Impedance spectroscopy of vanadium modified BaBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics

In recent years a wide range of Aurivillius layered materials have been introduced. These novel materials are produced in many various forms such as fibers, thin films as well as bulk by using a number of processing routes. As advanced materials they are they have many interesting properties which include a number of useful electrical properties related to separated grain and grain boundary conductivity, impedance, activation energies, etc. In this paper these properties are described and discussed in detail. The electrical properties of the vanadium doped BaBi₂Nb₂O₉ ceramic was measured over a wide range of temperatures by impedance spectroscopy (IS). The separated grain activation energy, calculated from Arrhenius characteristics at temperatures between room temperature and 600 °C, was 1 eV for 0 at.% of vanadium dopant and 1.2 eV for 10 at.%, whereas the activation energies in the grain boundary region were 0.97 and 1.15 eV, respectively. The obtained results suggest the significant role of vanadium dopant, causing ordering the crystalline structure.     

Impedance spectroscopy study on the ionic conductivity processes of the novel LiFeVO<Subscript>4</Subscript> phase

The recently discovered compound LiFeVO₄ was prepared by solid-state reaction at 570 °C during a 7-h period. The X-ray diffraction pattern revealed an orthorhombic crystal structure. Thermogravimetric measurements revealed a reversible mechanism which was attributed to absorption–desorption of humidity. Impedance spectroscopy measurements were carried out at 25 °C steps in the temperature range from 25 to 500 °C and equivalent circuits were drawn to fit the impedance measurement results at each temperature level. The elements of the equivalent circuits were assigned to bulk, grain boundary, and along grain boundary conductivity. All three conduction mechanisms were found to be humidity sensitive. Arrhenius plots were plotted for the bulk and grain boundary conductivity processes. The activation energy for the bulk conductivity process was calculated to be 0.25 eV over the temperature range from 175 to 500 °C and the activation energy for the grain boundary conductivity process was calculated to be 0.41 eV from 300 to 500 °C and 0.20 eV from 175 to 275 °C. An explanation for the existence of these two grain boundary activation energies is attempted. The dependence of the material conductivity mechanisms on humidity suggests that LiFeVO4 could be used as a humidity sensor.     

Electrical and complex dielectric behaviour of composite polymer electrolyte based on PEO,alumina and tetrapropylammonium iodide

In this study, the electrical, dielectric and morphological analysis of composite solid polymer electrolytes containing polyethylene oxide, alumina nano-fillers and tetrapropylammonium iodide are conducted. The temperature dependence of conductivity shows activation energy of 0.23, 0.20 and 0.29 eV for electrolytes containing 0, 5 and 15 wt.% alumina, respectively, when data fitted to the Arrhenius equation. These activation energy values are in good agreement with those determined from dielectric measurements. The result confirms the fact that conductivity is activated by both the mobility and the charge carrier density. The conductivity isotherms demonstrated the existence of two peaks, at 5 and 15 wt.% Al₂O₃ composition. The highest conductivity values of 2.4 × 10^?4, 3.3 × 10^?4 and 4.2 × 10^?4 S cm^?1 are obtained for the sample with 5 wt.% Al₂O₃ at 0, 12 and 24 °C, respectively, suggesting an enhancement of conductivity compared with that of alumina free samples.     

Electrical conductivity of Na2SO4(I)

The electrical conductivity of the solid phase Na₂SO₄(I) has been measured between the melting point at 884°C and the first order phase transition at about 240°C. The measurements have been performed using complex impedance measurements on pellet samples as well as on U-cells. The electrical conductivity is strongly dependent on sample at low temperatures and the activation energy ranges from 0.5 eV to 1.7 eV over the measured temperature range.     

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.     

Trap characterization for Bi4Ti3O12 thin films by thermally stimulated currents

Thermally stimulated current (TSC) measurements performed in the 100 K–400 K temperature range on Bi₄Ti₃O₁₂ (BiT) thin films annealed at 550 °C and 700 °C had revealed two trapping levels having activation energies of 0.55 eV and 0.6 eV. The total trap concentration was estimated at 10¹⁵ cm⁻³ for the samples annealed at 550 °C and 3×10¹⁵ cm⁻³ for a 700 °C annealing and the trap capture cross-section was estimated about 10⁻¹⁸ cm². From the temperature dependence of the dark current in the temperature range 20 °C–120 °C the conduction mechanism activation energy was found to be about 0.956–0.978 eV. The electrical conductivity depends not only on the sample annealing temperature but also whether the measurement is performed in vacuum or air. The results on the dark conductivity are discussed considering the influence of oxygen atoms and oxygen vacancies. Received: 28 January 1998 / Accepted: 8 January 1999 / Published online: 5 May 1999     

Low-temperature sintering effects on NASICON-structured LiSn<Subscript>2</Subscript>P<Subscript>3</Subscript>O<Subscript>12</Subscript> solid electrolytes prepared via citric acid-assisted sol-gel method

LiSn₂P₃O₁₂ with sodium (Na) super ionic conductor (NASICON)-type rhombohedral structure was successfully obtained at low sintering temperature, 600 °C via citric acid-assisted sol-gel method. However, when the sintering temperature increased to 650 °C, triclinic structure coexisted with the rhombohedral structure as confirmed by X-ray diffraction analysis. Conductivity–temperature dependence of all samples were studied using impedance spectroscopy in the temperature range 30 to 500 °C, and bulk, grain boundary and total conductivity increased as the temperature increased. The highest bulk conductivity found was 3.64?×?10^?5 S/cm at 500 °C for LiSn₂P₃O₁₂ sample sintered at 650 °C, and the lowest bulk activation energy at low temperature was 0.008 eV, showing that sintering temperature affect the conductivity value. The voltage stability window for LiSn₂P₃O₁₂ sample sintered at 600 °C at ambient temperature was up to 4.4 V. These results indicated the suitability of the LiSn₂P₃O₁₂ to be exploiting further for potential applications as solid electrolytes in electrochemical devices.     

Incorporation of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript> into MC-PVA blend-based polymer to prepare proton-conducting polymer electrolyte films

Proton-conducting solid polymer blend electrolytes based on methylcellulose-polyvinyl alcohol:ammonium nitrate (MC-PVA:NH₄NO₃) were prepared by the solution cast technique. The structural and electrical properties of the samples were examined by X-ray diffraction (XRD), Fourier transform infrared (FTIR), and electrical impedance (EI) spectroscopy. The shifting and change in the intensity of FTIR bands of the electrolyte samples confirm the complex formation between the MC-PVA polymer blend and the NH₄NO₃ added salt. The observed broadening in the XRD pattern of the doped samples reveals the increase of the amorphous fraction of polymer electrolyte samples. The increase in electrical conductivity of polymer electrolyte samples with increasing salt concentration attributed to the formation of charge-transfer complexes, and to increase in the amorphous domains. A maximum ionic conductivity of about 7.39 × 10^?5 S cm^?1 was achieved at room temperature for the sample incorporating 20 wt% of NH₄NO₃. The DC conductivity of the present polymer system exhibits Arrhenius-type dependence with temperature. The decrease in the values of activation energies with increasing salt concentration indicates the ease mobility of ions. The decrease in dielectric constant with increasing frequency was observed at all temperatures. Optical properties such as absorption edge, optical band gap, and tail of localized state were estimated for polymer blend and their electrolyte films. It was found that the optical band gap values shifted towards lower photon energy from 6.06 to 4.75 eV by altering the NH₄NO₃ salt content.     

LiClO4-doped plasticized chitosan and poly(ethylene glycol) blend as biodegradable polymer electrolyte for supercapacitors

Biodegradable polymer electrolyte comprising the blend of chitosan (CS) and poly(ethylene glycol) (PEG) plasticized with ethylene carbonate and propylene carbonate, as host polymer, and lithium perchlorate (LiClO₄), as a dopant, was prepared by solution casting technique. The ionic conductivity has been calculated using the bulk impedance obtained through impedance spectroscopy. The variation of conductivity and dielectric properties has been investigated as a function of polymer blend ratio, plasticizer content and LiClO₄ concentration at temperature range of 298–343 K. The DSC thermograms show two broad peaks for CS/PEG blend and increased with increase in the LiClO₄ content. The maximum conductivity has been found to be 1.1?×?10^?4 S cm^?1 at room temperature for 70:30 (CS/PEG) concentration. The electric modulus of the electrolyte film exhibits a long tail feature indicative of good capacitance. The activation energy of all samples was calculated using the Arrhenius plot, and it has been found to be 0.12 to 0.38 eV. A carbon–carbon supercapacitor has been fabricated using this electrolyte, and its electrochemical characteristics and performance have been studied. The supercapacitor showed a fairly good specific capacitance of 47 F?g^?1.     

A new anode material LiZnVO4: synthesis and electrochemical measurements

LiZnVO₄ particles ware synthesized via solid-state reaction route. It was characterized by X-ray diffraction and scanning electron microscopy. As anode material for rechargeable lithium-ion battery, the electrochemical performance of the LiZnVO₄ samples was measured. It was found that a large capacity of 330 mAh g^?1 can be retained after 70 cycles. The electrochemical measurements indicate that the anode material made of LiZnVO₄ exhibits excellent cycling stability even at a high current density.     

Preparation,structural characterization and conductivity of LiZr2(PO4)3

Amorphous LiZr₂(PO₄)₃ has been prepared at room temperature starting from aqueous solutions of ZrOCl₂, H₃PO₄, and LiOH and then crystallized by heating at temperatures between 600 and 900°C. The material obtained at 900°C has been characterized by X-ray powder diffractometry, DSC analysis, and ac conductivity. It is monoclinic from 20 up to about 300°C and orthorhombic at higher temperatures. A change in the activation energy for conduction (from 0.79 to 0.43 eV) and a weak endothermic effect (0.9–1.7 cal/g) are associated with the phase transition. The ac conductivity of sintered pellets is, on average, 7×10⁻⁴ S cm⁻¹ at 300°C.     

Experimental measurement of the electrical conductivity of pyroxenite at high temperature and high pressure under different oxygen fugacities

Electrical conductivities of pyroxenite were measured between frequencies of 10^?1 and 10⁶ Hz in a multi-anvil pressure apparatus using different solid buffers (Ni+NiO, Fe+Fe₃O₄, Fe+FeO and Mo+MoO₂) to stabilize the partial pressure of oxygen. The temperature ranged from 1073 to 1423 K (800 to 1200 °C) and the pressure from 1.0 to 4.0 GPa. We observe that: (1) the electrical conductivity (σ) of pyroxenite depends on frequency; (2) σ tends to increase with rising temperature (T), and Log σ and 1/T obey a linear Arrhenius relationship; (3) under control of the buffer Fe+Fe₃O₄, σ tends to decrease with rising pressure, nevertheless the activation enthalpy tends to increase. For the first time we have obtained values for the activation energy and activation bulk volume of the main charge carriers, which are (1.60±0.07) eV and (0.05±0.03) cm³/mol, respectively; (4) for a given pressure and temperature, σ tends to rise with increased oxygen fugacity, whereas the activation enthalpy and preexponential factor tend to decrease; and (5) the behaviour of the electrical conductivity at high temperature and high pressure can be reasonably interpreted by assuming that small polarons provide the dominant conduction mechanism in the pyroxenite samples.     

Thermal analysis, Raman spectroscopy and complex impedance analysis of Cu2+-doped KDP

Raman spectroscopy and differential thermal analysis (DTA) and thermogravimetric analysis have been carried out on Cu-doped KH₂PO₄ (Cu-KDP). X-ray diffraction powder data reveal that the structure of the KDP crystal does not change with the additive Cu²⁺ ion. DTA analysis and Raman study of Cu-KDP as a function of temperature reveal that this compound undergoes two phase transitions at about Ttr =453 and 473 K. The electrical conductivity measurements on polycrystalline pellet of Cu-KDP (5) are performed from room temperature (RT) up to 495 K. Only one phase transition is observed at 470 K. The activation energy in the migration is 0.42 eV in the temperature range from RT to 470 K. For temperature above 470 K, the activation energy of the superprotonic phase is 1.87 eV.     

Transport phenomena in superionic Na<Subscript><Emphasis Type="Italic">х</Emphasis></Subscript>Cu<Subscript>2 − <Emphasis Type="Italic">х</Emphasis></Subscript>S (<Emphasis Type="Italic">х</Emphasis> = 0.05; 0.1; 0.15; 0.2) compounds

The electronic and ionic conductivity, the electronic and ionic Seebeck coefficients, and the thermal conductivity of Na _x Cu_2 ? x S (x = 0.05, 0.1, 0.15, 0.2) compounds were measured in the temperature range of 20–450 °С. The total cationic conductivity of Na_0.2Cu_1.8S is about 2 S/cm at 400 °С (the activation energy ≈ 0.21 eV). Over the studied compounds, the composition Na_0.2Cu_1.8S has the highest electronic conductivity (500–800 S/cm) in the temperature range from 20 to 300 °С, and the highest electronic Seebeck coefficient (about 0.2 mV/K) in the same temperature range is observed for Na_0.15Cu_1.85S composition; the electronic Seebeck coefficient increases abruptly above 300 °С for all compounds. The thermal conductivity of superionic Na_0.2Cu_1.8S is low, which causes high values of the dimensionless thermoelectric figure of merit ZT from 0.4 to 1 at temperatures from 150 to 340 °С.     

Impedance spectroscopy and dielectric analysis in KH2PO4 single crystal

Optical observation, differential scanning calorimetry, thermogravimetric analysis, and differential thermogravimetric measurements have been carried out on KH₂PO₄ single crystals. As compared with the optical observation of crystal under polarizing microscope, the dehydration process occurred gradually over the crystal surface at temperatures above 195 °C and then the interior of the sample. The ac impedance measurements were performed as a function of both frequency and temperature. The electrical conduction and dielectric relaxation have been studied. The activation energy of migration is 1.02 eV in the temperature range between 150 and 179 °C. The conduction mechanism in this temperature range is attributed to the hopping of proton among hydrogen vacancies. At temperatures above 186 °C, a higher conductivity activation energy with 2.94 eV is obtained. In addition to the proton conduction, the migration of the heavier ions (such as potassium ion) is also suggested.     

Effect of NH4I and I2 concentration on agar gel polymer electrolyte properties for a dye-sensitized solar cell

Gel polymer electrolytes were prepared using agar polymer host, NH₄I, and I₂ salts. The sample of agar paste with 1.0 M of NH₄I and 0.2 μM of I₂ exhibits the highest conductivity and lowest viscosity values at room temperature of (2.64?±?0.19)?×?10^?3?S?cm^?1 and 1.17?±?0.29 Pa?s, respectively. All of the gel polymer electrolytes display Arrhenian behavior, and the optimum agar paste gave the lowest activation energy of 0.25 eV. It also had a good physical appearance compared with the other samples. This gel polymer electrolyte had a good potential and was applicable to a role as electrolyte in ITO-ZnO (N719 dye)/agar paste?+?1.0 M NH₄I?+?0.2 μM I₂/Au-Pd-ITO dye-sensitized solar cell.     

Ionic conductivity in three crystalline phases of LiBH4 under pressure

The AC electrical conductivity of LiBH₄ was investigated below 2 GPa between 1 Hz and 1.6 MHz. The high-temperature phase has an ionic conductivity of up to 0.01 S cm^?1, while the low-temperature phases have conductivities two orders of magnitude lower. All phases show an Arrhenius behaviour with activation energies E _a between 0.5 and 0.7 eV, in good agreement with earlier data except for phase III, which is found to have the highest activation energy of the phases studied. The high-temperature phase has a minimum in E _a near 1 GPa, close to the triple point, correlated with a sudden change in activation volume. These features may indicate an isostructural phase transition. The conductivities of the ambient temperature phases increase temporarily by an order of magnitude after transitions between these phases, probably due to new diffusion channels via structural defects. The phase diagram agrees well with earlier results.     

Structural and electrical characterization of the NASICON-type Li2FeZr(PO4)3 and Li2FeTi(PO4)3 compounds

In order to develop new electrolytes for all-solid-state rocking chair lithium batteries, the NASICON-type compounds Li₂FeZr(PO₄)₃ and Li₂FeTi(PO₄)₃ were investigated by powder X-ray diffraction technique and impedance spectroscopy. Li₂FeZr(PO₄)₃ is orthorhombic Pbna (a=8.706(3), b=8.786(2), c=12.220(5) Å) and Li₂FeTi(PO₄)₃ is orthorhombic Pbca (a=8.557(3), b=8.624(3), c=23.919(6) Å). They show no phase transitions from RT to 800 °C. In the same temperature range logσT vs. 1/T show no slope variations. The activation energies for the ionic conductivity were 0.62 and 0.64 eV for Li₂FeTi(PO₄)₃ and Li₂FeTi(PO₄)₃, respectively. In order to better evaluate the present results they were compared with those of α and β-LiZr₂(PO₄)₃ phases, which were also prepared and characterised. A change of activation energy from 0.47 eV to 1.03 eV was observed in the case of β phase, at about 300 °C; attributed to the β (orthorhombic) ? β′ (monoclinic) phase transition. In the α phase the activation energy 0.47 eV in the temperature range 150 – 850 °C. The Li₂FeZr(PO₄)₃ and Li₂FeTi(PO₄)₃ compounds can be interesting for applications as solid electrolytes in high temperature (>300 °C) lithium batteries.     

Li4SiO4-Li3VO4赝二元系和Li4GeO4-Li4SiO4-Li3VO4赝三元系中新的锂离子导体

本文在室温到300℃的温度范围内研究了Li₄SiO₄-Li₃VO₄和Li₄GeO₄-Li₄SiO₄-Li₃VO₄体系中的离子导电性,发现γ_II相固溶体Li_3+xV_1-xSi_xO₄是好的锂离子导体。所研究的成分中Li_3.3V_0.7Si_0.3O₄的离子电导率最高,室温下为1×10^-5Ω^-1·cm^-1,在42—192℃的电导激活能为0.36eV,电子电导率可以忽略,因而这是迄今所发现的最好的锂离子导体之一。粗略确定了Li₄GeO₄-Li₄SiO₄-Li₃VO₄三元系中电导率高的范围,发现在Li_3.5V_0.5Ge_0.5O₄中Si部分取代Ge可以使电导率进一步提高,Li_3.5V_0.5Ge_0.4Si_0.1O₄的室温电导率可达1.3×10^-5Ω^-1·cm^-1,电导激活能为0.40eV。 关键词：