Specific features in the synthesis, crystal structure and electrical conductivity of BICUTIVOX

The formation of solid solutions Bi₄V_2 − xCu_x/2Ti_x/2O_11 − x (0.025 ≤ x ≤ 0.5) known as BICUTIVOX, synthesized by three different methods (a conventional solid-state synthesis, solid-state synthesis enhanced by mechanical activation, and through liquid precursors), has been studied. Based on crystal structure investigations carried out at different temperatures, ranges of stability and temperatures of phase transitions for different polymorphous modifications have been defined. The morphology and the local chemical composition of the ceramic samples obtained have been studied. Thermal expansion coefficients have been measured. The electrical conductivity of ceramic samples has been investigated in a wide range of temperatures and partial oxygen pressures.     

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.     

Characterisation of the oxygen transfer in BIMEVOX membranes under applied current conditions

Oxygen isotopic exchange has been studied for a number of materials in the BIMEVOX family of compounds. The exchanges were undertaken at 620 °C with gold grid electrodes on the samples and with a constant current flowing through the samples during the exchange anneals. These conditions simulate those used when these materials are employed in oxygen separation devices where substantial oxygen fluxes can be sustained using such simple gold grid electrodes.The results showed that samples exchanged under current flow conditions exhibit substantial oxygen exchange at the cathode, in contrast to samples where no electrical bias is applied. This effect was sustained in regions remote from the sputtered gold electrode. Complementary studies of the samples using X-ray diffraction revealed subtle changes in the diffraction patterns following experiments with current flow. These changes are ascribed to a reduction of V⁵⁺ to V⁴⁺ at the cathode locally transforming the BIMEVOX material into a mixed conducting material, and hence enhancing the oxygen isotopic exchange process.     

Synthesis,structure, and conductivity of BIMEVOX oxide ceramics

The methods using solid-phase synthesis or liquid precursors converted compounds of BIMEVOX family (ME is a bi- to pentavalent cation) into stable materials in a sufficiently wide concentration and temperature ranges. The crystal structure of various BIMEVOX polymorphic modifications was refined and their behavior was analyzed with respect to temperature and oxygen partial pressure. The phase transition temperature ranges were fixed. The particle size distribution was determined by means of laser diffraction and optical microscopy. The impedance measurements of BIMEVOX electroconductivity against temperature, composition, oxygen partial pressure detected the most promising compositions with respect to the absolute conductivity value and linear conductivity relationship to temperature and Po₂. Different conductivity of specimens was noted with respect to method of synthesis.     

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.     

Electrotransport Properties of Ceramics Based on Bi<Subscript>4</Subscript>V<Subscript>2 − <Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript>x</Subscript>O<Subscript>11 − <Emphasis Type="Italic">x</Emphasis></Subscript>

Conditions for the formation of single-phase compounds in the synthesis of solid solutions Bi₄V_{2 − x} Fe_xO_{11 − x} are studied. The sequence of phase transitions is determined. Parameters of unit cells of solid solutions are determined. The net conductance as a function of temperature and composition is studied.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 607–609.Original Russian Text Copyright © 2005 by Emel’yanova, Buyanova, Zhukovskii.     

Structural and electrical properties of hexavalent-substituted BIMEVOX synthesized by a microwave-assisted route

The microwave (MW)-assisted solid synthesis route was employed to prepare a new Aurivillius-type compound with the general formula Bi₂Cr _x V_1?x O_5.5+x?δ; 0≤x≤0.20 (BICRVOX). This novel synthesis method revealed that polycrystalline products of the BICRVOX system can effectively be obtained after being irradiated for 25 min rather than for the many hours of high-temperature heating needed in other conventional routes. The phase structure of MW-prepared samples was characterized by comparison with those obtained from the conventional solid-state reaction, using powder X-ray diffraction, FT-IR and differential thermal analysis techniques. Importantly, the substitution of Cr(VI) for V(V) in the parent compound resulted in stabilization of only the α - and β -phases. AC impedance spectroscopy confirmed that the MW-prepared samples possess slightly lower oxide-ion performance compared with the conventionally-prepared ones; it did, however, evidence the significant role of powerful dielectric heating of MWs in lowering the charge carrier accumulation.     

Composition dependence of oxide anion conduction in the BIMEVOX family

Partial substitution for vanadium in Bi₄V₂O₁₁ can lead to the stabilization at room temperature of one of the three polymorphs , β, γ exhibited by the mother compound. A tentative classification of the BIMEVOX phases based on these structural polytypes is carried out, and a review of the different identified ways to stabilize the γ-type phases, the most performant ones in term of oxide anion conduction, is proposed. The experimental results clearly indicate that the predominant parameter is not the size or the valence state of the dopant, but rather the structural parameter correlated with the ability for the dopant to regularize the diffusion slab between the Bi₂O₂ sheets in these layered materials.