Mixed electronic and ionic conductivity of LaCo(M)O3 (M=Ga, Cr, Fe or Ni).: V. Oxygen permeability of Mg-doped La(Ga, Co)O3−δ perovskites

The LaGa_1−x−yCo_xMg_yO_3−δ solid solutions with rhombohedrally-distorted perovskite structure were ascertained to form in the concentration range of 0≤y≤0.10 at x=0.60 and 0≤y≤0.20 at x=0.35–0.40. Increasing cobalt content results in increasing electrical conductivity and thermal expansion of the perovskites. Thermal expansion coefficients of the LaGa_1−x−yCo_xMg_yO_3−δ ceramics were calculated from the dilatometric data to vary in the range of 12.4–19.8×10⁻⁶ K⁻¹ at 300–1100 K. Doping La(Ga,Co)O_3−δ solid solutions with magnesium leads to increasing oxygen nonstoichiometry, electronic and oxygen ionic conductivity. Oxygen permeation fluxes through LaGa_1−x−yCo_xMg_yO_3−δ membranes were found to be limited by the bulk ionic conduction and to increase with magnesium concentration, being essentially independent of cobalt content.     

Electrical properties of perovskite-type La(Cr1−xMnx)O3+δ

Perovskite-type La(Cr_1−xMn_x)O_3+δ (0.0x1.0) was synthesized using a sol–gel process. The crystal structure of La(Cr_1−xMn_x)O_3+δ changes from orthorhombic to rhombohedral at x=0.6. The Mn⁴⁺ ion content increases monotonically in the range 0.2x1.0. The magnetic measurement of La(Cr_1−xMn_x)O_3+δ indicates that a Mn³⁺ ion is a high-spin state with (d)³(dγ)¹. The variation of the average (Cr, Mn)-O distance is explained by ionic radii of the Cr³⁺, the Mn³⁺, the Mn⁴⁺ ions. Since the log σT–1/T curve is linear and the Seebeck coefficient (α) is independent of temperature, it is considered that La(Cr_1−xMn_x)O_3+δ is a p-type semiconductor and exhibits the hopping conductivity.     

Oxygen nonstoichiometry of Sr(Co,Fe)O3−δ-based perovskites: I. Coulometric titration of SrCo0.85Fe0.10Cr0.05O3−δ by the two-electrode technique

The p(O₂)–T–δ diagram of perovskite-type SrCo_0.85Fe_0.10Cr_0.05O_3−δ was determined by the coulometric titration technique in the temperature range 770–1250 K at oxygen partial pressures from 8 10⁻¹⁰ to 0.5 atm. Stability of the cubic perovskite phase of SrCo_0.85Fe_0.10Cr_0.05O_3−δ, existing down to the oxygen pressures of 10⁻³–10⁻⁵ atm, was found to be slightly higher than that of SrCo_0.80Fe_0.20O_3−δ, probably due to stabilization of oxygen octahedra neighboring Cr⁴⁺ cations. When the oxygen nonstoichiometry of the Cr-containing perovskite decreases from 0.47 to 0.38, the partial molar enthalpy and entropy for overall oxygen incorporation reaction vary in the ranges −165 to −60 kJ mol⁻¹ and 90 to 150 J mol⁻¹ K⁻¹, respectively. Within the stability limits of the single perovskite phase, the p(O₂)–T–δ diagram can be adequately described by equilibrium processes of oxygen incorporation, cobalt disproportionation and interaction of cobalt and iron cations, with the thermodynamic functions independent of defect concentrations. Increasing grain size in SrCo_0.85Fe_0.10Cr_0.05O_3−δ ceramics from submicron size to 100–200 μm has no effect on the oxygen thermodynamics. The two-electrode coulometric titration technique, based on the alternate use of electrodes for oxygen pumping and e.m.f. measurements, is described and verified by studying oxygen nonstoichiometry of La_0.3Sr_0.7CoO_3−δ and PrO_x.     

Oxygen permeability of La2Cu(Co)O4+δ solid solutions

Formation of the La₂Cu_1−xCo_xO_4+δ solid solutions with orthorhombic K₂NiF₄-type structure was found to be in the range of 0≤x≤0.30 at temperatures above 1270 K. Incorporating cobalt into the copper sublattice of lanthanum cuprate leads to increasing oxygen hyperstoichiometry and decreasing electrical conductivity. Thermal expansion coefficients of the La₂Cu_1−xCo_xO_4+δ (x=0.02–0.30) ceramics at 470–1100 K were calculated from the dilatometric data to vary in the range (12.2–13.2)×10⁻⁶ K⁻¹. Studying the dependence of oxygen permeation fluxes through La₂Cu(Co)O_4+δ on the membrane thickness demonstrated that the oxygen transport at the thickness values below 1 mm is limited by both surface exchange rate and bulk ionic conductivity. Oxygen permeability of the La₂Cu_1−xCo_xO_4+δ solid solutions was ascertained to increase with cobalt concentration at x=0.02–0.10 and to decrease with further dopant additions, indicating a participation of interstitial oxygen in the ionic transport.     

Current–voltage characteristic of BaTiO3−δ in its mixed n/p regime under oxygen potential gradients

Current (I)–voltage (V) characteristic under oxygen potential gradients was experimentally examined on single crystal BaTiO_3−δ in its mixed ion/electron/hole regime at 1000 °C. The variation of I vs. V appears similar to that of an n/p junction, but with the limiting slope (dI/dV) approaching the maximum and minimum possible equilibrium conductances in the given oxygen potential gradient as increasing forward and reverse bias, respectively. This characteristic has been precisely traced theoretically by using the partial ionic and electronic conductivities of BaTiO_3−δ as measured against uniform oxygen chemical potential in equilibrium state. The nonlinear characteristic is attributed to the redistribution of oxygen chemical potential that is caused by a non-vanishing gradient of the ionic transference number of the oxide under the given oxygen potential gradient. It is demonstrated that the bulk transport properties of a mixed conductor may be tailored by terminal voltage in a chemical potential gradient.     

Defect chemistry and oxygen transport of (La0.6Sr0.4 − xMx)0.99Co0.2Fe0.8O3 − δ, M = Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2), Sr: Part I: Defect chemistry

This paper is the first part of a two part series, where the effects of varying the A-site dopant on the defect chemistry, the diffusion coefficient and the surface catalytic properties of the materials (La_0.6Sr_0.4 − xM_x)_0.99Co_0.2Fe_0.8O_3 − δ, M = Sr, Ca (x = 0.05, 0.1), Ba (x = 0.1, 0.2) (LSMFC) have been investigated. In part I, the findings on the defect chemistry are reported, while the transport properties are reported in part II. Substitution of Sr²⁺ ions with Ca²⁺ ions (smaller ionic radius) and Ba²⁺ ions (larger ionic radius) strains the crystal structure differently for each composition while keeping the average valence of the cations constant. The Ba²⁺ containing materials show the largest oxygen loss at elevated temperatures, while the purely Sr²⁺ doped material showed the smallest oxygen loss. This was reflected in the partial oxidation entropy of the materials. The measured oxygen loss was modelled with point defect chemistry models. Measurements at very low p_O2 showed several phase transitions.     

Germanium and iron co-substituted SrCoO2.5+δ as oxygen permeable membrane

Germanium and iron co-doped SrCoO_2.5+δ was investigated in terms of phase stability, oxygen permeability and electrical conductivity. The favorable high-temperature cubic structure of SrCoO_2.5+δ was stabilized to lower temperatures by co-doping Ge (10 mol%) and Fe (10 mol%) that substituted for Co, which however could not be achieved by doping Ge (20 mol%) alone. In contrast to SrCo_0.8Ge_0.2O_2.5+δ sample which showed a sharp decrease in oxygen permeability at temperature of 875 °C upon cooling, SrGe_0.1Co_0.8Fe_0.1O_3−δ sample remained well-permeable to oxygen at lower temperatures down to at least 820 °C; an abrupt change in electrical conductivity in SrCo_0.8Ge_0.2O_2.5+δ also occurred accompanying the phase transition. The oxygen permeation flux for SrGe_0.1Co_0.8Fe_0.1O_3−δ increased significantly with the decrease of the membrane thickness, indicating the transport of oxygen ions in the bulk of the membrane as the rate-limiting step.     

Transport properties of SrCe0.95Y0.05O3−δ and its application for hydrogen separation

Transport properties of SrCe_0.95Y_0.05O_3−δ were studied by impedance spectroscopy and by measuring open-cell voltage (OCV) and gas permeation. Ionic transference numbers were determined by measuring the OCV of concentration cells and water vapor evolution of an O₂/H₂ fuel cell. We observed interfacial polarization on the basis of the I–V curves obtained by discharging a hydrogen concentration cell or an O₂/H₂ fuel cell. The observed high protonic conductivity (high proton and low oxide ion transference numbers) makes SrCe_0.95Y_0.05O_3−δ a potential material for hydrogen separation. From proton conductivity measurements, under a given hydrogen partial pressure difference of 4%/0.488%, the hydrogen permeation rate (of a dense membrane with 0.11 cm in thickness) was calculated to be ≈0.072 cm³ (STP) cm⁻² min⁻¹ at 800°C, whereas the permeation rate calculated from short-circuit current measurements was ≈0.023 cm³ (STP) cm⁻² min⁻¹ at 800°C. The difference between calculated and observed permeation rates is probably due to interfacial polarization.     

Surface reaction kinetics in oxygen nonstoichiometry re-equilibration of BaTiO3−δ

We report the (bare) surface redox-reaction rate constant that was determined, along with the chemical diffusivity , by a conductivity relaxation technique on Al-doped single crystal and undoped polycrystal BaTiO_3−δ as a function of oxygen activity in its range of −16≤log a_O2≤0 at elevated temperatures of 800–1100 °C. It takes a value in the range of −4<log( /cm s⁻¹)≤−1, which is even larger than that of the oxides that are considered best as oxygen membranes. It has been found that the surface reaction step grows more rate controlling as the electronic transference number gets smaller or the electronic stoichiometric composition (δ≈0) is approached. The oxygen potential drop due to the surface reaction was estimated by an oxygen concentration cell technique. The oxygen potential drop grows larger as the stoichiometric composition is approached, that is in accord with the variation of against oxygen activity.     

Crystal structure, electrical and magnetic properties of La1 − xSrxCoO3 − y

The crystal structure and properties of La_{1 − x}Sr_xCoO_{3 − y} with strontium contents ranging from x = 0.1 to x = 0.7 have been studied. The lattice parameters were measured as a function of temperature (4.2–400 K) and the crystal structure was found to change from rhombohedral (at low temperatures and values of x) to cubic. While LaCoO₃ is paramagnetic the oxides in the composition range 0.2 < x < 0.6 are soft ferromagnets. The strontium additions are compensated by the formation of Co⁴⁺ (cobalt ions with one positive effective charge, Co_Co^.) and oxygen vacancies (V_o^..). From the results it is concluded that the relative importance of oxygen vacancies increases with increasing temperature and decreasing oxygen activity. As a result the concentration of electronic charge carriers — and the resultant electrical conductivity — decrease with increasing temperature. The defect structure is discussed and it is concluded that defect associations — probably between oxygen vacancies and strontium ions — and formation of microdomains of perovskite-related phases are important aspects of the overall structure of these perovskite phases.     

On ionic conduction in the α-phase of PbSnF4

The structure re-refinement of tetragonal PbSnF₄ was executed using data reported earlier. The rms amplitude in M2(Sn) site is larger in (001) plane than along the c-axis and the thermal vibrations of F3 fluorine ions are very large, i.e. B_eq = 12.415(20) A². M2F₈ polyhedra form a distorted cube. The fluorine ions on the F3 site are present between the M2 ion layers. The fluorine ions on the F3 site are located between the M2 ion layers and their weak bonds to Sn ions play an important role in the conduction. The ionic conductivity in the (001) plane is higher than that in the 001 direction.     

Peak effect and oxygen ordering in YBa2Cu3O7−δ single crystals

We have investigated the second magnetization peak in pure YBa₂Cu₃O_7−δ single crystals with various oxygen contents (6.91<7−δ<6.97) and degrees of oxygen vacancy ordering, as achieved by low (1 bar) and high (100 bar) oxygen pressure annealing. Although the position of the peak changes drastically with oxygen stoichiometry, no dependence on the distribution of oxygen vacancies has been found for temperatures below 70 K. For T>70 K, however, ordering effects become important as demonstrated by the disappearance of the peak for the high pressure annealed samples. These results suggest that while at low temperatures, pinning of the vortex system by clusters or a more homogeneous distribution of oxygen vacancies is similar, at elevated T, the former are much stronger pinning sites leading to larger hysteresis and the presence of the peak.     

Effect of the RE ionic size on the REBa2Cu3O7−δ ceramics oxygenated at 250 bar

REBa₂Cu₃O_7−δ (RE=Ho, Y, Dy, Gd, Sm, Nd) ceramics have been oxygenated at 1 bar pressure (LP) and, subsequently, at 250 bar (HP). Despite the noticed slight uptake of oxygen (up to the value of 0.07), after the HP processing, the electrical resistivity (ρ) of all samples increased, what was attributed to the deterioration of the grain boundaries. The increase of ρ was much more pronounced and also accompanied by a change of ρ(T) characteristics into a semiconducting-like one in the case of 123 compounds based on REs which ionic size is large enough to form solid solutions of RE_1+xBa_2−xCu₃O_y type (i.e., RE=Gd, Sm, Nd). As shown in the literature, such 123s usually contain more structural defects. Thus, the observed effect may be attributed to the migration of the defects induced by the elevated pressure oxygenation. The defects could be trapped near the grain boundaries resulting in the deterioration of their electrical properties. The possible role of the oxygen-pressure-induced modifications of the impurity phases has been also discussed. The materials obtained in the HP process may be regarded as 3D arrays of superconducting grains coupled by the Josephson junction or weak links only, as was shown in a tunneling experiment.     

The fragile magnetic structures of Fe/CeH2−δ multilayers

Fe/CeH_2−δ multilayers exhibit at room temperature evidence of interlayer exchange coupling. Subsequent Fe layers are either parallel or antiparallel to each other, depending on the Fe and CeH_2−δ layer thickness. However, when both layers have thickness larger than 15 Å, the antiferromagnetic structure becomes fragmented into domains laterally limited to a few microns, and the magnetic structures become very fragile. Small magnetic fields of a few Oersteds acting on the samples during growth induce helimagnetic configurations which coexist with antiferromagnetic coupling. The magnetic structures can be permanently destroyed by applying magnetic fields larger than 150 Oe.     

Electrochemical behaviour of (La1 − xSrx)sCo1 − yNiyO3 − δ as porous SOFC cathodes

This paper shows that storage at room temperature and ambient atmosphere appears to affect the polarisation resistance significantly and R_P decreased initially with storage time. This improvement was more pronounced when stored in moisturised air. The performance was, however, also found to decrease when stored for sufficiently long periods. The absolute values of the electrode response of these materials are very difficult to reproduce and the performance appears to be largely dependent on the manufacturing process of the powder or the electrode itself. In spite of this, the electrode behaviours exhibited similar patterns with respect to the dependence on T and P_O2. An increase in polarisation resistance with time at SOFC operating conditions was observed, which was related exclusively to the electrode reaction kinetics and not to oxygen concentration polarisation. It was also found to be higher when measured in moisturised air.     

Influence of octahedral tilting and composition on electrical properties of the Li0.2 − xNaxLa0.6TiO3 (0 ≤ x ≤ 0.2) series

The Rietveld analysis of ND patterns of polycrystalline Li_0.2 − xNa_xLa_0.6TiO₃ (0 ≤ x < 0.2) samples, recorded between 300 and 1075 K, shows an orthorhombic–tetragonal transformation, in which the octahedral tilting along the b axis is eliminated at ~ 773 K, but the vacancy ordering along the c axis remains. In Li rich samples, conductivity (10^− 3 Ω^− 1 cm^− 1 at 300 K) departs from the Arrhenius behaviour, decreasing activation energies from 0.37 to 0.14 eV when octahedral tilting is eliminated. Successive Maxwell–Wagner blocking processes, detected in the real part of dielectric constant plots, have been ascribed to the Li blocking at interior domains, grain-boundary and electrode–electrolyte interfaces. The substitution of Li⁺ by Na⁺ decreases the amount of vacant A-sites, decreasing several orders of magnitude the conductivity when the amount of vacancies approaches the vacancy percolation threshold (n_p = 0.27). Below the percolation threshold, Li ions only display local mobility, remaining confined into small domains of perovskites.     

Synthesis and ionic conductivity of new layered perovskite compound, Ag2La2Ti3O10

A new layered perovskite compound, Ag₂La₂Ti₃O₁₀, was synthesized by an ion-exchange reaction of M₂La₂Ti₃O₁₀ (M = Na,K) with a AgNO₃ molten salt. The crystal structure and the ionic conductivity of the ion-exchanged compound were investigated. The ionic conductivities attributed to the interlayer silver ions were observed at high temperatures. The ionic conductivity of Ag₂La₂Ti₃O₁₀ was much higher than that of Na₂La₂Ti₃O₁₀, while the interlayer sodium ions in Na₂La₂Ti₃O₁₀ and silver ions in Ag₂La₂Ti₃O₁₀ have almost the same rock-salt type coordination. The higher conductivity of Ag₂La₂Ti₃O₁₀ is probably due to the higher polarizability of silver ions.     

Oxygen diffusion and surface exchange in La1−xSrxFe0.8Cr0.2O3−δ (x=0.2, 0.4 and 0.6)

Oxygen tracer diffusion (D*) and surface exchange rate constant (k*) have been measured, using isotopic exchange and depth profiling by secondary ion mass spectrometry (SIMS), in La_1−xSr_xFe_0.8Cr_0.2O_3−δ (x=0.2, 0.4 and 0.6). Measurements were made as a function of temperature (700–1000 °C) and oxygen partial pressure (0.21–10⁻²¹ atm) in dry oxygen, water vapour and water vapour/hydrogen/nitrogen mixtures. At high oxygen activity, D* was found to increase with increasing temperature and Sr content. The activation energies for D* in air are 2.13 eV (x=0.2), 1.53 eV (x=0.4) and 1.21 eV (x=0.6). As the oxygen activity decreases, D* increases as expected qualitatively from the increase in oxygen vacancy concentration. Under strongly reducing conditions, the measured values of D* at 1000 °C range from 10⁻⁸ cm² s⁻¹ for x=0.2 to 10⁻⁷ cm² s⁻¹ for x=0.4 and 0.6. The activation energies determined at constant H₂O/H₂ ratio are 1.21 eV (x=0.2), 1.59 eV (x=0.4) and 0.82 eV (x=0.6).

The surface exchange rate constant of oxygen for the H₂O molecule is similar in magnitude to that for the O₂ molecule and both increase with increasing Sr concentration.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ