-wavelength transmission spectra of Na_0.4 R _0.6F_2.2 crystals with R = Y, Yb, or Lu have been investigated. For these crystals, the VUV transmission cutoffs are 78750, 58820, and 75200 cm^?1, respectively. The 4f ⁿ–4f ^n?15d absorption and excitation spectra of Na_0.4Y_0.6F_2.2 crystals activated with Ce³⁺, Pr³⁺, Nd³⁺, Er³⁺, Tm³⁺, and Yb³⁺ ions have been analyzed in the range 30000–80000 cm^?1. The energy positions of the lowest levels of the 4f ^n?15d configurations of these ions in the fluorite crystal matrix Na_0.4Y_0.6F_2.2 are determined. The absorption band in the spectral range 60600–70000 cm^?1 in Na_0.4(Y, Yb)_0.6F_2.2 crystals is due to the charge transfer from F^? to Yb³⁺. It is shown that the environmental symmetry of Ce³⁺ ions in Na_0.4R_0.6F_2.2 (R = Y, Yb, Lu) crystals is almost identical.     

Di-urethanesil hybrid electrolytes doped with Mg(CF3SO3)2

Two siloxane-based di-urethanesil frameworks incorporating poly(oxyethylene) (POE) chains have been synthesized by the sol–gel process and doped with magnesium triflate (Mg(CF₃SO₃)₂) with the goal of developing electrolytes for the fabrication of solid-state rechargeable magnesium batteries. In these matrices, short POE chains are covalently bonded to the siloxane network via urethane linkages. The xerogels have been represented by the notation d-Ut(Y) _n Mg(CF₃SO₃)₂, where Y?=?300 and 600 represents the average molecular weight of the POE chains and n stands for salt composition (molar ratio of OCH₂CH₂ units per Mg²⁺). Xerogels with compositions ranging from 2?≤?n?<?∞ were prepared. A crystalline POE/Mg(CF₃SO₃)₂ complex of unknown stoichiometry is formed in the d-Ut(300) _n Mg(CF₃SO₃)₂ materials with n?≤?6 and in the d-Ut(600) _n Mg(CF₃SO₃)₂ materials with n?≤?5. The organically modified silicate electrolytes with the highest conductivity of the d-Ut(300) _n Mg(CF₃SO₃)₂ and d-Ut(600) _n Mg(CF₃SO₃)₂ series are the samples with n?=?6 (3.9?×?10^?8 S cm^?1 at 26 °C and 8.7?×?10^?5 S cm^?1 at 97 °C) and n?=?100 (2.63?×?10^?7 S cm^?1 at 20 °C and 1.4?×?10^?5 S cm^?1 at 85 °C), respectively. Since the electrolytes for Mg batteries that have been proposed up to now have many intrinsic problems and although the room temperature conductivity values exhibited by the systems developed in the present study are still low in view of practical application, this work opens new directions for the development of solid-state Mg ion electrolytes.     

The chemical stability and conductivity improvement of protonic conductor BaCe0.8 − x Zr x Y0.2O3 − δ

A series of BaCe_0.8???x Zr _x Y_0.2O_3???δ (BCZYx) (x?=?0, 0.2, 0.4, 0.6, 0.8) powders were prepared by EDTA–citrate complexing sol–gel process in this paper. The electrical conducting behavior, as well as chemical stability, was investigated. X-ray diffraction (XRD) results reveal that all samples are homogenous perovskite phases. Observed from XRD patterns and thermogravimetric curves, the samples with x?≥?0.4 survive in the pure CO₂, while samples with various Zr contents all present structurally stable against steam at 800 °C. The Zr-free sample of BaCe_0.8Y_0.2O_3???δ possesses the maximum bulk conductivity, 4.25?×?10^?2 S/cm, but decomposes into Ba(OH)₂ and Ce_0.8Y_0.2O_3???δ in steam. A negative influence of increasing Zr content on the conductivity of BCZYx can be observed by impedance tests. Considering the effect of temperature on the bulk conductivity, BCZY0.4 is preferred to be applied in SOFC as a protonic conductor, ranging from 1.52?×?10^?4 to 1.51?×?10^?3 S/cm (500–850 °C) with E _a?=?0.859 eV, which is proved to be a good protonic conductor with t _H+?≥?0.9.     

Synthesis and characterisation of the Fe(II–III) hydroxy-formate green rust

A new methodology was envisioned in order to prepare green rust compounds build on organic anions that could intervene in microbiologically influenced corrosion processes of iron and steel. The formate ion was chosen as an example. The formation of rust was simulated by the oxidation of aqueous suspensions of Fe(OH)₂ precipitated from Fe(II) lactate and sodium hydroxide, in the presence of sodium formate to promote the formation of the corresponding green rust. The evolution of the precipitate with time was followed by transmission Mössbauer spectroscopy at 15 K. It was observed that the initial hydroxide was transformed into a new GR compound. Its spectrum is composed of three quadrupole doublets, D ₁ (δ?=?1.28 mm s^?1, Δ?=?2.75 mm s^?1) and D ₂ (δ?=?1.28 mm s^?1, Δ?=?2.48 mm s^?1) that correspond to Fe(II) and D ₃ (δ?=?0.49 mm s^?1, Δ?=?0.37 mm s^?1) that corresponds to Fe(III). The relative area of D ₃, close to the proportion of Fe(III) in the GR, was found at 28.5?±?1.5% (～2/7). Raman spectroscopy confirmed that the intermediate compound was a Fe(II–III) hydroxy-formate, GR(HCOO^?).     

Dipotassium sodium niobium dioxide tetrafluoride,K2NaNbO2F4, crystal structure and characterization

The paper presents a new data on the crystal structure of K₂NaNbO₂F₄. Single crystals of K₂NaNbO₂F₄, were obtained from the system of KF–NaF–Nb₂O₅. The compound is cubic, space group Fm3?m (No. 225), and the unit cell parameters are a=8.4726(4) Å, Z=4, Volume=608.21(5) Å³. The structure was solved by the direct methods and refined to the reliability factors R₁=0.0116 (wR₂=0.0302). Its structure can be described as three-dimensional frameworks formed of (0 1 0) [Na₂Nb₂O₄F₈]∞ layers stacked along b axis. In the framework, niobium, oxygen, fluorine atoms form a rare [NbO₂F₄]^3? anion group in an anhydrous solid state environment. The IR spectrum further confirmed the presence of NbO₂ and NbF₄ groups in the structure. The thermal analysis suggests that K₂NaNbO₂F₄ is an incongruently melting compound.     

Study on ammonium acetate salt-added polyvinyl alcohol-based solid proton-conducting polymer electrolytes

Polyvinyl alcohol (PVA) complexes with different compositions of ammonium acetate (AA) are prepared by solution cast technique. Polyvinyl alcohol crystallinity decreased with increasing ammonium acetate salt content. Molecular weight and density of polyvinyl alcohol complex increased with the addition of ammonium acetate salt. The ammonium acetate salt addition resulted in plasticization and hence decreased glass transition temperature (T _g) as well as hardness number (HV). 80PVA:20AA presented maximum conductivity (σ?=?1.3?×?10^?7S cm^?1 at 303 K) with minimum activation energy (E _a) 0.151 eV below the T _g. The proton transport number determined using EMF method found ≈0.98 for polymer complex with ammonium acetate content >15 mol%. The complex impedance is measured as a function of frequency, temperature, relative humidity, and hydrogen partial pressure. Enhanced bulk conductivity with increased H₂ partial pressure and relative humidity suggested H⁺ mobility within complex polymer electrolyte.