Synthesis and structural,magnetic, and resonance properties of the LiCuFe<Subscript>2</Subscript>(VO<Subscript>4</Subscript>)<Subscript>3</Subscript> compound

Complex studies have been performed for the structural, static magnetic, and resonance properties of a new magnet LiCuFe₂(VO₄)₃ prepared by solid-phase synthesis. The temperature dependence of the susceptibility has an anomaly at temperature T_max = 9.6 K. At high temperatures, the LiCuFe₂(VO₄)₃ sample is in the paramagnetic state described by the Curie–Weiss law at T > 50 K and mainly determined by iron ions with effective magnetic moment μ_eff(exp) = 8.6μ_B per formula unit. At low temperatures, a long-range magnetic order is observed in the magnetic subsystem of the sample; the order is predominantly characterized by the antiferromagnetic exchange interaction and high frustration level. The exchange interaction parameters are estimated in a six-sublattice representation of the LiCuFe₂(VO₄)₃ magnet. It is shown that the LiCuFe₂(VO₄)₃ compound is an antiferromagnet with strong intrachain and frustrating interchain exchange interactions.     

Electrical properties and conduction mechanism in the sodium nickel diphosphate

The Na_3.6Ni_2.2(P₂O₇)₂ compound was obtained by the conventional solid-state reaction. The sample was characterized by X-ray powder diffraction and vibrational and impedance spectroscopy. The AC electrical conductivity and the dielectric relaxation properties of this compound have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 209 kHz–1 MHz and 564–729 K, respectively. Dielectric data were analyzed using complex electrical modulus M* at various temperatures. The peak positions ω _m of M″ spectra shift toward higher frequencies with increase in temperature. The AC conductivity data fulfill the power law. Application of the correlated barrier hopping model revealed that the ionic conduction takes place by single-polaron and bipolaron hopping processes.     

Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

AC electrical properties of the mixed crystal (NH4)3H(SO4)1.42(SeO4)0.58

The frequency dependence of the AC conductivity of (NH₄)₃H(SO₄)_1.42(SeO₄)_0.58 (NHSSe) has been presented in the temperature range (299-393 K). The conductivity data has been analysed in terms of two theoretical models: hopping over a potential barrier model and quantum-tunnelling model. Values of the exponent s, decrease from 1.08 to 0.91 with increasing temperature and the experimental data revel that the hopping model is the rate determining mechanism.     

AC conductivity and dielectric behavior of bulk Furfurylidenemalononitrile

AC conductivity and dielectric behavior for bulk Furfurylidenemalononitrile have been studied over a temperature range (293–333 K) and frequency range (50–5×10⁶ Hz). The frequency dependence of ac conductivity, σ_ac, has been investigated by the universal power law, σ_ac(ω)=Aω^s. The variation of the frequency exponent (s) with temperature was analyzed in terms of different conduction mechanisms, and it was found that the correlated barrier hopping (CBH) model is the predominant conduction mechanism. The temperature dependence of σ_ac(ω) showed a linear increase with the increase in temperature at different frequencies. The ac activation energy was determined at different frequencies. Dielectric data were analyzed using complex permittivity and complex electric modulus for bulk Furfurylidenemalononitrile at various temperatures.     

AC impedance studies on proton-conducting PAN : NH4SCN polymer electrolytes

Solid polymer electrolytes based on polyacrylonitrile (PAN) doped with ammonium thiocyanate (NH₄SCN) in different molar ratios of polymer and salt have been prepared by solution-casting method using DMF as solvent. The increase in amorphous nature of the polymer electrolytes has been confirmed by XRD analysis. A shift in glass transition temperature (T _g) of the PAN?:?NH₄SCN electrolytes has been observed from the DSC thermograms which indicates the interaction between the polymer and the salt. From the AC impedance spectroscopic analysis, the ionic conductivity has been found to increase with increasing salt concentration up to 30 mol% of NH₄SCN beyond which the conductivity decreases and the highest ambient temperature conductivity has been found to be 5.79?×?10^?3 S cm^?1. The temperature-dependent conductivity of the polymer electrolyte follows an Arrhenius relationship which shows hopping of ions in the polymer matrix. The dielectric loss curves for the sample 70 mol% PAN?:?30 mol% NH₄SCN reveal the low-frequency β-relaxation peak pronounced at high temperature, and it may be caused by side group dipoles. The ionic transference number of polymer electrolyte has been estimated by Wagner’s polarization method, and the results reveal that the conductivity species are predominantly ions.     

Enhancement of the electrochemical properties with the effect of alkali metal systems on PEO/PVdF-HFP complex polymer electrolytes

Polymer blend electrolytes based on poly(ethylene oxide) (PEO) and poly(vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) were prepared by using different lithium salts LiX (X = ClO₄, BF₄, CF₃SO₃, and N [CF₃SO₂]₂) using solution casting technique. To confirm the structure and complexation of the electrolyte films, the prepared electrolytes were subjected to X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analysis. Alternating current (AC) impedance analysis was performed for all the electrolyte samples at various temperatures from 303 to 343 K. The result suggests that among the various lithium salts, LiN[CF₃SO₂]₂-based electrolytes exhibited the highest ionic conductivity at 8.20 × 10^?4 S/cm. The linear variation of the ionic conductivity of the polymer electrolytes with increasing temperature suggests the Arrhenius-type thermally activated process. Activation energies were found to decrease when doping with lithium imide salt. The dielectric behavior has been analyzed using dielectric permittivity (ε*), electric modulus (M*), and dissipation factor (tanδ) of the samples. Cyclic voltammetry has been performed for the electrolyte films to study their cyclability and reversibility. Thermogravimetric and differential thermal analysis (TG/DTA) was used to ascertain the thermal stability of the electrolytes, and the porous nature of the electrolytes was identified using scanning electron microscopy via ion hopping conduction. Surface morphology of the sample having maximum conductivity was studied by an atomic force microscope (AFM).     

Li<Superscript>+</Superscript> ion conductivity and transport properties of LiYP<Subscript>2</Subscript>O<Subscript>7</Subscript> compound

A lithium yttrium diphosphate LiYP₂O₇ was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. The infrared and Raman spectrum of this compound was interpreted on the basis of P₂O₇ ^4? vibrations. The AC conductivity was measured in the frequency range from 100 to 10⁶ Hz and temperatures between 473 and 673 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The Cole–Cole diagram determined complex impedance for different temperatures. The angular frequency dependence of the AC conductivity is found to obey Jonscher’s relation. The temperature dependence of σ _AC could be described in terms of Arrhenius relation with two activation energies, 0.87 eV in region I and 1.36 eV in region II. The study of temperature variation of the exponent(s) reveals two conduction models: the AC conduction dependence upon temperature is governed by the correlated barrier hopping (CBH) model in region I (T < 540 K) and non-overlapping small polaron tunneling (NSPT) model in region II (T > 540 K). The near value of activation energies obtained from the equivalent circuit and DC conductivity confirms that the transport is through ion hopping mechanism dominated by the motion of the Li⁺ ion in the structure of the investigated material.     

Electrical conductivity and dielectric relaxation behavior of AgFeP2O7 compound

In the present study, AgFeP₂O₇ was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. Not only were the impedance spectroscopy measurements of our compound carried out from 209 Hz to 5 MHz over the temperature range of 553 K–698 K but its AC conductivity as well as the dielectric relaxation were evaluated. Impedance measurements show AgFeP₂O₇ an ionic conductor being the conductivity 1.04?×?10^–?5(Ω^–?1cm^–?1) at 573 K. The conductivity and modulus formalisms provide nearly the same activation energies for electrical relaxation of mobile ions revealing that transport properties in this material appear to be due to an ionic hopping mechanism dominated by the motion of the Ag⁺ ions along tunnels presented in the structure of the investigated material.     

Magnetic and electric studies of a new Co(II) perovskite-like material

Structural phase transitions in the perovskite-like material [(CH₄)₁₂(NH₃)₂]CoCl₄ have been observed using differential thermal scanning. The material shows an order-disorder transition at T ₁ = 396 ± 5 K with entropy, (ΔS ₁) = 12.8 J/mole/K. A "chain melting" transition with a major endothermic peak at T ₂ = 337 ± 3 K and a minor one at T ′ = 316 ± 2 K, has total entropy ΔS = 28 J/mole/K. At low temperatures, the transitions at T ₃ = 288 ± 3 K and at T ₄ = 188 ± 3 K, have entropies of ΔS ₃ = 14.4 J/mole/K and ΔS ₄ = 2.6 J/mole/K respectively. AC magnetic susceptibility in the temperature range 78-290 K, in a magnetic field of 160 A/m and at a frequency of 320 Hz is presented. The results indicate changes in symmetry at 188 K. Dielectric permittivity has been studied as a function of temperature in the range 300-430 K and frequency range (60 Hz-100 kHz), confirming the observed transitions. The dielectric permittivity reflects rotational and conformational transition for the material. The variation of the real part of the conductivity with temperature is thermally activated with different activation energies in the range of ionic hopping. The temperature dependence of the dc conductivity and that of the ions hopping rate have indicated that the concentration of mobile ions is independent of temperature. The dependence of the conductivity on frequency follows the universal power law, <artwork name="GPHT31040ei1"> in the temperature range 340 K<T<390 K. Values 0 <s ₁ <1 dominate at low frequency and correspond to translational hopping motion and values 1<s ₂<2 dominate at high frequencies and correspond to well localized hopping and/or reorientational motion. For T > 396 K, the AC conductivity was fitted to <artwork name="GPHT31040ei2"> with 0<s<1. Comparison with the corresponding Cu-containing material is discussed.     

Investigation on (EC/DMC)(70−x)wt% to LiBETI(x)wt% impact on PVdF-co-HFP/octadecylamine-MMT(montmorillonite) nano clay composite electrolytes

The composition dependence of plasticizer (ethylenecarbonate(EC)/dimethyl carbonate(DMC))_(70?x)wt% to Lithium bis(perfluoroethanesulfonyl)imide(LIBETI)_(x)wt% salt (where x?=?1.5, 3.0, 4.5, 6.0 wt%) on PVdF-co-HFP (25 wt%)/surface modified octadecylamine containing montmorrillonite (ODA-MMT) nano clay (5 wt%) matrix has been investigated by AC impedance, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and dielectric and cyclic voltammetry studies. The enhanced conductivity 2.1?×?10^?5 Scm^?1 is noted in salt rich phase (EC/DMC)_(70–6)wt% /LiBETI_(x=6)wt% (VK4). In XRD, 2θ at 20.9° confirms β-phase. In FTIR studies, vibrational bands 838, 522 and 611 cm^?1 confirm β-phase of PVdF due to clay intercalation. In DSC studies, the melting of α-phase crystallites is noted between 140–150 °C. In SEM studies, one of the membranes presents fern leaf texture confirming swelling of clay. The increase in dielectric constant and dielectric loss with decrease in frequency is attributed to high contribution of charge accumulation at the electrode–electrolyte interface. In cyclic voltammetry studies, salt-rich phase membrane (VK4) shows good cyclability than other membranes.     

Study of complex impedance spectroscopic properties of the KFeP2O7 compound

The KFeP₂O₇ compound was prepared by the conventional solid-state reaction. The sample was characterized by X-ray powder diffraction. The AC electrical conductivity and the dielectric relaxation properties of this compound have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures, 200 Hz–5 MHz and 553–699 K, respectively. Both impedance and modulus analysis exhibit the grain and grain boundary contribution to the electrical response of the sample. The temperature dependence of the bulk and grain boundary conductivity were found to obey the Arrhenius law with activation energies Eg?=?0.94 (3)?eV and Egb?=?0.89 (1)?eV. The grain-and-grain boundary conductivities at 573 K are 1.07?×?10^?4 and 1.16?×?10^?5 (Ω^?1 cm^?1). The scaling behavior of the imaginary part of the complex impedance suggests that the relaxation describes the same mechanism at various temperatures. The near value of the activation energies obtained from the equivalent circuit, conductivity data, and analysis of M″ confirms that the transport is through ion hopping mechanism.     

AC conductivity and mechanism of conduction study of lithium barium pyrophosphate Li<Subscript>2</Subscript>BaP<Subscript>2</Subscript>O<Subscript>7</Subscript> using impedance spectroscopy

The Li₂BaP₂O₇ compound has been obtained by the conventional solid-state reaction and characterized by X-ray powder diffraction. The title material crystallizes in the monoclinic system with C2/c space group. Electrical properties of the compound have been studied using complex impedance spectroscopy in the frequency range 200 Hz–5 MHz and temperature range 589–724 K. Temperature dependence of the DC conductivity and modulus was found to obey the Arrhenius law. The obtained values of activation energy are different which confirms that transport in the titled compound is not due to a simple hopping mechanism. AC conductivity measured follows the power-law dependence σ _AC?～?ω ^s typical for charge transport. Therefore, the experimental results are analyzed with various theoretical models. Temperature dependence of the power law exponent s strongly suggests that tunneling of large polarons is the dominant transport process.     

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.     

Studies on structural and electrical properties of Mg<Subscript>0. 5+y</Subscript> (Zr<Subscript>2-y</Subscript>Fe<Subscript>y</Subscript>) <Subscript>2</Subscript> (PO<Subscript>4</Subscript>) <Subscript>3</Subscript> ceramic electrolytes

The sample of Mg_{0. 5+y} (Zr_1-y Fe_y) ₂ (PO₄) ₃ (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg_0.5Zr (PO₄) ₃. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe³⁺ with Zr⁴⁺ in the Mg_0.5Zr (PO₄) ₃ structure was introduced as an extrainterstitial Mg²⁺ ion in the modified structured. The compound of Mg_0.5+y (Zr_1-y Fe_y)₂(PO₄)₃ with y?=?0.4 gives a maximum conductivity value of 1.25?×?10^?5 S cm^?1 at room temperature and 7.18?×?10^?5 S cm^?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ _ac (ω)?=?σ _o ? +?Aω ^α . The charge carrier concentration and mobile ion concentration increases with increase of Fe³⁺ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg²⁺ ions.     

AC conductivity and dielectric properties of bulk tungsten trioxide (WO3)

AC conductivity and dielectric properties of tungsten trioxide (WO₃) in a pellet form were studied in the frequency range from 42 Hz to 5 MHz with a variation of temperature in the range from 303 K to 463 K. AC conductivity, σ_ac(ω) was found to be a function of ω^s where ω is the angular frequency and s is the frequency exponent. The values of s were found to be less than unity and decrease with increasing temperature, which supports the correlated barrier hopping mechanism (CBH) as the dominant mechanism for the conduction in WO₃. The dielectric constant (ε′) and dielectric loss (ε″) were measured. The Cole–Cole diagram determined complex impedance for different temperatures.     

Synthesis,refinement of the structure,and AC conductivity behavior of sodium lithium orthonavadates

The Na _x Li_1-x CdVO₄ (x = 0.5, 1) orthovanadates were prepared using a solid-state reaction method. The x-ray diffraction patterns (XRDP) of both materials reveal the formation of the Na₂CrO₄ structure. Vibrational study confirms the existence of [VO₄]^3? group. Electrical measurements of our compounds have been investigated using complex impedance spectroscopy (CIS) in the frequency and temperature range 209 Hz–1 MHz and 589–703 K, respectively. Nyquist plots reveal the presence of tow contributions, an equivalent circuit was proposed. DC conductivity shows electrical conduction in the material as a thermally activated process. The AC conductivity is explained using the non-overlapping small polaron tunneling (NSPT) conduction mechanism. A relationship between crystal structure and ionic conductivity was established and discussed.     

Electrical conduction mechanism in nanocrystalline CdTe (nc-CdTe) thin films

The present paper reports the electrical characterization of nc-CdTe thin films in different temperature ranges. Thin films of nc-CdTe are deposited on the glass substrates by Physical Vapor Deposition (PVD) using the Inert Gas Condensation (IGC) method. The Transmission Electron Microscopy (TEM) studies are made on the CdTe nanocrystals. The surface morphology and structure of the thin films are studied by the Scanning Electron Microscope (SEM) and X-Ray Diffraction (XRD) measurements. Dark conductivity measurements are made on the nc-CdTe thin films in the temperature range 110–370 K in order to identify the conduction mechanism in this temperature range. The obtained results reveal three distinct regions at high, low, and sufficiently low temperature regions with decreasing activation energies. The analysis of the high temperature conductivity data is based on the Seto’s model of thermionic emission. At very low temperatures, dc conductivity (σ _d) obeys the law: lnσT ^1/2∝T ^?1/4, indicating variable-range hopping in localized states near the Fermi level. The density of the localized states N(E _F) and various other Mott’s parameters like the degree of disorder (T _O), hopping distance (R), and hopping energy (W) near the Fermi level are calculated using dc conductivity measurements at low temperatures. Carrier type, carrier concentration, and mobility are determined from the Hall measurements. The transient photoconductivity decay measurements are performed on the nc-CdTe thin films at different intensities in order to know the nature of the decay process.     

A.C. hopping conductivity in VO2

The a.c. hopping conductivity is investigated in VO₂ between 25 kHz and 10⁹ Hz as a function of temperature. The ω^s law with 0.7 < s < 1 is observed over a large range of frequencies, which is interpreted in terms of electron hopping among a wide distribution of localized levels. A detailed analysis of the results leads to the conclusion that two hopping processes are involved: a low frequency process, thermally excited with an activation energy of 30 meV, with a cutoff frequency of about 10⁸ Hz, and a high frequency process, extending to very high frequencies and nearly temperature independent.     

57Fe-Mössbauer study of electrically conducting barium iron vanadate glass after heat treatment

Local structure and thermal durability of semiconducting xBaO·(90?? x)V₂O₅ · 10Fe₂O₃ glasses (x = 20, 30 and 40), NTA glass ^TM, before and after isothermal annealing were investigated by ⁵⁷Fe-Mössbauer spectroscopy and differential thermal analysis (DTA). An identical isomer shift ( $\mathit{\delta}$ ) of 0.39 ± 0.01 mm s^???1 and a systematic increase in the quadrupole splitting (Δ) were observed from 0.70 ± 0.02 to 0.80 ± 0.02 mm s^???1 with an increasing BaO content, showing an increase in the local distortion of Fe^IIIO₄ tetrahedra. From the slope of the straight line in the T _g–Δ plot of NTA glass ^TM, it proved that Fe^III plays a role of network former. Large Debye temperature (Θ _D) values of 1000 and 486 K were respectively obtained for 20BaO · 70V₂O₅ · 10Fe₂O₃ glass before and after isothermal annealing at 400°C for 60 min, respectively. This result also suggests that Fe^III atoms constitute the glass network composed of tetrahedral FeO₄, tetrahedral VO₄ and pyramidal VO₅ units. The electric conductivity of 20BaO · 70V₂O₅ · 10Fe₂O₃ glass increased from 1.6 × 10^???5 to 5.8 × 10^???2 S cm^???1 after isothermal annealing at 450°C for 2,000 min. These results suggest that the drastic increase in the electric conductivity caused by heat treatment is closely related to the structural relaxation of the glass network structure.