Influence of Sr substitution on thermoelectric properties of La1−xSrxFeO3 ceramics

Perovskite La_1−xSr_xFeO₃ (0.10 ⩽ x ⩽ 0.20) ceramics have been synthesized by the conventional solid-state reaction technique. Their electrical resistivity, Seebeck coefficient and thermal conductivity have been measured. It has been found that the increase of Sr content reduces significantly both the electrical resistivity and the Seebeck coefficient, but slightly increases the high-temperature thermal conductivity. An adiabatic hopping conduction mechanism of small polaron is suggested from the analysis of the temperature dependence of the electrical resistivity. Seebeck coefficients decrease with increasing temperature, and saturate at temperature above 573 K. The saturated value of Seebeck coefficient decreases with increasing of Sr contents, from 200 μV/K for x = 0.10 to 100 μV/K for x = 0.20. All samples exhibit lower thermal conductivity with values around 2.6 W/m K. The highest dimensionless figure of merit is 0.031 at temperature 973 K in La_0.88Sr_0.12FeO₃.     

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.     

Structure,stability and electrical properties of the La(2−x)SrxMnO4±δ solid solution series

Single phase materials of the La_(2−x)Sr_xMnO_4±δ (0.6 ≤ x ≤ 2.0) solid solution series were prepared via solid state reaction. The structure of each material was examined at room temperature and determined to be tetragonal for all phases examined. An expansion in lattice volume was observed on increasing lanthanum content. The stability and thermal expansion of each member of the solid solution series was determined via the use of in situ high temperature X-ray diffraction. It was found that all materials remained stable up to a temperature of 800 °C. Thermal expansion coefficients were found to be in the region of 15 × 10^− 6 K^− 1 for La_(2−x)Sr_xMnO_4±δ compounds where x > 1.4. The electrical conductivity of each phase was also determined over a similar temperature range with a maximum value of ∼6 Scm^− 1 at 900 °C for the x = 1.8 phase.     

An oxygen permeable membrane La0.8Sr0.2(Ga0.8Mg0.2)1 − xCrxO3 − δ for a reduced atmosphere

Mixed electron hole and oxide ion conducting perovskite-type oxides, La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ (0 ≤ x ≤ 1.0)_, were prepared by solid state reaction. The phase stability and the oxygen permeation properties of the oxides were examined as a function of the content of Cr. La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ has a perovskite related tetragonal phase with x = 0.1 to 0.8. The total electrical conductivity of La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ increases with increasing x. The oxygen permeation flux across the La_0.8Sr_0.2(Ga_0.8Mg_0.2)_1 ? xCr_xO_3 ? δ membranes at higher temperatures increases with x up to x = 04. The maximum oxygen permeation flux of 1.6 × 10^? 7 mol^? 1 cm^? 2 at 1100 °C in a oxygen activity gradient of air/10^? 2 Pa is observed in La_0.8Sr_0.2(Ga_0.8Mg_0.2)_0.6Cr_0.4O_3 ? δ. This perovskite-type oxide is stable under an oxygen partial pressure of 7 × 10^? 10 Pa at 1000 °C.     

Enhancement microwave dielectric properties of La(Mg0.5Sn0.5)O3 ceramics by substituting La3+ with Sm3+

The microwave dielectric properties of La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1?xSm_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. Apparent density of 6.59 g/cm³, dielectric constant (ε_r) of 19.9, quality factor (Q×f) of 70,200 GHz, and temperature coefficient of resonant frequency (τ_f) of ?77 ppm/°C were obtained for La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h. The dielectric constant, and τ_f of La_0.97Sm_0.03(Mg_0.5Sn_0.5)O₃ ceramics were almost independent with the sintering temperature as the sintering temperature varied from 1450 to 1600 °C.     

Electrical properties of yttrium doped strontium titanate with A-site deficiency as potential anode materials for solid oxide fuel cells

Yttrium doped strontium titanate with A-site deficiency ((Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ) was synthesized by conventional solid state reaction. The deficiency limit of A-site in (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ is below 6 mol% in Ar/H₂ (5%) at 1500 °C. The sinterability of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples decreases slightly with increasing A-site deficiency level (x). The ionic conductivity of (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ samples increases while the electronic conductivity decreases with increasing A-site deficient amount. The defect chemistry analysis indicates that the introduction of A-site deficiency results in not only the increase of oxygen vacancy concentration but also the decrease of Ti³⁺-ion concentration. The latter plays the main role in the electrical conduction. (Y_0.08Sr_0.92)_1 ? xTiO_3 ? δ shows good thermal-cyclic performance in electrical conductivity and has an excellent chemical compatibility with YSZ electrolyte below 1500 °C.     

Electrical conductivity and thermal expansion of La0.8Sr0.2(Mn,Fe,Co)O3-δ perovskites

La_1−xSr_xMeO₃ (Me = Mn, Co, Fe) perovskites are used as cathodes and are also attractive materials for application as the contact layer between cathode and interconnect in solid oxide fuel cells. In this contribution, three perovskite series, La_0.8Sr_0.2Mn_1−xCo_xO_3-δ (series 1), La_0.8Sr_0.2Fe_1−xCo_xO_3-δ (series 2) and La_0.8Sr_0.2Mn_1−x/2Fe_(1−x)/2Co_xO_3-δ (series 3) with x = 0, 0.25, 0.5, 0.75 and 1 were re-investigated under identical synthesis and measurement conditions with the aim of obtaining a full overview of the quasi-ternary system La_0.8Sr_0.2MnO_3-δ–La_0.8Sr_0.2FeO_3-δ–La_0.8Sr_0.2CoO_3-δ. The distribution of the different crystallographic phases in the selected series, the DC electrical conductivity and the thermal expansion coefficients are presented.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.     

Oxygen nonstoichiometry and transport properties of strontium substituted lanthanum cobaltite

Oxygen nonstoichiometry, structure and transport properties of the two compositions (La_0.6Sr_0.4)_0.99CoO_3−δ (LSC40) and La_0.85Sr_0.15CoO_3−δ (LSC15) were measured. It was found that the oxygen nonstoichiometry as a function of the temperature and oxygen partial pressure could be described using the itinerant electron model. The electrical conductivity, σ, of the materials is high (σ > 500 S cm^− 1) in the measured temperature range (650–1000 °C) and oxygen partial pressure range (0.209–10^− 4 atm). At 900 °C the electrical conductivity is 1365 and 1491 S cm^− 1 in air for LSC40 and LSC15, respectively. A linear correlation between the electrical conductivity and the oxygen vacancy concentration was found for both samples. The mobility of the electron-holes was inversely proportional with the absolute temperature indicating a metallic type conductivity for LSC40. Using electrical conductivity relaxation the chemical diffusion coefficient of oxygen was determined. It was found that accurate values of the chemical diffusion coefficient could only be obtained using a sample with a porous surface coating. The porous surface coating increased the surface exchange reaction thereby unmasking the chemical diffusion coefficient. The ionic conductivity deduced from electrical conductivity relaxation was determined to be 0.45 S cm^− 1 and 0.01 S cm^− 1 at 1000 and 650 °C, respectively. The activation energy for the ionic conductivity at a constant vacancy concentration (δ = 0.125) was found to be 0.90 eV.     

Development and characterization of a quasi-ternary diagram based on La0.8Sr0.2(Co,Cu,Fe)O3 oxides in view of application as a cathode contact material for solid oxide fuel cells

Oxides resulting from discrete changes in composition within the quasi-ternary system La_0.8Sr_0.2CuO_2.4 + δ–La_0.8Sr_0.2CoO_3 ? δ–La_0.8Sr_0.2FeO_3 ? δ were investigated under similar experimental conditions with the objective of obtaining an overview of the variation of the relevant properties for possible applications as cathode contact layer in SOFCs. Twenty-two oxide compositions within this system were systematically selected and synthesized under identical conditions by the Pechini method. The distribution of the different crystallographic phases at 1050 °C within this quasi-ternary phase diagram, the DC electrical conductivity at 800 °C and the thermal expansion coefficients are presented. Perovskites of different compositions issued from this ternary diagram were tested as cathode contact material between an La_0.8Sr_0.2FeO₃ cathode and a Crofer22APU interconnect by resistance measurements at 800 °C. The application of a MnCo_1.9Fe_0.1O₄ spinel protection reduced the interfacial reaction between the Crofer22APU and the cathode contact material. Electrical resistance measurements at 800 °C in air up to 1000 h and the analysis by scanning electron microscopy/energy-dispersive X-ray spectroscopy of the sample cross-sections were carried out to verify the surface stability and the electrical performance.     

A ceria layer as diffusion barrier between LAMOX and lanthanum strontium cobalt ferrite along with the impedance analysis

A thin interlayer of samarium doped ceria (SDC) is applied as diffusion barrier between La_1 ? xSr_xCo_yFe_1 ? yO₃ x = 0.1–0.4, y = 0.2–0.8 (LSCF) cathode and La_1.8Dy_0.2Mo_1.6W_0.4O₉ (LDMW82) electrolyte to obstruct Mo–Sr diffusion and solid state reaction in the intermediate temperature range of SOFC. We demonstrate the effectiveness of the diffusion barrier through contrasting the clearly defined interfaces of LSCF/SDC/LDMW82 against a rugged growing product layer of LSCF/LDMW82 in 800 °C thermal annealing, and analyze the product composition and the probable new phase. In addition, the measured polarization resistance is considerably lower for the half-cell with a diffusion barrier. Therefore, the electrochemical performance of the LSCF cathode is investigated on the SDC-protected LDMW82. The cell with LSCF (x = 0.4) persistently outperforms the one with x = 0.2 in polarization resistance because of its small low-frequency contribution. The activation energy of polarization resistance is also lower for La_0.6Sr_0.4Co_yFe_1 ? yO₃ (112–135 kJ/mol), than that for La_0.8Sr_0.2Co_yFe_1 ? yO₃ (156–164 kJ/mol). La_0.6Sr_0.4Co_yFe_1 ? yO₃ y = 0.4–0.8 is the proper composition for the cathode interfaced to SDC/LDMW82.     

High temperature properties of the n = 2 Ruddlesden–Popper phases (La,Sr)3(Fe,Ni)2O7−δ

The crystal chemistry and mixed conductor properties of the n = 2 member of the Ruddlesden–Popper (R–P) phases Sr_3−xLa_xFe_2−yNi_yO_7−δ with 0 ≤ x ≤ 0.3 and 0 ≤ y ≤ 1.0 have been studied at high temperature. High-temperature X-ray diffraction and thermogravimetric measurements of the equilibrium pO₂ (10^− 5 ≤ pO₂ ≤ 1 atm) in the temperature range 400 ≤ T ≤ 1000 °C indicate that the Sr₃FeNiO_7−δ phase is able to accommodate a large oxygen non-stoichiometry (δ ∼ 1.5) without structural transformations. The electrical conductivity and oxygen permeability increase with the substitution of Ni for Fe in the range 550 ≤ T ≤ 1000 °C. The electrical transport of the Sr₃FeNiO_7−δ phase is thermally activated and the activation energy decreases with the substitution of Ni for Fe for a given oxygen content. The increase in the oxygen permeation flux with increasing Ni content is due to an increasing oxygen non-stoichiometry and a lower activation energy for permeation.     

Electronic transport in the novel SOFC anode material La1−xSrxCr0.5Mn0.5O3±δ

Electronic conductivity in the potential SOFC anode material La_1−xSr_xCr_0.5Mn_0.5O_3±δ has been investigated in the range 0.2 < x < 0.3. log(σT) vs. 1/T plots indicate conduction via thermally activated polaron hopping. At 900 °C, conductivity in air increases with Sr²⁺ via an increase in [B_B] holes (B—transition metal). X-ray absorption spectroscopy (XAS) studies indicate that compensation for A-site Sr substitution and oxygen vacancy formation is via the Mn cation only; Cr maintains a 3+ oxidation state and 6-fold oxygen coordination. Electronic transport occurs by percolation between Mn cations in a disordered B-site sub-lattice. Conductivity decreases with p(O₂), which is indicative of p-type conduction behaviour, but the relationship cannot be explained by a simple redox equilibrium involving Mn³⁺, Mn⁴⁺ and oxygen, possibly due to co-existence of Mn²⁺, Mn³⁺ and Mn⁴⁺ via disproportionation as with La_1−xSr_xMnO_3±δ.     

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.     

Thermal diffusivity and electrical conductivity in fast ion conducting composites: A correlation

The thermal diffusivity and electrical conductivity have been measured for two ion conducting polyethylene oxide (PEO) based polymer–ceramic composites viz. (PEO:NH₄I) + xAl₂O₃, (PEO:LiBF₄) + xBa_0.70Sr_0.30TiO₃ and two solid–solid composites viz. AgI + xAl₂O₃, AgI +xBa_0.70Sr_0.30TiO₃. The thermal diffusivity has been measured by the novel photoacoustic technique while the electrical conductivity has been measured by impedance spectroscopy technique using complex impedance plots. The pattern of variation in the electrical conductivity (σ) vs. composition plot and that in the thermal diffusivity (α_s) vs. composition plot are similar. Interestingly, the correlation between α_s and σ is not only qualitative but is quantitative as well in the sense that the ratio (α_s / σ) remains constant for all the samples within the same system (though their conductivities are different) similar to Wiedmann–Franz law applicable to metallic conductors.     

Structure and electrochemical properties of Sm0.5Sr0.5Co1 − xFexO3 − δ cathodes for solid oxide fuel cells

Crystal structure, thermal expansion coefficient, electrical conductivity and cathodic polarization of compositions in the system Sm_0.5Sr_0.5Co_1 − xFe_xO_3 − δ with 0 ≤ x ≤ 0.9 were studied as function of Co / Fe ratio and temperature, in air. Two phases, including an Orthorhombic symmetry for 0 ≤ x ≤ 0.4 and a cubic symmetry for 0.5 ≤ x ≤ 0.9, were observed in samples of Sm_0.5Sr_0.5Co_1 − xFe_xO_3 − δ at room temperature. The adjustment of thermal expansion coefficient (TEC) to electrolyte, which is one of the main problems of SSC, could be achieved to lower TEC values with more Fe substitution. High electrical conductivity above 100 S/cm at 800 °C was obtained for all specimens, so they could be good conductors as cathodes of IT-SOFC. The polarization behavior of SSCF as a function of Fe content was evaluated by means of AC impedance using LSGM electrolyte. It was discovered that the Area Specific Resistance (ASR) of SSCF increased as the amount of substitution of Fe for Co increased. When the amount of Fe reached to 0.4, the highest ASR was obtained and then the resistance started decreasing above that. The electrode with a composition of Sm_0.5Sr_0.5Co_0.2Fe_0.8O_3 − δ showed high catalytic activity for oxygen reduction operating at temperature ranging from 700 to 800 °C.     

A-deficit LSCF for intermediate temperature solid oxide fuel cells

A-deficit La_0.54Sr_0.44Co_0.2Fe_0.8O_3 ? δ cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) was synthesized by a citrate complexation (Pechini) route. Using La_0.54Sr_0.44Co_0.2Fe_0.8O_3 ? δ as cathode material, a superior cell performance with the maximum power density of 309, 470 and 855 mW cm^? 2 at 600, 650 and 700 °C was achieved, in contrast with the maximum power density of 266, 354 and 589 mW cm^? 2 using conventional La_0.6Sr_0.4Co_0.2Fe_0.8O_3 ? δ as cathode material at the same temperatures. The reason of this improvement was analyzed on the basis of defect chemistry. Thermal shrinkage experiment testified that the oxygen vacancies in La_0.54Sr_0.44Co_0.2Fe_0.8O_3 ? δ are more mobile than in La_0.6Sr_0.4Co_0.2Fe_0.8O_3 ? δ. Furthermore, theoretical calculation in terms of their composition and the shift of peak position in XRD pattern showed that the concentration of oxygen vacancies of La_0.54Sr_0.44Co_0.2Fe_0.8O_3 ? δ is higher than that of La_0.6Sr_0.4Co_0.2Fe_0.8O_3 ? δ. Therefore, the oxygen ion conductivity via vacancies transfer mechanism is enhanced, which induces the polarization resistance of La_0.54Sr_0.44Co_0.2Fe_0.8O_3 ? δ being decreased with a result of cell performance improved.     

Sintering kinetics and oxide ion conduction in Sr-doped apatite-type lanthanum silicates,La9Sr1Si6O26.5

These last past years, a major interest has been devoted to decrease the working temperature of solid oxide fuel cells (SOFCs) down to about 700 °C.Apatite materials (La_10 ? xSr_xSi₆O_27?x/2) are attractive candidates for solid electrolytes, with a high ionic conductivity at these intermediate temperatures. An apatite powder (x = 1) with a 0.75 µm mean particle size, produced by solid state reaction, was tape cast to obtain green sheets with a thickness of about 260 µm.On one hand, the densification mechanism of the apatite ceramic during the intermediate solid state sintering has been approached. It appeared from the kinetical tests performed under isothermal conditions between 1250 and 1550 °C, that densification could be controlled by the diffusion at grain boundaries of the rare-earth element, La, with an activation energy of 470 kJ/mol.On the other hand, conductivity measurements were performed on apatite samples sintered at 1400 and 1500 °C. The ionic conductivity was mainly sensitive to the presence of secondary phases at 1400 °C. The ionic conductivity of the apatite sintered at 1500 °C (mean grain size = 3.9 µm) is equal to 1.2 × 10^? 2 S/cm at 700 °C.     

Mixed conducting perovskite-like ceramics on the base of lanthanum gallate

Ceramic perovskite solid solutions (La_0.9Sr_0.1)[(Ga_1−xM_x)_0.8Mg_0.2]O_3−y, 0 ≤ x ≤ 0.5, M = Fe, Ni, Cr (systems I–III) and brownmillerite solid solutions (La_0.2Sr_1.8)[Ga(Fe_1−xMg_x)]O_5−z, 0 ≤ x ≤ 0.5, (system IV) have been prepared. The samples have been studied by X-ray diffraction and electron microscopy methods, dielectric spectroscopy and permeability measurements. The correlation between the composition, unit cell parameter changes, electrical transport and oxygen permeation properties has been revealed. Introduction of transition metals (Fe, Ni, or Cr), substituting for gallium, ensures the enhancement of the electronic constituent of the conductivity in the perovskite systems I–III. Stabilization of the transition metal high valence states 4+ or 5+ has been suggested for compositions I and III. This leads to a unit cell volume contraction and provides a decrease in the concentration of oxygen vacancies. The oxygen permeability reaches its maximum values in compositions I–III with x ∼ 0.3. On the contrary, increasing concentration of the doping element with lower valence state (magnesium), substituting for iron, determines the expansion of the brownmillerite unit cell volume and provides an increase of the oxygen vacancy concentration, which in turn, favors the enhancement of oxygen permeability of composition IV.     

Chemical diffusion of water in the double perovskites Ba4Ca2Nb2O11 and Sr6Ta2O11

The mechanism and kinetics of water incorporation in the double perovskites Ва₄Ca₂Nb₂O₁₁ and Sr₆Ta₂O₁₁ has been investigated (T = 300÷500 °C and aH₂O = 1 · 10^− 3÷2.2 · 10^− 2). The formation of hydration products Ba₄Ca₂Nb₂O₁₁·xH₂O and Sr₆Ta₂O₁₁·xH₂O (0.2 < x < 0.50) was limited by the diffusion of H₂O. It has been found that the concentration dependences of D˜_H2O are the same for both samples: small increasing of D˜_H2O with increasing x. The temperature dependences of the chemical diffusion coefficients of water for compositions of Ba₄Ca₂Nb₂O₁₁·0.35H₂O and Sr₆Ta₂O₁₁·0.35H₂O could be described with close activation energies of E_a = 0.38 ± 0.03 eV and E_a = 0.49 ± 0.03 eV, respectively. The chemical diffusion coefficients of water are nearly one order of magnitude smaller for tantalate Sr₆Ta₂O₁₁. This result correlates with lower oxygen and proton conductivities in Sr₆Ta₂O₁₁ as the consequence of lower mobilities.