Effect of Zn–Ti double substitution on the electrical properties of Bi4V2O11

New samples of the Bi₂Zn_0.1–xTi_xV_0.9O_5.35+x; 0.02 ≤ x ≤ 0.08 system have been synthesized through a standard solid-state reaction route. XRD analysis and differential thermal analysis have been used to characterize the phase structure of samples. The γ′ phase is stabilized to room temperature in all investigated samples. The electrical properties of the BIZNTIVOX system have been studied by using AC impedance spectroscopy. An AC impedance response as a function of frequency (20 Hz–1 MHz) has been used to investigate the electrical conductivity and the dielectric permittivity in the temperature range of 150 °C–700 °C. In this temperature range, the phase transition γ′ to γ has been observed in all the compositions studied. AC impedance spectroscopy indicates that the resistance of samples decreases with increase of temperature. The ionic conductivity of samples appeared as a two-line region in Arrhenius dependence. At 300 °C, the highest ionic conductivity is shown by the composition x = 0.05 (σ₃₀₀ = 1.35 × 10^?4 S cm^?1).     

Effect of Cu–Al double substitution on the electrical properties of Bi4V2O11

Bi₂Cu_0.1?xAl_xV_0.9O_5.35?x/2?δ, 0.02 ≤ x ≤ 0.08, were synthesized by standard solid-state reaction route. Structural and electrical properties of samples are characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), Fourier transform infrared (FT-IR) and alternating current (AC) impedance spectroscopy. The tetragonal γ′ phase structure is preserved to room temperature with compound x = 0.02. The stabilization of β orthorhombic phase is observed for compositions 0.04 ≤ x ≤ 0.05. As the Al content increases, the monoclinic α phase is evidenced for materials 0.06 ≤ x ≤ 0.08. The electrical investigation of Bi₂Cu_0.1?xAl_xV_0.9O_5.35?x/2?δ system has been performed in the frequency range from 20 Hz to 1 MHz using AC impedance spectroscopy. The impedance spectra indicate the two semicircle arcs associated with the bulk and grain boundary resistances at temperature below ～450 ^○C. The conductivity generally changes when Al is substituted. The highest conductivity at 300 ^○C (σ = 2.55 × 10^?4 S cm^?1) is shown for x = 0.02.     

Study on electrical conductivity and phase transition in singly doped BIPBVOX (Bi2V1−xPbxO5.5−x/2) solid electrolyte

Samples of bismuth lead vanadium oxide (BIPBVOX) (Bi₂V_1–xPb_xO_5.5–x/2) singly substituted system in the composition range 0.05 ≤ x ≤ 0.20 were prepared by sol–gel synthesis route. Structural investigations were carried out by using a combination of differential thermal analysis (DTA) and powder X-ray diffraction (PXRD) technique. Energy dispersive X-ray spectroscopy analysis (EDXA) of doped samples was carried out to predict the sample purity and doping concentration. Transitions, α?β, β?γ and γ′?γ were detected by XRD, DTA and variation in the Arrhenius plots of conductivity. The ionic conductivity was measured by AC impedance spectroscopy. The solid solutions with composition x ≤ 0.07 undergo α?β phase transition, at 329 °C and β?γ phase transition at 419 °C. The highly conducting γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.17 whose thermal stability increases with Pb content. At 300 °C, the highest value of conductivity 6.234 × 10^?5 S cm^?1 was obtained for composition x = 0.15 and at 600 °C the highest value of conductivity 0.65 S cm^?1 is observed for x = 0.17. AC impedance plots reveal that the conductivity is mainly due to the grain contribution to oxide ion conductivity.     

Study on phase stabilization and electrical performance of BICO0.20−xNIxVOX solid electrolyte

BICO_0.20?xNI_xVOX solid electrolyte in the composition range 0 ≤ x ≤ 0.20 was synthesized by standard solid-state reactions. The influence of Ni substitution for Co on the relationship between the phase stabilization and electrical performance was investigated by means of X-ray powder diffraction (XRPD), differential thermal analysis (DTA) and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x ≥ 0.13 whose thermal stability increases with Ni content. On the other hand, complex plane plots of impedance suggested a major contribution of polycrystalline grain interiors to the overall electrical conductivity and the fastest oxygen-vacancy diffusion in the perovskite vanadate layers at x = 0.13. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. However, a maximum ionic conductivity at lower temperatures (～2.56 × 10^?4 S cm^?1 at 300 °C) was observed for the composition with x = 0.13.     

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.     

Influence of calcium substitution on the phase transition and ionic conductivity in BICAVOX oxide ion conductor

Samples of Bi₄Ca _x V_{2? x} O_{11?(3 x /2)?δ} in the composition range 0.07 ≤ x ≤ 0.30 were prepared by conventional solid state reactions. The stability of different phases as a function of composition was analysed by X-ray powder diffraction, FT-IR spectra, differential thermal analysis and AC impedance spectroscopy. For the compositions x ≤ 0.10, monoclinic α-phase structure is retained at room temperature. For x = 0.13, orthorhombic β-phase is observed, whereas for x ≥ 0.17, high O^2?conducting tetragonal γ-phase is stabilised. However, the highest ionic conductivity σ_300°C = 3.27 × 10^?4 S cm^?1 was observed for x = 0.17. This higher value of conductivity of the substituted compound as compared to the parent compound can be attributed to the increased oxygen ion vacancies generated as a result of cation doping. AC impedance spectroscopy reveals the fact that this ionic conductivity is mainly due to the grain contribution.     

Electrical properties of MWCNT-composite (Se80Te20)100−xAgx (0 ≤ x ≤ 4) chalcogenide glasses

This article describes the preparation of multi-walled carbon nanotube (MWCNT) chalcogenide glass composite by the melt-quenching technique. MWCNT composite (Se₈₀Te₂₀)_100?xAg_x (0 ≤ x ≤ 4) bulk samples are characterized by the XRD, SEM and EDX. The electrical measurements were carried out in the temperature range of the 308-388 K. Cole–Cole plot has been used to determine the electrical conductivity at room temperature. It has been observed that MWCNT chalcogenide composite have higher value of electrical conductivity than pure glass. The results have been discussed on the basis of increased ionic conductivity (Ag⁺ ions) in MWCNT doped (Se₈₀Te₂₀)_100?xAg_x (0 ≤ x ≤ 4) bulk samples.     

CO(III)–NI(II) double substituted bismuth vanadate: synthesis,phase stabilization,and structural and electrical characterization

Samples of Co–Ni double substituted bismuth vanadate, BICO_0.20?x NI _x VOX (Bi₄Co_0.20???x ^(III)Ni _x ^(II)V_1.8O_{10.8???(x/2)???δ} ;0?≤?x?≤?0.20) were synthesized by standard solid state reactions. The influence of Ni substitution for Co on phase stabilization and oxide-ion performance have been investigated using X-ray powder diffraction, differential thermal analysis, and AC impedance spectroscopy. The high conducting γ′-phase was effectively stabilized at room temperature for compositions with x?≥?0.13 whose thermal stability increases with Ni content. The complex plane plots of impedance were typically represented at temperatures below 380 °C, suggesting a major contribution of polycrystalline grains to the overall electrical conductivity. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. Interestingly, the maximum ionic conductivity at lower temperatures (～2.56?×?10^?4 S cm^?1 at 300 °C) was observed for the composition with x?=?0.13. However, a good agreement was generally found between the values of electrical conductivity and corresponding activation energies of conduction.     

Correlation between phase structure and electrical conduction in BISNVOX system for intermediate temperature solid oxide fuel cells (IT-SOFC)

Samples of Sn⁴⁺-substituted bismuth vanadate, formulated as Bi₄Sn _x V_{2? x} O_{11?( x /2)? δ} in the composition range 0.07 ≤ x ≤ 0.30, were prepared by standard solid-state reactions. Sample characterization and the principal phase transitions (α ? β, β ? γ and γ′ ? γ) were investigated by FT-IR spectroscopy, X-ray powder diffraction, differential thermal analysis (DTA) and AC impedance spectroscopy. For composition x = 0.07, the α ? β and β ? γ phase transitions were observed at temperatures of 451 and 536°C, respectively. DTA thermograms and Arrhenius plots of conductivities revealed the γ′ ? γ phase transition at 411 and 423°C for x = 0.20 and 0.30, respectively. AC impedance plots showed that conductivity is mainly due to the grain contribution, which is evident in the enhanced short-range diffusion of oxide ion vacancy in the grains with increasing temperature. The highest ionic conductivity (5.03 × 10^?5 S cm^?1 at 300°C) was observed for the x = 0.17 solid solution with less pronounced thermal hysteresis.     

Electrical characterization of porous La-doped BaSnO<Subscript>3</Subscript> using impedance spectroscopy

A few compositions in the system Ba_1???x La _x SnO₃ (x?=?0.00, 0.01, 0.05, and 0.10) have been synthesized via the solid state ceramic route. The synthesized powders have been characterized using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, Raman spectroscopy, Fourier transformation infrared, thermogravimetrical analysis, and differential thermal analysis techniques. The powder X-ray diffraction pattern of the samples confirms the formation of a single-phase solid solution only up to 0.50?≤?x. It was found that all the samples have a cubic crystal structure. The electrical properties of La-modified BaSnO₃ were studied using ac impedance spectroscopy technique over a wide range of temperatures (50–650 °C) in the frequency range of 10 Hz–13 MHz. The complex impedance plots above 300 °C show that total impedance is due to the contributions of grain and grain boundaries. The resistance of these contributions has been determined. Variation of these resistances with temperature shows the presence of two different regions with different slopes. The nature of the variation of conductivity of the grain and grain boundaries is different in different regions. Based on the value of activation energy, it is proposed that conduction via hopping of doubly ionized oxygen vacancies (V_O ^??) is taking place in the temperature region of 300–450 °C, whereas in the temperature region of 450–650 °C, it is due to proton, i.e., OH^? ions, hopping.     

Influence of Gd3+ and Dy3+ co-doping and sintering regime on enhancement of electrical conductivity of ceria-based solid electrolyte

In order to improve the conductivity of ceria-based solid electrolytes, effect of co-doped Gd³⁺ and Dy³⁺ was evaluated. For this purpose, nano-crystalline Gd_0.2???x Dy _x Ce_0.8O_1.9 powders with various composition ranges (x?=?0.05, 0.1, 0.15, 0.2) were initially synthesized by high-energy milling method. The effect of micro-structural evolution and co-doping on electrical properties of the dense sintered samples fabricated by two-step sintering and conventional sintering of the synthesized powders were investigated. Electrical conductivity of the samples was discussed based on the results obtained by AC impedance spectroscopy at temperatures in the range of 300–700 °C. The co-doping and sintering regime were found to significantly influence the conductivity of the electrolytes. The electrical conductivity of the co-doped samples depends on Dy³⁺ content and the maximum conductivity obtained by 0.15 mol% Dy and 0.05 mol% Gd. The conductivity of Gd_0.2???x Dy _x Ce_0.8O_1.9 (x?=?0.15) was 0.03 S/cm at 700 °C. A thorough discussion was made, based on the present experimental data.     

Synthesis,phase stability and oxide ion conductivity of Ce(IV)–Cd(II) double substituted bismuth vanadate

Bi₄V₂O_11-δ has been doped with Ce and Cd to study double substitution. The system with various dopant concentrations (0.07 ≤ x ≤ 0.30) was prepared by the standard solid-state reaction method. The correlation between the polymorphism and oxide ion performance was well investigated as a function of temperature and composition with the help of thermal analysis, X-ray diffraction (XRD) and AC impedance spectroscopy. From XRD results it is seen that the high oxide ion conducting tetragonal γ-phase is stabilized for x = 0.17. For the compositions x ≤ 0.10, monoclinic α-phase is retained at room temperature with clear evidence for two successive phase transitions α ? β and β ? γ. For x = 0.13, β ? γ phase transition is seen. However, the existence of order–disorder, γ' ? γ transition was confirmed for x = 0.17. It is seen that the highest low-temperature ionic conductivity at 320 °C is 3.19 × 10^?4 S cm^?1 which was observed for x = 0.17.     

Structural and transport properties of Li-intercalated vanadium pentoxide nanocrystalline films

The X-ray diffraction (XRD), transmission electron microscopy, density, electrical and thermoelectric power (TEP) properties of nanocrystalline Li _x V₂O₅ ? nH₂O xerogel films (0 ≤ x ≤ 22 mol.%) were investigated. The films were produced by the sol–gel technique (colloidal route), which was used to enable high-purity, uniform preparation. The relative intensity of the (002) XRD line increased with increasing Li content. The particle size was found to be about 6.0 nm. Electrical conductivity and thermoelectric power were measured parallel to the substrate surface in the temperature range 300–480 K for the as-prepared films. The electrical conductivity showed that all the samples were semiconductors and that conductivity increased with increasing Li content. The conductivity of the present system was primarily determined by hopping carrier mobility, which was found to vary from 6.81 × 10^?6 to 0.33 × 10^?6 cm² V^?1 s^?1 at 380 K. The carrier density was evaluated to be 8.73 × 10¹⁹–1.118 × 10²¹ cm^?3. The conduction was confirmed to obey non-adiabatic small polaron hopping. The thermoelectric power, or Seebeck effect, increased with increasing Li content. The results obtained indicate an n-type semiconducting behavior within the temperature range investigated.     

Effect of iron doping at Mn-site on complex impedance spectroscopy properties of Nd0.67Ba0.33MnO3 perovskite

The effect of Fe-doping at Mn-site on the structural and electrical properties of Nd_0.67Ba_0.33Mn_1?xFe_xO₃ (0 ≤ x ≤ 0.05) perovskites has been investigated. X-ray diffraction patterns show that the structural parameters change slightly due to the fact that the Fe³⁺ ions replacing the Mn³⁺ have similar ionic radius. The electrical properties of these samples have been investigated using complex impedance spectroscopy technique. a function of the frequency at different temperatures. When increasing the Fe-content, a decrease of dc conductivity was observed throughout the whole explored temperature range and the deduced activation energy values are found to increase from 128 meV for x = 0 to 166 meV for x = 0.05. The curves of the imaginary part of impedance (Z″) show the presence of relaxation phenomenon in our samples. The complex impedance spectra show semicircle arcs at different temperatures and an equivalent circuit of the type of R_g + (R_gb//C_gb) has been proposed to explain the impedance results.     

Effect of Ni(II) substitution on phase stabilization electrical properties of BICo(III)VOX.20 oxide-ion conductor

The BICO_0.20–xNI_xVOX solid electrolyte was synthesized by the standard solid-state reaction. The effect of Ni(II) substitution for Co(III) on phase stabilization and oxide-ion performance has been investigated in the compositional range 0?≤?x?≤?0.20 using X-ray powder diffraction, differential thermal analysis and AC impedance spectroscopy. The highly conductive γ′-phase was effectively stabilized at room temperature for compositions with x?≥?0.13 whose thermal stability increases with Ni content. The complex plane plots of impedance were typically represented at temperatures below 380?°C, suggesting a major contribution of polycrystalline grains to the overall electrical conductivity. The dielectric permittivity measurements revealed the fact that suppression of the ferroelectric transition is compositionally dependent. Interestingly, the maximum ionic conductivity at lower temperatures (~2.56?×?10^?4?S^?cm^?1 at 300?°C) was observed for the composition with x?=?0.13. The variation of low-temperature conductivity with Ni content was accompanied with a general drop in the corresponding values of ΔE_LT. However, the local minimum high-temperature conductivity, σ₆₀₀?°C?~?2.26?×?10^?2?S^?cm^?1 for x?=?0.10, coupled with a local maximum value of ΔE_HT?~?0.48?eV was attributed to an increased defect trapping effect correlated with the V(V)?→?V(IV) reduction at elevated temperatures.     

Study of complex impedance spectroscopic properties of the α-NaCuPO<Subscript>4</Subscript> compound

In the present study, α-NaCuPO₄ compound was prepared by solid-state reaction method and characterized by X-ray powder diffraction and infrared spectroscopy. The AC electrical conductivity and dielectric relaxation properties of this compound have been investigated by means of impedance spectroscopy measurements over a wide range of frequencies and temperatures 209 Hz–1 MHz and 598–708 K, respectively. Both impedance and modulus analysis exhibit the grain and grain boundary contribution in the electrical response of the sample. It was found that the data of the AC measurements follow the overlapping large polaron tunneling model and the model’s parameters were determined.     

Effect of laser irradiation on the electrical properties of dysprosium doped LiCo-Ferrite

The effect of laser irradiation on the electrical properties of Li_0.5+z Co _z Dy _x Fe_2.5?2z?x O₄ ferrite (0.0 ≤ x ≤ 0.2, z = 0.1) has been studied in the temperature range 300 K ≤ T ≤ 750 K at frequencies of 10 kHz?5 MHz, using a LIMO-IR laser diode, at a wavelength of 808 nm. It was found that laser irradiation increases the polarization, the resistivity and the paramagnetic region. As the result of electronic rearrangement and lattice defects, small polorons and clusters were created. The doping of LiCo-Ferrite by Dy³⁺ increases both the AC and DC resistance of the investigated material. The variation of the AC and DC resistance with the Dy-content (x) obeys the following correlations R _ac/100 = 50x ²+4x+0.005 and R _dc/1000 = 31x ²+0.099x+0.09, respectively. A peculiar behaviour was obtained for the sample with Dy-content x = 0.075, as the resistance notably decreases. The applicable result is that laser irradiation increases the resistance of LiCo-ferrite by about 17% while its doping by dysprosium at x = 0.15 increases the resistance by about 23%. Its value is nearly stable for the temperature range from 340 to 480 K.     

Impedance spectroscopy of Gd-doped BiFeO3 multiferroics

The polycrystalline Bi_1?x Gd _x FeO₃ (BGFO) (x=0.0, 0.05, 0.10, 0.15, 0.20) materials were synthesized by a solid-state reaction (mixed oxide) technique. Preliminary X-ray structural analysis of the compounds confirmed the formation of single-phase polycrystalline samples. Room temperature scanning electron micrographs of the materials revealed the size, type and distribution of grains on the surface of samples. Studies of impedance, electrical modulus and electric conductivity of the materials in a wide frequency (10–1000 kHz) and temperature (30–500 ^°C) range using a complex impedance spectroscopy technique have provided considerable vital information on contribution of grains, grain boundary and interface in these parameters. A strong correlation between these electrical parameters and microstructures (bulk, grain boundary, nature of charge carrier, etc.) of the materials was established. The frequency dependence of electric modulus and impedance of the material shows the presence of non-Debye type of relaxation.     

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.