Oxygen nonstoichiometry and defect structure of the double perovskite GdBaCo2O6 − δ

The results of oxygen nonstoichiometry, δ, measured by means of coulometric technique as a function of oxygen partial pressure, p_O2, in temperature range 900 ≤ T °C ≤ 1050 are presented for GdBaCo₂O_6 − δ with double perovskite structure. Partial molar enthalpy and entropy of oxygen in GdBaCo₂O_6 − δ structure were calculated. Both thermodynamic properties were shown to increase dramatically in the vicinity of the oxygen nonstoichiometry value equal to 1. The p_O2 dependences of oxygen nonstoichiometry and the δ dependences of the partial molar properties were found to have inflections when the oxygen content of GdBaCo₂O_6 − δ is equal to 5.0 exactly. The modeling of the defect structure of the double perovskite GdBaCo₂O_6 − δ was carried out by considering different reference states. Only the model based on the cubic perovskite GdCoO₃ as a reference state was shown to fit the experimental data on oxygen nonstoichiometry of GdBaCo₂O_6 − δ good enough. Equilibrium constants of the appropriate defects reactions were, therefore, determined. Concentrations of all defect species defined within the framework of this model were calculated as functions of temperature and oxygen nonstoichiometry. Oxygen vacancies were shown to be formed during p_O2 diminution in gas environment in the layers of GdBaCo₂O_6 − δ crystal lattice where they are ordered until oxygen nonstoichiometry of the oxide becomes equal to unity afterwards oxygen vacancies are formed randomly in oxygen polyhedrons.     

Extraordinary fast oxide ion conductivity in La1.61GeO5−δ thin film consisting of nano-size grain

Thin films of La_1.61GeO_5−δ, a new oxide ionic conductor, were fabricated on dense polycrystalline Al₂O₃ substrates by a pulsed laser deposition (PLD) method and the effect of the film thickness on the oxide ionic conductivity was investigated on the nanoscale. The deposition parameters were optimized to obtain La_1.61GeO_5−δ thin films with stoichiometric composition. Annealing was found necessary to get crystalline La_1.61GeO_5−δ thin films. It was also found that the annealed La_1.61GeO_5−δ film exhibited extraordinarily high oxide ionic conductivity. Due to the nano-size effects, the oxide ion conductivity of La_1.61GeO_5−δ thin films increased with the decreasing thickness as compared to that in bulk La_1.61GeO_5−δ. In particular, the improvement in conductivity of the film at low temperature was significant .The electrical conductivity of the La_1.61GeO_5−δ film with a thickness of 373 nm is as high as 0.05 S cm^− 1 (log(σ/S cm^− 1) = − 1.3) at 573 K.     

Redox behaviour,chemical compatibility and electrochemical performance of Sr2MgMoO6 − δ as SOFC anode

The double perovskite Sr₂MgMoO_6 − δ (SMM) has been proposed as a potential anode material for direct hydrocarbon oxidation in solid oxide fuel cells (SOFCs). The oxygen nonstoichiometry and electrical conductivity dependence of Sr₂MgMoO_6 − δ have been determined as a function of the oxygen partial pressure by coulometric titration and impedance spectroscopy techniques. The chemical compatibility of Sr₂MgMoO_6 − δ with most of the typical electrolytes commonly used in SOFCs i.e. La_0.8Sr_0.2Ga_0.8Mg_0.2O_3 − δ (LSGM), Ce_0.8Gd_0.2O_2 − δ (CGO) and Zr_0.84Y_0.16O_2 − δ (YSZ), was investigated. Reactivity between SMM and all these electrolytes has been found above 1000 °C, although the reaction is most severe with ZrO₂-based electrolytes. Area-specific polarisation resistance of the SMM/LSGM/SMM symmetrical cells indicates that the polarisation resistance increases with the firing temperature of the electrodes due to chemical interaction between LSGM and SMM layers. A CGO buffer layer between the anode and electrolyte was also used to prevent an excessive interdiffusion of ionic species between these components, resulting in better performance. Power densities of 330 and 270 mW cm^− 2 were reached at 800 °C for SMM/CGO/LSGM/LSCF and SMM/LSGM/LSCF electrolyte-supported cells, respectively; with 600-μm-thick LSGM electrolyte, using humidified H₂ as fuel and air as oxidant. XPS and XRPD studies on SMM powders annealed in air and diluted CH₄ atmospheres showed that the surface of SMM powders is mainly formed by SrMoO₄ and metal carbonates.     

Oxygen nonstoichiometry,mixed valency and mixed conduction in (La,Sr)(Co,Fe)O3−δ

Defect chemistry for a mixed conductor, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ was studied. Samples were treated under controlled oxygen partial pressure, P(O₂), conditions at 1273 K [10^− 11.1 ≤ P(O₂)/atm ≤ 1], and cooled to room temperature. Oxygen nonstoichiometry and valences of transition metal ions for the treated samples were evaluated by iodometry and X-ray absorption spectroscopy, respectively. With decreasing P(O₂), preferential reduction of Co³⁺ to Co²⁺ was observed, while iron preserved its higher valence above 3 under conditions studied. A dependency of its electrical conductivity on P(O₂) was discussed along with a change in concentration of oxygen vacancies and mixed valences.     

Transport properties and structural stability of tetragonal CeNbO4+δ

The electrical properties of CeNbO_4+δ have been investigated at 1073–1223 K in the oxygen partial pressure range 10^− 17 to 0.36 atm. The conductivity and Seebeck coefficient behaviour indicates that, at oxygen chemical potentials close to atmospheric, tetragonal CeNbO_4+δ possesses a mixed ionic and p-type electronic conductivity. The ion transference numbers under the p(O₂) gradient of 0.93/0.21 atm, measured by the modified e.m.f. technique, are close to 0.4 decreasing in more reducing environments. The variations of partial ionic and electronic conductivities can be described in terms of the oxygen intercalation into the scheelite-type lattice, which results in increasing concentrations of both dominant charge carriers, oxygen interstitials and holes, when p(O₂) increases. Reduction leads to p(O₂)-independent electrical properties, followed by a drastic decrease in the conductivity at oxygen pressures below 10^− 15–10^− 9 atm due to a reversible transition into the monoclinic phase. Contrary to the zircon-type CeVO_4±δ, no traces of the parent binary oxides were detected in the reduced cerium niobate.     

Electrical conductivity of (Ba0.3Sr0.2La0.5)(In1−xFex)O3−δ

We have synthesized the perovskite oxides of the (Ba_0.3Sr_0.2La_0.5)(In_1−xFe_x)O_3−δ system and measured the total electrical conductivity as a function of temperature and oxygen partial pressure. It was found that the single-phase composition region extended from x = 0.0 to x = 1.0, and that the Fe valence increased from 3.06 to 3.50 in that region. The electrical conductivity was semiconducting from x = 0.0 to x = 0.40 and metallic from x = 0.50 to x = 1.0. The total electrical conductivity at 800 °C also increased with the Fe content and achieved a maximum value of 140 (S/cm) at x = 1.0. From the dependence of the electrical conductivity on the oxygen partial pressure, we conclude that above x = 0.50, the majority carriers are holes. The estimated hole conductivity increased exponentially with the amount of Fe⁴⁺ cation present. The oxide ion conductivity was dependent on the oxygen vacancy content.     

Ion and electron conduction in SrFe1−xScxO3−δ

The oxygen ion and electron transport in SrFe_1−xSc_xO_3−δ  (x = 0.1–0.3) system at 700–950 °C were studied analyzing the total conductivity dependencies on the oxygen partial pressure, pO₂. The conductivity measurements were performed both under reducing conditions (10^− 19 ≤ pO₂ ≤ 10^− 8 atm) comprising the electron-hole equilibrium point, and in oxidizing atmospheres (10^− 5 ≤ pO₂ ≤ 0.5 atm) which are characterized by extensive variations of the oxygen content studied by coulometric titration technique. The incorporation of 10% Sc³⁺ cations into the iron sublattice suppresses transition of the cubic perovskite phase into vacancy-ordered brownmillerite, thus improving ion conduction at temperatures below 850 °C. When scandium content increases, the ion conductivity becomes considerably lower. The hole mobility is thermally-activated and varies in the range of 0.001 to 0.05 cm² V^− 1 s^− 1, increasing with oxygen concentration and decreasing on Sc doping.     

Synthesis and investigations on the stability of La0.8Sr0.2CuO2.4+δ at high temperatures

For application in solid oxide fuel cells La_0.8Sr_0.2CuO_2.4+δ was synthesized and the phase evolution was characterized after quenching from different temperatures and after slow cooling. A single phase perovskite was found after quenching from 950 °C. The electrical conductivity of the La_0.8Sr_0.2CuO_2.4+δ perovskite exhibited metallic behavior reaching values of about 270 S/cm at 800 °C in air. The thermal expansion between 30 and 800 °C gave a thermal expansion coefficient of 11.1 × 10^− 6 K^− 1.At higher temperatures, the perovskite was transformed to the K₂NiF₄-type structure via an intermediate stage that can be best described as a LaSrCuO₄ phase with preferential growing of {020} lattice planes. After sintering at 1100 °C and slow cooling in the furnace a phase mixture of (La,Sr)CuO_4+δ and (La,Sr)CuO_2.4+δ perovskite was obtained. This phase mixture showed higher electrical conductivity (400 S/cm at 800 °C) and smaller thermal expansion coefficient (9.6 × 10^− 6 K^− 1) than the single phase La_0.8Sr_0.2CuO_2.4+δ perovskite.     

Oxygen ionic conductivity of La2NiO4+δ via interstitial oxygen defect

The ionic conduction properties of La₂NiO_4+δ were studied from oxygen permeation flux and defect-related transport properties. The effects of the applied oxygen chemical potential gradient and temperature on the oxygen permeability of La₂NiO_4+δ at various thickness are reported. The thermally activated oxygen permeation flux increased monotonically with increasing oxygen chemical potential gradient, yielding a maximum of 0.15 cc min^?1 cm^?2 under air/N₂ conditions for the 0.95 mm-thick La₂NiO_4+δ specimen at 900 °C. The oxygen ion conductivity of La₂NiO_4+δ was calculated as a function of temperature and oxygen partial pressure by differentiating the chemical diffusion equation for the oxygen permeation flux based on the dominant electronic transference number. In addition, the oxygen ion conductivity was extracted successfully by solving the Nernst–Einstein equation combining with the calculated self-diffusion coefficient of oxygen from the chemical diffusivity and thermodynamic enhancement factor from the equilibrium oxygen nonstoichoimetry of a La₂NiO_4+δ specimen, and a deviation of the OPP dependence of 1/6 power was observed.     

Electric property of mixed conductor BaIn1−xCoxO3−δ

We synthesized BaIn_1−xCo_xO_3−δ (x = 0–0.8) with a defective perovskite structure by partly replacing In with Co in Ba₂In₂O₅. Based on XRD measurements, the synthesized compound was found to have cubic perovskite and orthorhombic brownmillerite structures depending on the amount of Co. BaIn_1−xCo_xO_3−δ (x = 0.2 and 0.3) showed high total electrical conductivities without undergoing the structural transformation that the original Ba₂In₂O₅ undergoes. Some of the samples showed both electronic and oxide ionic conductivities. At the same time, the oxide ionic conductivity was comparable with that of Ba₂In₂O₅. For example, the sample with x = 0.1 had a total electrical conductivity of 4.7 × 10^− 1 S cm^− 1 and an oxide ion transport number of 0.52 at 850 °C.     

Electronic conductivity and chemical diffusion in n-conducting barium titanate ceramics at high temperatures

The electronic conductivity as well as the chemical diffusion coefficient of barium titanate ceramics doped with Y and Mn (donor-doped and acceptor co-doped) have been determined by application of conductivity relaxation experiments. The equilibrium values of the electronic conductivity of n-conducting BaTiO₃ have been analyzed by application of a defect chemical model involving electrons and cation vacancies as the predominant defect species at oxidizing conditions (fairly high oxygen partial pressures). The relaxation curves of the electronic conductivity yield the chemical diffusion coefficient of the bulk by employing a spherical grain model where the appropriate diffusion length is the radius of grains (average grain size). The conductivity relaxation experiments have been performed as a function of temperature ranging from 1100 to 1250 °C at oxygen partial pressures between 0.01 and 1 bar. The kinetics of the oxygen exchange process can be interpreted in terms of extremely fast diffusion of oxygen via oxygen vacancies along the grain boundaries and slow diffusion of Ti (cation)-vacancies from the grain boundaries into the grains. The Ti-vacancy diffusion coefficients were extracted from the chemical diffusion coefficients as a function of temperature. Typical values for the Ti-vacancy diffusivity are around 10^− 15 cm² s^− 1 with an activation energy of 3.9 ± 0.7 eV.     

The effect of cation nonstoichiometry on the electrical conductivity of acceptor-doped CaZrO3

The electrical properties of acceptor-doped Ca_1−xZr_0.99M_0.01O_3−δ (M = Mg²⁺, In³⁺) systems were investigated as a function of cation nonstoichiometry (0 ≤ x ≤ 0.05). The characterization was carried out using the impedance spectroscopy between 550 °C and 1100 °C in dry air. The contributions of the grain and grain boundary conductivity to the total conductivity were obtained from the impedance data. When the Ca deficiency (x) increased, the total conductivity rapidly decreased with the corresponding increase in activation energy. Although the grain conductivity increased slightly with increasing x, the total conductivity is mostly determined by the highly resistive grain boundary. With varying x, the activation energy of total conductivity showed the percolation behavior. The percolation threshold values vary according to the doped species. It may be due to the difference in concentration of oxygen vacancies of the specimens.     

Fabrication of Gd0.5Sr0.5CoO3 film for SOFC cathode by pulsed laser deposition

Gd_0.5Sr_0.5CoO₃ (GSCO) film has been fabricated by pulsed laser deposition (PLD) to be used as the cathode of the solid oxide fuel cell (SOFC). The GSCO thin film obtained has a columnar crystalline structure so that it will have a high permeation property. The PLD technique has been found suitable for growing a film of complex composition because of its good control of stoichiometry and thus for fabricating a GSCO film used as the cathode of the SOFC. The GSCO film has been studied for porosity electrical conductivity and power density. The GSCO film grown at a substrate temperature of 1100 K and oxygen gas pressure of 100 Pa has high electrical conductivity which is 820 S cm^− 1 at 973 K with post annealing at a rather low temperature (1000 K). This value is higher than that of the GSCO film prepared by RF-sputtering with post annealing at a higher temperature (1273 K).     

Ionic conductivity of brownmillerite-type calcium ferrite under oxidizing conditions

The thermogravimetric and Mössbauer spectroscopy studies showed that, at atmospheric oxygen pressure, the oxygen content in Ca₂Fe₂O₅ brownmillerite is very close to stoichiometric at 300–1270 K. The orthorhombic lattice of calcium ferrite undergoes a transition from primitive (space group Pnma) to body-centered (I2mb) at 950–1000 K, which is accompanied with decreasing thermal expansion coefficient (TEC) and increasing activation energy for the total conductivity, predominantly p-type electronic. The steady-state oxygen permeation through dense Ca₂Fe₂O₅ ceramics is limited by the bulk ionic conduction. The ion transference numbers in air vary in the range 0.002–0.007 at 1123–1273 K, increasing with temperature. Analysis of stereological factors, which may affect oxygen diffusivity, suggests a dominant role of the ion jumps along octahedral and, possibly, tetrahedral layers of the brownmillerite structure. The ionic conductivity of calcium ferrite is higher than that of Ca₂FeAlO_5+δ, but lower compared to the oxygen-deficient perovskite phases based on SrFeO_3−δ where the diffusion pathways form a three-dimensional network. The average TECs of Ca₂Fe₂O₅ ceramics, calculated from dilatometric data in air, are 13.1 × 10^− 6 K^− 1 at 370–950 K and 11.3 × 10^− 6 K^− 1 at 970–1270 K.     

Mesopore size dependence of the ionic diffusivity in alumina based composite lithium ionic conductors

Ordered-mesoporous Al₂O₃ was synthesized by a sol–gel method using neutral copolymer surfactants as structure-directing agents. The pore size was controlled over the 3–15 nm range by the use of various surfactants. Composites composed of the synthesized mesoporous Al₂O₃ and a lithium ion conductor (LiI) were prepared. The maximum dc electrical conductivity, 2.6 × 10^− 4 S cm^− 1 at 298 K, was observed for 50 LiI·50 Al₂O₃ composite with 4.2 nm average mesopore size, which was considerably higher than the previously reported LiI-alumina composites. A systematic dependence of conductivity upon pore size was observed, in which conductivity increased with decreasing pore size, except for samples with a pore size of 2.8 nm. The lithium ion diffusion coefficient determined by the ⁷Li pulsed field gradient nuclear magnetic resonance (PFG-NMR) showed excellent agreement with the measured conductivity calculated by the Nernst-Einstein equation. On the other hand, lithium migration activation energies obtained by quasielastic neutron scattering (QENS) and ⁷Li NMR spin-lattice relaxation time (T₁) were considerably smaller than those obtained from electrical conductivity and PFG-NMR. This could be explained by the ion migration mechanism in heterogeneous composites and a possible enhancement of conductivity in mesoscopically confined spaces.     

Determination of the ionic conductivity of Sr-doped lanthanum manganite by modified Hebb–Wagner technique

The Hebb–Wagner polarization method with the electron blocking electrode has been discussed in this paper in aim to determine a partial ionic conductivity of Sr-doped lanthanum manganite. The “limiting current” in the proposed system was measured using the two-point DC technique with additional Pt electrode between LSM and blocking electrode. The electrochemical model based on bulk diffusion processes and Boltzmann statistics has been also described. The ionic conductivity calculated with the use of proposed model for La_0.7Sr_0.3MnO_3+δ was 5.3×10⁻⁴ S cm⁻¹ at 800 °C and the activation energy of ionic conductivity was found to be (0.60±0.02) eV. This result is in agreement with previous literature reports and indicates the workability of the modified Hebb–Wagner system.     

Defect equilibria and partial molar properties of (La,Sr)(Co,Fe)O3−δ

The oxygen nonstoichiometry δ of La_1−xSr_xCo_1−yFe_yO_3−δ (x = 0.6 and y = 0.2, 0.4) was investigated by thermogravimetry in the range 703 ≤ T/°C ≤ 903 and 1E−5 < pO₂/atm < 1. The oxygen deficit increases with increasing T and decreasing pO₂. Electronic conductivities σ were measured as a function of pO₂ in the range 1E−5 < pO₂/atm < 1 at 700 ≤ T/°C ≤ 900. At constant T, a p-type pO₂-dependence of σ is observed. Oxygen nonstoichiometry data are analyzed with regard to the enthalpy and entropy of oxidation ΔH_ox^θ and ΔS_ox^θ, as well as to the partial molar enthalpy and entropy of oxygen with respect to the standard state of oxygen (pO₂^θ = 1 atm), (h_O − H_O^θ) and (s_O − S_O^θ), respectively. For 2.67 ≤ (3 − δ) ≤ 2.79, (h_O − H_O^θ) decreases with increasing δ, while (s_O − S_O^θ) is constant within the limits of error. Defect chemical modelling was performed by an ideal solution model under consideration of three different valence states for B-site ions (Co or Fe). The dependence of σ on δ is modelled, using calculated defect concentrations as functions of δ. Deviations from the ideal behaviour suggest an immobilization of n-type charge carriers by oxygen vacancies.     

Transport and phase dynamics of poly(vinyl pyrrolidone) doped plastically crystalline N-methyl-N-propylpyrrolidinium tetrafluoroborate

The plastic crystal phase forming N-methyl-N-propylpyrrolidinium tetrafluoroborate organic salt (P₁₃BF₄) was combined with 2, 5 and 10 wt.% poly(vinyl pyrrolidone) (PVP). The ternary 2 wt.% PVP/2 wt.% LiBF₄/P₁₃BF₄ was also investigated. Thermal analysis, conductivity, optical thermomicroscopy, and Nuclear Magnetic Resonance (¹¹B, ¹⁹F, ¹H, ⁷Li) were used to probe the fundamental transport processes. Both the onset of phase I and the final melting temperature were reduced with increasing additions of PVP. Conductivity in phase I was 2.6 × 10^− 4 S cm^− 1 5.2 × 10^− 4 S cm^− 1 1.1 × 10^− 4 S cm^− 1 and 3.9 × 10^− 5 S cm^− 1 for 0, 2, 5 and 10 wt.%PVP/P₁₃BF₄, respectively. Doping with 2 wt.% LiBF₄ increased the conductivity by up to an order of magnitude in phase II. Further additions of 2 wt.% PVP slightly reduced the conductivity, although it remained higher than for pure P₁₃BF₄.     

Oxygen transport in La2NiO4 + δ: Assessment of surface limitations and multilayer membrane architectures

The steady-state oxygen permeation through dense La₂NiO_4 + δ ceramics, limited by both surface exchange and bulk ambipolar conduction, can be increased by deposition of porous layers onto the membrane surfaces. This makes it possible, in particular, to analyze the interfacial exchange kinetics by numerical modelling using experimental data on the oxygen fluxes and equilibrium relationships between the oxygen chemical potential, nonstoichiometry and total conductivity. The simulations showed that the role of exchange limitations increases on reducing oxygen pressure, and becomes critical at relatively large chemical potential gradients important for practical applications. The calculated oxygen diffusion coefficients in La₂NiO_4 + δ are in a good agreement with literature. In order to enhance membrane performance, the multilayer ceramics with different architecture combining dense and porous components were prepared via tape-casting and tested. The maximum oxygen fluxes were observed in the case when one dense layer, ~ 60 μm in thickness, is sandwiched between relatively thin (< 150 μm) porous layers. Whilst the permeability of such membranes is still affected by surface-exchange kinetics, increasing thickness of the porous supporting components leads to gas diffusion limitations.     

Mixed conductivity,stability and thermomechanical properties of Ni-doped La(Ga,Mg)O3−δ

Perovskite-type LaGa_0.65Mg_0.15Ni_0.20O_3−δ exhibiting oxygen transport comparable to that in K₂NiF₄-type nickelates was characterized as a model material for ceramic membrane reactors, employing mechanical tests, dilatometry, oxygen permeability and faradaic efficiency measurements, thermogravimetry (TG), and determination of the total conductivity and Seebeck coefficient in the oxygen partial pressure range from 10^− 15 Pa to 40 kPa. Within the phase stability domain which is similar to La₂NiO_4+δ, the defect chemistry of LaGa_0.65Mg_0.15Ni_0.20O_3−δ can be adequately described by the ideal solution model with oxygen vacancies and electron holes to be the only mobile defects, assuming that Ni²⁺ may provide two energetically equivalent sites for hole location. This assumption is in agreement with the density of states, estimated from thermopower, and the coulometric titration and TG data suggesting Ni⁴⁺ formation in air at T < 1150 K. The hole conductivity prevailing under oxidizing conditions occurs via small-polaron mechanism as indicated by relatively low, temperature-activated mobility. The ionic transport increases with vacancy concentration on reducing p(O₂) and becomes dominant at oxygen pressures below 10^− 7–10^− 5 Pa. The average thermal expansion coefficients in air are 11.9 × 10^− 6 and 18.4 × 10^− 6 K^− 1 at 370–850 and 850–1270 K, respectively. The chemical strain of LaGa_0.65Mg_0.15Ni_0.20O_3−δ ceramics at 1073–1123 K, induced by the oxygen partial pressure variations, is substantially lower compared to perovskite ferrites. The flexural strength determined by 3-point and 4-point bending tests is 167–189 MPa at room temperature and 85–97 MPa at 773–1173 K. The mechanical properties are almost independent of temperature and oxygen pressure at p(O₂) = 1–2.1 × 10⁴ Pa and 773–1173 K.