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.     

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.     

AC and DC conductivity study of LiH<Subscript>2</Subscript>PO<Subscript>4</Subscript> compound using impedance spectroscopy

The lithium dihydrogen phosphate LiH₂PO₄ has been investigated by X-ray powder diffraction, scanning electron microscopy (SEM), and electrical impedance spectroscopy. The Rietveld refinements based on the XRD patterns show that the compound is crystallized in the orthorhombic system with Pna2₁ space group, and the refined unit cell parameters are a = 6.2428 Å, b = 7.6445 Å, and c = 6.873 Å. The electrical properties were studied using complex impedance spectroscopy as a function of frequency (10⁴–10⁷ Hz) at various temperatures (300–400 K). The Nyquist plots are well fitted to an equivalent circuit consisting of a series of combination of grains and inhomogeneous electrode surface effect. The frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. Moreover, the near value of the activation energies obtained from the equivalent circuit and analysis of M″ confirms that the transport is through ion hopping mechanism dominated by the motion of the proton in the structure of the investigated material.     

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 properties and conductivity mechanism of LiCuFe2(VO4)3

This paper reports conduction mechanism in LiCuFe₂(VO₄)₃ over a wide range of temperatures (300 to 712 K) and frequencies (209 Hz to 5 MHz). The DC conductivity of the material is thermally activated with activation energy about 0.66 eV. In LiCuFe₂(VO₄)₃, the electrical conductivity is probably due to the hopping of alkali lithium ion along the channel [001]. Temperature dependence of AC conductivity is studied at different frequencies. Frequency exponent s is found to decrease with increase in temperature. The results have been explained on the basis of correlated barrier hopping (CBH) model. Numerical calculations agree well with experimental results. The results show that the frequency and temperature-dependent behavior of AC conductivity of the studied materials are predominantly due to single polaron hopping.     

AC conduction mechanism of the zinc potassium diphosphate

Zinc potassium pyrophosphate K₂ZnP₂O₇ was synthesized using the conventional solid-state reaction. X-ray powder diffraction analysis proves the formation of a pure phase which crystallizes in the tetragonal system. The electrical conductivity and modulus characteristics of the system have been investigated in the temperature and the frequency range 614–718 K and 200 Hz–1 MHz, respectively, by means of impedance spectroscopy. The alternating current (AC) conductivity for grain contribution follows the universal Jonscher’s power law. The frequency exponent s is temperature independent and equal to 0.8. The QMT model was proposed to be the most suitable model to characterize the electrical conduction mechanism in the titled sample. Dielectric data were analyzed using complex electrical modulus M* at various temperatures. The bulk relaxation time was found from the peaks position of the above spectra and the thermodynamic parameters were also found using the Eyring theory.     

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.     

Crystal structure and electrical properties study of 4-aminopyridinium chloridobismuthate (III) (C5N2H7)4.HBi2Cl11

The crystal structure of (C₅N₂H₇)₄.HBi₂Cl₁₁ has been determined at room temperature by single crystal X-ray diffraction. The compound crystallizes in the triclinic system with Pī space group. The crystal structure consists of two asymmetric inequivalent molecules of 4-aminopyridinium and anionic HBi₂Cl₁₁ chains. The HBi₂Cl₁₁ anionic chains stacked along the a-axis are formed with Bi₂Cl₁₁ dimers connected to each other via hydrogen atoms. The crystal packing is stabilized with N–H...Cl hydrogen bonds connecting aminopyridinium units to the HBi₂Cl₁₁ anionic chains. The title compound exhibits an order–disorder phase transition at 338 K. The AC electrical conductivity properties of (C₅N₂H₇)₄.HBi₂Cl₁₁ compound have been investigated by means of impedance spectroscopy measurements over wide ranges of frequencies and temperatures, 200 Hz to 5 MHz and 303 to 418 K, respectively. Detailed analysis of the impedance spectrum suggests that the electrical properties of the material are strongly temperature dependent. The frequency-dependent conductivity data were fitted in the Jonscher's law: $ \sigma \left( \omega \right) = \sigma (0) + A{\omega^n} $ . The nature of variation of DC conductivity suggests Arrhenius type of electrical conductivity.     

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.     

Dielectric relaxation and ionic conductivity studies of LiCaPO<Subscript>4</Subscript>

The AC conductivity of the LiCaPO₄ compound has been measured in the temperature range 634–755 K and the frequency range 300 Hz–5 MHz. The impedance data were fitted to an equivalent circuit consisting of series combination of grains, grains boundary, and electrode elements. Dielectric data were analyzed using complex electrical modulus M* at various temperatures. The modulus plots are characterized by the presence of two relaxation peaks thermally activated. The activation energies obtained from the analysis of M″ (0.90 eV) and conductivity data (0.94 eV) are very close, revealing an ionic hopping mechanism.     

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.     

Electrical conduction and thermodynamic properties of K2NiP2O7

The pyrophosphate K₂NiP₂O₇ has been synthesized by the classic ceramic method and characterized by X-ray diffraction, solid-state ³¹P magic angle spinning (MAS) NMR, and IR and electrical impedance spectroscopy. The solid-state ³¹P MAS NMR, performed at 121.49 MHz, shows two isotropic resonances at ?17.66 and ?19.94 ppm, revealing the existence of two phosphorus environments in the structure. The electrical conductivity and dielectric properties have been investigated in the frequency and the temperature range of 200 Hz–1 MHz and 603–728 K, respectively. The frequency dependence of the conductivity is interpreted using the augmented Jonscher relation. The close values of activation energies obtained from the analysis of hopping frequency and dc conductivity imply that the transport is through ion hopping mechanism. The charge carrier concentration in the investigated sample has been evaluated using the Almond–West formalism and shown to be independent of temperature. Thermodynamic parameters such as the free energy of activation ΔF, the enthalpy ΔH, and the change in entropy ΔS have been calculated.     

Thermodynamic properties and application of CBH model in the ac conductivity of LiNi1.5P2O7 ceramic

The LiNi_1.5P₂O₇ compound was prepared by the solid-state reaction method at 923 K and characterized through XRD and Raman spectroscopy techniques. The impedance spectroscopy measurements were performed in the frequency and the temperature range (300 Hz–5 MHz) and (633–729 K), respectively. The ac conductivity for grain contribution is interpreted using the universal Jonscher’s power low. The exponent n decreases with increasing temperature which reveals that the conduction inside the studied material is insured by the correlated barrier hopping (CBH) model. The parameters of CBH model were determined showing that the ac conduction is realised by single-polaron hopping mechanism. Thermodynamic parameters such as the free energy for dipole relaxation ΔF, the enthalpy ΔH, and the change in entropy ΔS have been calculated.     

Preparation and characterization of LiNi<Subscript>0.495</Subscript>M<Subscript>0.01</Subscript>Mn<Subscript>0.495</Subscript>O<Subscript>2</Subscript> (M = Zn,Co, and Y) for lithium ion batteries

Layered structured LiNi_0.5Mn_0.5O₂ and LiNi_0.495M_0.01Mn_0.495O₂ (M = Zn, Co, and Y) compounds were prepared by PVP (poly(vinyl pyrrolidone))-assisted sol-gel method, and their structural, morphological, vibrational, transport, and electrochemical properties were characterized by XRD, SEM, FTIR, Raman, AC impedance, and galvanostatic charge and discharge analysis. XRD patterns reveal that doping does not change the crystal structure of the LiNi_0.5Mn_0.5O₂ compound. SEM images show that the average size of the particle is in sub-micron ranges. The AC impedance studies shows an electrical conductivity of ～2.5 × 10^?7 S/cm for the parent compound. The introduction of Zn/Co/Y at equivalent sites increased the electrical conductivity by one order ～10^?6 S/cm. The compound LiNi_0.495Co_0.01Mn_0.495O₂ shows the highest electrical conductivity of 2.85 × 10^?6 S/cm and delivers a specific discharge capacity of 110 mAh/g at the end of the 25th cycle in the voltage window of 2.5–4.4 V for a current density of 30 mA/g.     

Conductivity behavior of the new pyrophosphate NaNi<Subscript>1.5</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

NaNi_1.5P₂O₇ compound was obtained by the classic ceramic method at high temperature and was characterized by XRD. It was found to crystallize in the triclinic symmetry with the P-1 space group. The electrical conductivity and modulus characteristics of the system have been investigated in the temperature and the frequency range 586–723 K and 200 Hz–1 MHz, respectively, by means of impedance spectroscopy. The ac conductivity for grain contribution was interpreted using the universal Jonscher’s power law. The exponent s decreased with increasing temperature revealing that the conduction inside the studied material is insured by the correlated barrier hopping (CBH) model. The conduction mechanism was explained with the help of Elliot’s theory, and the Elliot’s parameters were determined. Thermodynamic parameters such as the free energy for dipole relaxation ΔG, the enthalpy ΔH, and the change in entropy ΔS have been calculated.     

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.     

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.     

Dielectric relaxation and ac conduction in multiferroic TbMnO3 ceramics: Impedance spectroscopy analysis

Polycrystalline samples of Tb_1−xAl_xMnO₃ (x = 0, 0.1, 0.2) have been synthesized by means of standard high-temperature solid-state reaction technique. Detailed studies on the effect of compositional variation of aluminum (Al) on the electrical behavior (complex impedance Z*, complex modulus M*, and relaxation mechanisms) of the parent TbMnO₃ have been performed by using the nondestructive complex impedance spectroscopy technique at temperatures above room temperature. In the temperature range covered, the impedance plots signalize that the grains are the unique responsible for the conduction mechanism of the concerned material. The impedance spectra are well modeled in terms of electrical equivalent circuit with a grain resistance (R_g) and constant phase element impedance (Z_CPE). The conductivity data of the undoped and Al-doped samples are well fitted by the universal Jonscher's power law. The resulting fitting parameters indicate that for the studied samples, the hopping process occurs between neighboring sites. Activation energy values for dc conductivity are calculated for undoped and Al-doped samples and found to decrease when Al is incorporated. In turn, the emergence of single arc in the complex modulus spectrum for all the compositions of Al suggests that for the studied samples only one type of relaxation behavior is present at the selected temperatures. A non-Debye-type relaxation is clearly verified. The relaxation process in the present samples seems to be composition and temperature dependent, particularly at higher frequencies.     

AC conductivity evolution in bulk and grain boundary response of sodium tungstate Na<Subscript>2</Subscript>WO<Subscript>4</Subscript>

The Na₂WO₄ compound has been obtained by the conventional solid-state reaction and characterized by X -ay powder diffraction. The title material crystallizes in the cubic system with Fd-3m space group. The electrical properties of the compound have been studied using complex impedance spectroscopy in the frequency range 200 Hz–5 MHz and temperature range 586–679 K. Two semicircles are observed in impedance plot indicating the presence of two relaxation processes in the compound associated with the grain and grain boundary. The relaxation behavior of the grain and grain boundary of the Na₂WO₄ are also obtained from the analyzed electrical modulus data. 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. The mechanism of conduction is probably due from the displacements of the Na+ ion in the tunnel-type cavities along [111] direction.     

Complex impedance spectroscopy studies of (La0.70−xNdx)Sr0.30Mn0.70Cr0.30O3 (x≤0.30) perovskite compounds

The transport properties of Nd-doped perovskite materials (La_0.7−xNd_x)Sr_0.3Mn_0.7Cr_0.3O₃ (x≤0.30) were investigated using impedance spectroscopy techniques over a wide range of temperatures and frequencies. AC conductance analyses indicate that the conduction mechanism is strongly dependent on temperature and frequency. The DC conductance plots can be described using the small polaron hopping (SPH) model, with an apparent reduction of the polaron activation energy below the Curie temperature T_C. Complex impedance plots exhibit semicircular arcs described by an electrical equivalent circuit. Off-centered semicircular impedance plots show that the Nd-doped compounds obey to a non-Debye relaxation process. The conductivity of grains and grain-boundaries has been estimated. The activation energies calculated from the conductance and from time relaxation analyses are comparable. This indicates that the same type of charge carriers is responsible for both the electrical conduction and relaxation phenomena.