Ionic conduction and effect of cation doping in Tl<Subscript>4</Subscript>HgI<Subscript>6</Subscript>

The ionic conduction properties of undoped and doped Tl₄HgI₆ were investigated using electrical conductivity, dielectrics, differential scanning calorimetry, and X-ray diffraction techniques. The heavy Tl⁺-ions diffusion was activated at high temperature, whereas low conductivity at the lower temperature suggested electronic contribution in undoped Tl₄HgI₆. The partial replacement of heavy Tl⁺ ion by suitable cations (Ag⁺ and Cu⁺) enhanced the conductivity by several orders of magnitude, whereas diminution in conductivity results with increasing dopants’ concentration in Tl₄HgI₆. These results can be interpreted in terms of a lattice contraction and vacancy–vacancy interaction (leading to the cluster formation), respectively. The dielectric values of undoped Tl₄HgI₆ system gradually increasing with temperature, followed by a sharp change, were observed around 385 K and can be explained on the basis of increasing number of space charge polarization and ions jump orientation effects. The activation energy of undoped and doped Tl₄HgI₆ systems were calculated, and it was found that ionic conductivity activation energy for 5 mol% of cation dopants is much lower than that of undoped one, and also 10 mol% doped Tl₄HgI₆ systems.     

Dipole ordering and ionic conductivity in NASICON-Type Na<Subscript>3</Subscript>Cr<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> structures

The aspects of structure, dipole ordering, and ionic conductivity of the Na₃Cr₂(PO₄)₃ crystal with the four polymorphic phases (α, α', β, and γ) have been investigated. The features of the α-Na₃Cr₂(PO₄)₃ crystal structure and its dipole ordering and relaxation polarization in the low-temperature α and α' phases have been refined. The occurrence of Na₃Cr₂(PO₄)₃ dipole ordering in the α and α' phases and high ionic conductivity in the β and γ phases is attributed to the structural changes in the rhombohedral [Me₂(PO₄)₃]^–3_3∞ crystal frame upon phase transformations α → α', α' → β, and β → γ. A model for explaining the dipole ordering and ionic conductivity phenomena in Na₃Cr₂(PO₄)₃ is proposed.     

Influence of Bi<Superscript>3+</Superscript> ions on low temperature D.C. conductivity of Na<Subscript>2</Subscript>SiCuO<Subscript>4</Subscript> glasses

Sodium silicate glasses doped with CuO and mixed with different contents of Bi₂O₃ (ranging from 4 to 16 mol%) were prepared. D.C. conductivity studies over a range of temperature from 225 to 325 K have been carried out. The conductivity is observed to decrease linearly with increase of Bi₂O₃ concentration. The results are analyzed using optical absorption, ESR, and IR spectral data. The spectroscopic studies have indicated that there is a gradual reduction divalent copper ions to monovalent ions with increase of Bi₂O₃ concentration. These studies have also indicated that such Cu⁺ ions participate in the glasses network forming and increase the polymerization of the glass network. The analysis of the results of D.C. conductivity indicated that in temperature region T > θ _D/2, the small polaron hoping model is valid, and the conduction is predicted to be adiabatic type. The analysis of the results has further revealed that there is a gradual change over of conduction mechanism from ionic to electronic with increase of Bi₂O₃ concentration. The low temperature part of D.C. conductivity is explained using variable range hopping (VRH) model.     

High-temperature conductivity and structure of Y<Subscript>2</Subscript>(WO<Subscript>4</Subscript>)<Subscript>3</Subscript> ceramics

The magnitude and character of conductivity were studied for Y₂(WO₄)₃ ceramics synthesized by the ceramic (from oxides) and organic-nitrate procedures. Investigation of the dependence \(\sigma \left( {{\alpha _{{o_2}}}} \right)\) and measurements of the ion transport numbers of charge carriers by the EMF method showed that Y₂(WO₄)₃ is basically an ion conductor. The conductivity is largely determined by the sample preparation conditions related to the dependence of the specific surface area and powder grain size on the synthetic procedure. The maximum high-temperature conductivity of Y₂(WO₄)₃ was 2.51 × 10^–4 S/cm, which roughly corresponds to the conductivities of Sc₂(WO₄)₃ and In₂(WO₄)₃ measured under the same conditions. It was confirmed that Y₂(WO₄)₃ crystallizes as a mixed monoclinic-orthorhombic structure at 1000°C. The character of water incorporation in hydrated Y₂(WO₄)₃ crystals was studied by thermogravimetry and diffuse reflectance IR spectroscopy. A qualitative model of water intercalation was suggested.     

Thermal properties and ionic conductivity of Li<Subscript>1,3</Subscript>Ti<Subscript>1,7</Subscript>Al<Subscript>0,3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> solid electrolytes sintered by field-assisted sintering

Li_1,3Ti_0,7Al_0,3(PO₄)₃ (LATP) powder was obtained by a conventional melt-quenching method and consolidated by field-assisted sintering technology (FAST) at different temperatures. Using this technique, the samples could be sintered to relative densities in the range of 93 to 99 % depending on the sintering conditions. Ionic and thermal conductivity were measured and the results are discussed under consideration of XRD and SEM analyses. Thermal conductivity values of 2 W/mK and ionic conductivities of 4?×?10^?4 Scm^?1 at room temperature were obtained using relatively large particles and a sintering temperature of 1000 °C at an applied uniaxial pressure of 50 MPa.     

High-temperature superconductors YBaCu<Subscript>2</Subscript>O<Subscript>5</Subscript> and Tl<Subscript>1.5</Subscript>BaCa<Subscript>2</Subscript>Cu<Subscript>2.5</Subscript>O<Subscript>8</Subscript> with a decreased content of heavy metals (Ba and Tl)

New high-temperature superconductors YBaCu₂O₅ and Tl_1.5BaCa₂Cu_2.5O₈ have been synthesized. They can be considered as a result of the removal of barium cuprate BaCuO₂ from YBa₂Cu₃O₇ and barium cuprate-tallate BaCu_0.5Tl_0.5O₂ from Tl₂Ba₂Ca₂Cu{ia3}O₁₀. The synthesized compounds contain a smaller amount of toxic Ba and Tl. Investigation of electrical conductivity has demonstrated that the values of T _c of synthesized materials are close to T _c of starting materials. The Meissner effect observed for these materials has confirmed their belonging to high-temperature superconductors.     

The transport and thermal properties of glassy LiPO<Subscript>3</Subscript>/crystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript> (ZrO<Subscript>2</Subscript>) composite electrolytes

Glassy LiPO₃/crystalline Al₂O₃ and glassy LiPO₃/crystalline ZrO₂ (0–12.5 vol.% of oxide fillers) composite solid electrolytes have been prepared by glass matrix softening. Their thermal and transport properties have been investigated by differential scanning calorimetry (DSC) and impedance spectroscopy methods. The addition of ZrO₂ leads to a decrease in the crystallization temperature of LiPO₃ glass. It was found that the conductivity behavior depends on the nature of the dispersed addition. In the case of the Al₂O₃ addition, the increase in the electrical conductivity is observed. The ionic conductivity of the LiPO₃/10% Al₂O₃ composite reaches 5.8 × 10^?8 S/cm at room temperature. In contrast, the conductivity in the LiPO₃/ZrO₂ composite system decreases.     

Dielectric and AC conductivity studies in Li<Subscript>2</Subscript>O-CoO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-TeO<Subscript>2</Subscript> glasses

CoO and Li₂O mixed with borotellurite glasses in the compositions, (B₂O₃)_0.2-(TeO₂)_0.3-(CoO) _x -(Li₂O)_0.5?x, where x = 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, and 0.50 were synthesized by fast cooling the melt to room temperature. Absence of crystalline phases in the samples was confirmed by X-ray diffraction studies. Changes in dielectric properties with frequency and temperature over wide ranges have been measured. Dielectric constant and loss increased with increase in CoO content. AC conductivity has been analyzed using Mott’s small polaron model and activation energy was determined. Activation energy decreased and conductivity increased with increase in CoO content up to 0.3 mole fractions, and they behaved oppositely for higher concentration of CoO. This observed change of trend in activation energy and conductivity at 0.3 mole fraction of CoO ascribed to switch over of conduction mechanism occurring from predominantly ionic to electronic regime. For the first time, a transition of conduction mechanism is observed in borotellurite glasses. Temperature and composition independent relaxation mechanism in these glasses has been confirmed by plotting the scaled conductivity master curves. Hunt’s model has been invoked to understand the frequency dispersion of conductivity.

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Graphical abstract Plots of ln(ε′′) versus ln(F) for BTCL2 glass at different temperatures

     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

Grain size effects on dynamics of Li-ions in Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> glass-ceramic nanocomposites

Li₃V₂(PO₄)₃ glass-ceramic nanocomposites, based on 37.5Li₂O-25V₂O₅-37.5P₂O₅ mol% glass, were successfully prepared via heat treatment (HT) process. The structure and morphology were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). XRD patterns exhibit the formation of Li₃V₂(PO₄)₃ NASICON type with monoclinic structure. The grain sizes were found to be in the range 32–56 nm. The effect of grain size on the dynamics of Li⁺ ions in these glass-ceramic nanocomposites has been studied in the frequency range of 20 Hz–1 MHz and in the temperature range of 333–373 K and analyzed by using both the conductivity and modulus formalisms. The frequency exponent obtained from the power law decreases with the increase of temperature, suggesting a weaker correlation among the Li⁺ ions. Scaling of the conductivity spectra has also been performed in order to obtain insight into the relaxation mechanisms. The imaginary modulus spectra are broader than the Debye peak-width, but are asymmetric and distorted toward the high frequency region of the maxima. The electric modulus data have been fitted to the non-exponential Kohlrausch–Williams–Watts (KWW) function and the value of the stretched exponent β is fairly low, suggesting a higher ionic conductivity in the glass and its glass-ceramic nanocomposites. The advantages of these glass-ceramic nanocomposites as cathode materials in Li-ion batteries are shortened diffusion paths for Li⁺ ions/electrons and higher surface area of contact between cathode and electrolyte.     

Effect of calcination conditions on lithium conductivity in Li<Subscript>1.3</Subscript>Ti<Subscript>1.7</Subscript>Al<Subscript>0.3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> prepared by sol-gel route

In order to study the influence of powder calcination temperature on lithium ion conductivity, synthesized Li_1.3Ti_1.7Al_0.3(PO₄)₃ (LATP) was calcined at temperatures between 750 and 900 °C. The shape and size of the particles were characterized employing scanning electron microscopy (SEM), and specific surface area of the obtained powder was measured. The crystallinity grade of different heat-treated powders was calculated from XRD spectra. Posteriorly, all powders were sintered at 1100 °C employing field-assisted sintering (SPS), and the electrical properties were correlated to the calcination conditions. The highest ionic conductivity was observed for samples made out of powders calcined at 900 °C.     

Effect of sintering conditions on the properties of sol-gel-derived Li<Subscript>1.3</Subscript>Al<Subscript>0.3</Subscript>Ti<Subscript>1.7</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Solid electrolyte Li_1.3Al_0.3Ti_1.7(PO₄)₃ was prepared by sol-gel method under different sintering conditions. The structural identification, surface morphology, electrochemical window, ionic conductivity, and activation energy of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellets were investigated by X-ray diffraction, scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. It is found that the sintering temperature and time have considerable effect on the properties of the Li_1.3Al_0.3Ti_1.7(PO₄)₃ sintered pellets. The Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellet sintered at 900 °C for 2 h is denser than the pellets sintered at other conditions. Different sintering conditions result in the sintered pellet with different porosity. However, the sintering conditions have little effect on the electrochemical window of Li_1.3Al_0.3Ti_1.7(PO₄)₃. Among the Li_1.3Al_0.3Ti_1.7(PO₄)₃ pellets sintered at various conditions, the pellet sintered at 900 °C for 2 h shows the highest ionic conductivity of 3.46 × 10⁻⁴ S cm⁻¹ and the lowest activation energy of 0.2821 eV.     

Effects of MnO<Subscript>2</Subscript> nano-particles on the conductivity of PMMA-PEO-LiClO<Subscript>4</Subscript>-EC polymer electrolytes

Li-ion rechargeable batteries based on polymer electrolytes are of great interest for solid state electrochemical devices nowadays. Many studies have been carried out to improve the ionic conductivity of polymer electrolytes, which include polymer blending, incorporating plasticizers and filler additives in the electrolyte systems. This paper describes the effects of incorporating nano-sized MnO₂ filler on the ionic conductivity enhancement of a plasticized polymer blend PMMA–PEO–LiClO₄–EC electrolyte system. The maximum conductivity achieved is within the range of 10⁻³ S cm⁻¹ by optimizing the composition of the polymers, salts, plasticizer, and filler. The temperature dependence of the polymer conductivity obeys the VTF relationship. DSC and XRD studies are carried out to clarify the complex formation between the polymers, salts, and plasticizer.     

Comparative study of solid-state reaction and sol-gel process for synthesis of Zr-doped Li<Subscript>0.5</Subscript>La<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> solid electrolytes

We investigated the synergistic influences of synthesis methods (solid-state reaction vs. sol-gel process) and Zr⁴⁺ doping on the structure and ionic conductivity of perovskite-structured Li_0.5La_0.5TiO₃ (LLTO) solid electrolytes. The lithium-ion conductivity of Li_0.5La_0.5Ti_1???x Zr _x O₃ ceramic specimens was evaluated as a function of x value and compared carefully between those two synthesis methods. Regarding the conductivity, sol-gel process is better for the synthesis of LLTO than solid-state reaction. As a result, the highest grain conductivity is obtained in the sol-gel-derived pure LLTO sample with x?=?0, reaching 1.10?×?10^?3 S?·?cm^?1. Partial substitution of Zr⁴⁺ enlarges the LLTO’s grain aggregate size and increases the total superficial area of aggregates. Consequently, Zr⁴⁺ substitution not only affects the grain (bulk) conductivity, but more importantly, also improves the grain boundary conductivity and the total conductivity. The highest total conductivity is 5.84?×?10^?5 S?·?cm^?1 with x?=?0.04 by sol-gel process.     

Synthesis and electrical conductivity of a new Ag<Subscript>6</Subscript>SnS<Subscript>4</Subscript>Br<Subscript>2</Subscript> superionic compound

The conditions of synthesizing a new Ag₆SnS₄Br₂ compound were studied. The crystallographic parameters of the unit cell were determined as follows: space group Pnma, a=6.67050(10) Å, b=7.82095(9) Å, c=23.1404(3) Å, and Z=4. The total electrical conductivity and its ionic component were measured by a dc probe method in the temperature range 210–380 K. Kinks in the conductivity curve and the differential thermogram of heating the alloy were revealed at 235 K. It was concluded that the mass and charge transfers in the compacted Ag₆SnS₄Br₂ alloy powder have an intragrain character.     

Crystal structure analysis of Li<Subscript>3</Subscript>PO<Subscript>4</Subscript> powder prepared by wet chemical reaction and solid-state reaction by using X-ray diffraction (XRD)

Lithium phosphate (Li₃PO₄) is one of the promising solid electrolyte materials for lithium-ion battery because of its high ionic conductivity. A crystalline form of Li₃PO₄ had been prepared by two different methods. The first method was wet chemical reaction between LiOH and H₃PO₄, and the second method was solid-state reaction between Li₂O and P₂O₅. Crystal structure of Li₃PO₄ white powder had been investigated by using an X-ray diffraction (XRD) analysis. The results show that Li₃PO₄ prepared by wet chemical reaction belongs to orthorhombic unit cell of β-Li₃PO₄ with space group Pmn2₁. Meanwhile, Li₃PO₄ powder prepared by solid-state reaction belongs to orthorhombic unit cell of γ-Li₃PO₄ with space group Pmnb and another unknown phase of Li₄P₂O₇. The impurity of Li₄P₂O₇ was due to phase transformation in solid state reaction during quenching of molten mixture from high temperature. Ionic conductivity of Li₃PO₄ prepared by solid-state reaction was ～3.10^?7 S/cm, which was higher than Li₃PO₄ prepared by wet chemical reaction ～4.10^?8 S/cm. This increasing ionic conductivity may due to mixed crystal structures that increased Li-ion mobility in Li₃PO₄.     

Investigation of ion transport in Li<Subscript>8</Subscript>ZrO<Subscript>6</Subscript> and Li<Subscript>6</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> solid electrolytes

Lithium ionic conductivity and spin-lattice relaxation rates were measured in Li₈ZrO₆ and Li₆Zr₂O₇ solid electrolytes. It was found that the Li₈ZrO₆ solid electrolyte undergoes a transition to the superionic state in the temperature range 673–703 K. It was shown that Li⁺ ions are mobile in particular lattice positions of the Li₆Zr₂O₇ phase, and that ionic conductivity is monotonic at an activation energy of 79.4 kJ/mol.     

Nano Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> as sulfur host for high-performance Li-S battery

S/Li₄Ti₅O₁₂ cathode with high lithium ionic conductivity was prepared for Li-S battery. Herein, nano Li₄Ti₅O₁₂ is used as sulfur host and fast Li⁺ conductor, which can adsorb effectively polysulfides and improve remarkably Li⁺ diffusion coefficient in sulfur cathode. At 0.5 C, S/Li₄Ti₅O₁₂ cathode has a stable discharge capacity of 616 mAh g^?1 at the 700th cycle and a capacity loss per cycle of 0.0196% from the second to the 700th cycle, but the corresponding values of S/C cathode are 437 mAh g^?1 and 0.0598%. Even at 2 C, the capacity loss per cycle of S/Li₄Ti₅O₁₂ cathode is only 0.0273% from the second to the 700th cycle. The results indicate that Li₄Ti₅O₁₂ as the sulfur host plays a key role on the high performance of Li-S battery due to reducing the shuttle effect and enhancing lithium ionic conductivity.     

Synthesis,thermal and electrical behavior of the superprotonic conductor phase in Rb<Subscript>3</Subscript>(HSeO<Subscript>4</Subscript>)<Subscript>2.5</Subscript>(H<Subscript>2</Subscript>PO<Subscript>4</Subscript>)<Subscript>0.5</Subscript> compound

The Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound was prepared and its thermal behavior and electric properties were investigated. The thermogravimetry (TGA) analysis and the differential scanning calorimetric (DSC) show the presence of a structural phase transition of the title compounds at 374 K which is confirmed by the variation of fp and σ_dc as a function of temperature. The complex impedance of the Rb₃(HSeO₄)_2.5(H₂PO₄)_0.5 compound has been investigated in the temperature range of 295–453 K and in the frequency range 209 Hz–1 MHz. The impedance plots show 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 Rp and constant phase elements CPE₁ in series with fractal capacity CPE₂. The frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. The conductivity dc follows the Arrhenius relation. The near value of activation energies obtained from the analysis of modulus, conductivity data, and circuit equivalent confirm that the transport is through the ion hopping mechanism, dominated by the motion of the H⁺ proton in the structure of the investigated materials.     

Effect of Al-Mo codoping on the structure and ionic conductivity of sol-gel derived Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript> ceramics

Al-Mo codoped Li₇La₃Zr₂O₁₂ ceramics with fine grain were prepared by sol-gel method. The influences of Al-Mo codoping on the structure, microstructure, and conductivity of Li₇La₃Zr₂O₁₂ were investigated by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and impedance spectroscopy. The cubic phase Li₇La₃Zr₂O₁₂ has been stabilized by partial substitution of Al for Li and Mo for Zr. Li_6.6-3yAl_yLa₃Zr_1.8Mo_0.2O₁₂ (0?≤?y?≤?0.1) has been sintered at 1040–1060 °C for 3 h. The liquid sintering facilitated its densification. The relative density of the composition with x?=?0.075 was approximately 96.4%. Results indicated that the Al-Mo codoped LLZO synthesized by sol-gel method effectively lowered its sintering temperature, accelerated densification, and improved the ionic conductivity.