The NASICON solid solution Li1−x La x /3Zr2(PO4)3: optimization of the sintering process and ionic conductivity measurements

The Li_1−x La _{x /3}Zr₂(PO₄)₃ NASICON-type compounds (0 ≤ x ≤ 1) have been synthesized in powder form by a sol-gel method and sintered for ionic conductivity measurements. In order to improve the compactness of the ceramic without decomposition of the compound, several sintering processes have been tested for one member of the solid solution (x = 0.6): the use of sintering aids (ZnO, B₂O₃, TiO₂ and LiNO₃), a ball-milling of the synthesized powder, a flash heating, high isostatic pressure, and spark plasma sintering. Finally, a satisfactory compactness of 85% is obtained compared to the referenced value (63%) obtained by uniaxial and isostatic pressing. The ionic conductivity study was performed by impedance spectroscopy. It shows that, despite the formation of vacancies, the substitution Li⁺→ 1/3 La³⁺ + 2/3 □ has unfortunately no influence on the conduction for 0 ≤ x ≤ 0.7 since the ionic conductivity remains identical to the LiZr₂(PO₄)₃ one. For higher x values, the ionic conductivity strongly decreases.     

Superprotonic solid solutions between CsHSO4 and CsH2PO4

Solid solutions of (CsHSO₄)_1 − x(CsH₂PO₄)_x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH₂PO₄. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10^− 2–10^− 3 S∙cm^− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO₄ (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.     

Co-precipitation synthesis and performance of multi-doped LiCrxNixMn2-2xO4-zFz cathode materials for lithium ion batteries

Multiple ion-doped lithium manganese oxides LiCr_xNi_xMn_2-2xO_4-zF_z (0 < x ≤ 0.25, z =  0.05, 0.1) with a spinel structure and space group Fd m were prepared by using the co-precipitation procedure carried out in water–alcohol solvent using adipic acid as the chelating agent. The electrochemical measurements indicated that the charge/discharge capacities of the samples prepared at 600 °C are higher than that of the treatment at 800 °C or microwave heating. The capacitance-voltage (CV) curves of LiCr_xNi_xMn_2-2xO_4-zF_z (0 < x ≤ 0.25, z = 0.05, 0.1) showed that when x ≤ 0.1, the samples had two reduction–oxidation peaks at 4.0 to 4.2-V region, whereas when x > 0.1, the samples had only one reduction–oxidation peak at 4.0- to 4.2-V region in CV measurements and could offer more stable voltage plateau in a 4-V region and also had stable electrical conductivity after 20 cycles. Another reduction–oxidation peak appeared in 4.6-4.8-V region (Ni²⁺–Ni⁴⁺ reduction–oxidation peaks); this suggests that the LiCr_xNi_xMn_2-2xO_4-zF_z (0.1 < x≤ 0.25, z = 0.05, 0.1) cathode material could offer 4.6 to 4.8-V charge/discharge plateaus, and its specific capacity increases with increasing Ni²⁺. The impedance measurements of the cell proved that the F⁻ anion doped can not only prevent Mn³⁺ from disproportion but also can prevent the passivation film from forming and can help keep stable the cell’s electrical properties. The LiCr_0.05Ni_0.05Mn_1.9O_3.9F_0.1 sintered at 600 °C shows the best cycle performance and the largest capacity in all prepared samples; its first discharge capacity is 120 mAh/g, and the discharge capacity loses only 1.78% after 20 cycles. After 100 cycles, it still remains in the spinel structure.     

Impact of ethylene carbonate on electrical properties of PVA/(NH4)2SO4/H2SO4 proton-conductive membrane

A new proton-conductive membrane (PCM) based on poly (vinyl alcohol) and ammonium sulfate (NH₄)₂SO₄ complexed with sulfuric acid and plasticized with ethylene carbonate (EC) at different weight percent were prepared by casting technique. The structural properties of these electrolyte films were examined by XRD studies. The XRD patterns of all the prepared polymer electrolytes reveal the amorphous nature of the films. ac conductivity and dielectric spectra of the electrolyte were studied with changing EC content from weight 0.00 to 0.75 g. A maximum conductivity of 7.3 × 10⁻⁵ S cm⁻¹ has been achieved at ambient temperature for PCM containing 0.25 g of ethylene carbonate. The electrical conductivity σ, dielectric constant ε′ and dielectric loss ε″ of PCM in frequency range (100 Hz to 100 KHz), and temperature range (300–400 K) were carried out. Measurement of transference number was carried out to investigate the nature of charge transport in these polymer electrolyte films using Wagner’s polarization technique. Transport number data showed that the charge transport in these polymer electrolyte systems was predominantly due to ions. The electrolyte with the highest electrical conductivity was used in the fabrication of a solid-state electrochemical cell with the configuration (Mg/PCM/PbO₂). Various cell parameters ldensity, and current density were determined. The fabricated cells gave capacity of 650 μAh and have an internal resistance of 11.6 kΩ.     

Reactivity at the oxygen/titania interface and the related charge transfer

The present paper reports the reactivity between TiO₂ and oxygen and the related charge transfer at 298 and 1,073 K. The studies were performed using work function measurements. It was found that oxidation of TiO₂ at 1,073 K and p(O₂) = 75 kPa, initially standardized at 1,173 K and p(O₂) = 10 Pa, results in work function changes that are consistent with the theoretical model of the charge transfer during oxygen chemisorption and oxygen incorporation at the absence of structural transitions. However, oxidation of TiO₂ at 298 K, p(O₂) = 75 kPa, which has been initially standardized at 1,173 K in extremely reducing conditions at p(O₂) = ∼10⁻¹⁰ Pa, results in work function changes that are consistent with low-dimensional structural changes of the surface layer. It is shown that oxidation of strongly reduced TiO₂ at 298 K results in a decrease of work function, which cannot be explained without assuming the structural changes of the outermost surface layer.     

Ionic conductivity and structural properties of MnO-doped Bi4V2O11 system

Bi₄V₂O₁₁ exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher conductivity by the partial substitution of metallic cations for vanadium in Bi₄V₂O₁₁. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn²⁺-doped compounds Bi₄V_2−x Mn _x O_{11− δ} (0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi₄V_2−x Mn _x O_{11− δ} samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy.     

Muon spin relaxation study on magnetism in high quality single crystal of a high transition temperature superconductor La2−xSrxCuO4−σ (0.11≤x≤0.14)

The positive muon spin relaxation method is applied to probe magnetic ordering in the superconducting phase of a high quality single crystal of La_2−xSr_xCuO_4−σ (0.11≤x≤0.14). The well characterized crystal ofx=0.11 (T _c=34.5 K) with nearly complete flux exclusion exhibits spin freezing at 8K(T _f) with significant spin fluctuation up to 20 K. The onset of spin fluctuation andT _f decrease against increasingx towardsx=0.15, suggesting an existence of a magnetic phase boundary aroundx whereT _c becomes maximum.     

Superconductivity and magnetic ordering in YBa2(Cu1−x Fe x )3O7

Transverse-and zero-field μSR measurements have been made for YBa₂(Cu_1−x Fe _x )₃O₇ withx=0.04, 0.08 and 0.12. The temperature range studied was from approximately 7.5 K to 100 K. The onset of magnetic ordering commences at about 7.5 K forx=0.04, 10 K forx=0.08 and 20 K forx=0.12. The Gaussian depolarization parameter, σ ofG _x (t) = exp(−σ² t ²/2), is depressed by a factor of about 0.6 forx=0.04, but for thex=0.08 sample σ is depressed by a factor of 10 and increasing suppression is seen as the temperature is lowered below 45 K. This decrease in σ is interpreted in terms of decreasing electronic mean free paths.     

Electrical conductivity and chemical stability of perovskite-type BaCe0.8-xTixY0.2O3-δ

Here we report the synthesis, chemical stability, and electrical conductivity of Ti-doped perovskite-type BaCe_0.8-x Ti _x Y_0.2O_3-δ (x = 0.05, 0.1, 0.2, and 0.3; BCTY). Samples were synthesized by conventional solid state (ceramic) reaction from corresponding metal salts and oxides at elevated temperature of 1,300–1,500 °C in air. The powder X-ray diffraction confirmed the formation of a simple cubic perovskite-type structure with a lattice constant of a = 4.374(1), 4.377(1), and 4.332(1) ? for x = 0.05, 0.1, and 0.2 members of BCTY, respectively. Like BaCe_0.8Y_0.2O_3-δ (BCY), Ti substituted BCTY was found to be chemically not stable in 100% CO₂ and form BaCO₃ at elevated temperature. The bulk electrical conductivity of BCTY decreased with increasing Ti content and the x = 0.05 member exhibited the highest conductivity of 2.3 × 10⁻³ S cm⁻¹ at 650 °C in air, while a slight increase in the conductivity, especially at low temperatures (below 600 °C), was observed in humidified atmospheres.     

An ab initio molecular dynamics study of ionic conductivity in hexagonal lithium lanthanum titanate oxide La0.5Li0.5TiO3

To date, the fastest lithium ion-conducting solid electrolytes known are the perovskite-type ABO₃ oxide, with A = Li, La and B = Ti, lithium lanthanum titanate (LLTO) Li_3x La_{( 2 \mathord}

Structure, ferroelectric and piezoelectric properties of?(Bi0.98?xLa0.02Na1?x)0.5BaxTiO3 lead-free ceramics

Lead-free (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction show that La²⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) exists at 0.04<x<0.10. Compared with pure Bi_0.5Na_0.5TiO₃ ceramics, the (Bi_0.98−x La_0.02Na_1−x )_0.5Ba _x TiO₃ ceramics possess much smaller coercive field E _c and larger remanent polarization P _r. Because of the low E _c (3.38 kV/mm), large P _r (46.2 μC/cm²) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly enhanced at x=0.06: d ₃₃=181 pC/N and k _p=36.3%. The depolarization temperature T _d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T _d.     

Synthesis and characterization of Bi-doped zirconia for solid electrolyte

(100-x)ZrO₂(x)Bi₂O₃ (x = 5, 10, 15) system has been synthesized by solid-state reaction technique. Tetragonal Bi_7.38Zr_0.62O_12.31 phase has formed in all the samples after sintering at 850 °C for 24 h. Apart from this, ZrO₂ and Bi₂O₃ are also identified as minority phases. The volume fraction of Bi_7.38Zr_0.62O_12.31 phase increases with increasing concentration of Bi₂O₃. The AC conductivity plots exhibit phase transition at 570 °C and 460 °C for x = 10 and x = 15 samples, respectively. The maximum conductivity is observed (1.60 mS/cm) in x = 15 sample. These results are correlated and supported with microstructural and thermal analysis.     

Charge density wave and superconductivity in 2H- and 4H-NbSe<Subscript>2</Subscript>: A revisit

Good-quality hexagonal NbSe₂ single crystals were prepared. In 2H-NbSe₂, superconducting and charge density wave (CDW) transitions were found at T _s = 7.4 K and T _c = 35 K respectively as reported previously. We have noticed that these two transitions are changed to T _c = 42 K and T _s = 6.5 K, in 4H-NbSe₂. Thermopower has shown clear anomaly at CDW transitions. The anisotropic upper critical field was calculated as ~3 and 6.3 for 2H- and 4H-single crystals around t = 0.81, where t = T/T _s, from resistivity and explained in terms of coherence length. From the relation, H_c2 (T)=H_c2 (0)[1-t²]H_{\rm c2} (T)=H_{\rm c2} (0)[1-t^2], H_c2^l (0)H_{\rm c2}^l (0) was calculated as ~8.15 T and 16.98 T at t = 0.84 in 2H-NbSe₂ and 4H-NbSe₂ respectively. However, H_c2^t (0) = 2.68H_{\rm c2}^t (0) = 2.68T for both single crystals.     

Non-steady-state photo-EMF in nanostructured GaN and polypyrrole within porous matrices

We report an experimental investigation of the non-steady-state photoelectromotive force in nanostructured GaN within porous glass and polypyrrole within chrysotile asbestos. The samples are illuminated by an oscillating interference pattern created by two coherent light beams and the alternating current is detected as a response of the material. Dependences of the signal amplitude versus temporal and spatial frequencies, light intensity, and temperature are studied for two wavelengths λ=442 and 532 nm. The conductivity of the GaN composite is measured: σ=(1.1–1.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=442 nm, I ₀=0.045–0.19 W/cm², T=293 K) and σ=(3.5–4.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=532 nm, I ₀=2.3 W/cm², T=249–388 K). The diffusion length of photocarriers in polypyrrole nanowires is also estimated: L _D=0.18 μm.     

Fluctuation-Induced Conductivity of Polycrystalline (Ho–Ce)Ba2Cu3O$_{7-\boldsymbol\delta}$ Superconductor

We report on systematic conductivity fluctuation measurements on samples of Ho_1 − x Ce _x Ba₂Cu₃O_7 − δ with x = 0.00, 0.05, and 0.10. The samples were produced by a standard solid-state reaction method, and the microstructure was analyzed by X-ray diffraction. To identify power-law divergences of the conductivity, the results were analyzed in terms of the temperature derivative of the resistivity dρ/dT and with the logarithmic derivative of the conductivity with respect to temperature − dln (Δσ)/dT. It was observed that the critical temperature decreases and that the transition width increases with increasing Ce doping. The data showed the occurrence of a two-stage transition besides the pairing transition splitting, associated with Ce doping and related with the occurrence of a phase separation. Above the critical temperature, the Gaussian and critical regimes were observed. On approaching the zero resistance state, our results showed a power-law behavior that corresponds to a phase transition from a paracoherent to a coherent state of the granular array.     

Lithium ion conductivity of Li5+xBaxLa3?xTa2O12 (x?=?0–2) with garnet-related structure in dependence of the barium content

The stoichiometry range and lithium ion conductivity of Li_5+x Ba _x La_3−x Ta₂O₁₂ (x = 0, 0.25, 0.50, 1.00, 1.25, 1.50, 1.75, 2.00) with garnet-like structure were studied. The powder X-ray diffraction data of Li_5+x Ba _x La_3−x Ta₂O₁₂ indicated that single phase oxides with garnet-like structure exist over the compositional range 0 ≤ x ≤ 1.25; while for x = 1.5, 1.75 and 2.00, the presence of second phase in addition to the major garnet like phase was observed. The cubic lattice parameter increases with increasing x and reaches a maximum at x = 1.25 then decreases slightly with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. The impedance plots of Li_5+x Ba _x La_3−x Ta₂O₁₂ samples obtained at 33 °C indicated a minimum grain-boundary resistance (R _gb) contribution to the total resistance (R _b + R _gb) at x = 1.0. The total (bulk + grain boundary) ionic conductivity increases with increasing lithium and barium content and reaches a maximum at x = 1.25 and then decreases with further increase in x in Li_5+x Ba _x La_3−x Ta₂O₁₂. Scanning electron microscope investigations revealed that Li_6.25Ba_1.25La_1.75Ta₂O₁₂ is much more dense, and the grains are more regular in shape. Among the investigated compounds, Li_6.25Ba_1.25La_1.75Ta₂O₁₂ exhibits the highest total (bulk + grain boundary) and bulk ionic conductivity of 5.0 × 10⁻⁵ and 7.4 × 10⁻⁵ S/cm at 33 °C, respectively.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

Synthesis, crystal structure, thermal and dielectric properties of bis(p-phenylenediammonium) chloride hexachlorobismuthate(III) monohydrate [C6H4(NH3)2]2ClBiCl6.H2O

Synthesis, crystal structure, and dielectric properties of [C₆H₄(NH₃)₂]₂ClBiCl₆.H₂O are reported. The compound crystallizes in the monoclinic system with space group P2₁/n. The unit cell dimensions are a = 9.836(5), b = 19.582(5), c = 13.082(5) ?, β = 104.731(5)° with Z = 4. The atomic arrangement can be described by an alternation of organic and inorganic layers. The anionic layer is built up of octahedral of [BiCl₆]^3- arranged in sandwich between the organic layers. The crystal packing is governed by means of the ionic N–H···Cl hydrogen bonds, forming a three-dimensional network. The dielectric properties have been investigated at temperature range from 297 to 410 K at various frequencies (10 Hz–100 kHz). Dielectric studies were performed to confirm results obtained with thermal analysis. The evolution of dielectric constant as a function of temperature and frequency of single crystal has been investigated in order to determine some related parameters.     

Electrical properties,equivalent circuit,and dielectric relaxation studies on [(C<Subscript>3</Subscript>H<Subscript>7</Subscript>)<Subscript>4</Subscript>N]<Subscript>2</Subscript>Cd<Subscript>2</Subscript>Cl<Subscript>6</Subscript> polycrystalline

The Ac electrical conductivity and the dielectric relaxation properties of the [(C₃H₇)₄N]₂Cd₂Cl₆ polycrystalline sample have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 209 Hz–5 MHz and 361–418 K, respectively. The purpose is to make a difference between the electrical and dielectric properties of the polycrystalline sample and single crystal. Besides, a detailed analysis of the impedance spectrum suggests that the electrical properties of the material are strongly temperature-dependent. Plots of (Z" versus Z') are well fitted to an equivalent circuit model consisting of a series combination of grains and grains boundary elements. Moreover, the temperature dependence of the electrical conductivity in the different phases follows the Arrhenius law and the frequency dependence of σ (ω) follows the Jonscher’s universal dynamic law. Furthermore, the modulus plots can be characterized by full width at half height or in terms of a nonexperiential decay function φ(t) = exp(t/t)^β. Finally, the imaginary part of the permittivity constant is analyzed with the Cole–Cole formalism.     

Enhanced cyclability of triple-metal-doped LiMn2O4 spinel as the cathode material for rechargeable lithium batteries

To improve the cycle performance of spinel LiMn₂O₄ as the cathode of 4-V-class lithium secondary batteries, spinel phases LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) were successfully prepared using the sol–gel method. The spinel materials were characterized by powder X-ray diffraction (XRD), elemental analysis, and scanning electron microscopy. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns. Electrochemical studies were carried out using the Li|LiM _x Mn_2 − x O₄ (M=Li, Fe, Co; x = 0, 0.05, 0.1, 0.15) and LiFe_0.05M _y Mn_{1.95 − y} O₄ (M=Li, Al, Ni, Co; y = 0.05, 0.1) cells. These cathodes were more tolerant to repeated lithium extraction and insertion than a standard LiMn₂O₄ spinel electrode in spite of a small reduction in the initial capacity. The improvement in cycling performance is attributed to the stabilization in the spinel structure by the doped metal cations.