Electronic conduction in La-based perovskite-type oxides

A systematic study of La-based perovskite-type oxides from the viewpoint of their electronic conduction properties was performed. LaCo_0.5Ni_0.5O_3±δ was found to be a promising candidate as a replacement for standard metals used in oxide electrodes and wiring that are operated at temperatures up to 1173 K in air because of its high electrical conductivity and stability at high temperatures. LaCo_0.5Ni_0.5O_3±δ exhibits a high conductivity of 1.9 × 10³ S cm⁻¹ at room temperature (R.T.) because of a high carrier concentration n of 2.2 × 10²² cm⁻³ and a small effective mass m∗ of 0.10 m_e. Notably, LaCo_0.5Ni_0.5O_3±δ exhibits this high electrical conductivity from R.T. to 1173 K, and little change in the oxygen content occurs under these conditions. LaCo_0.5Ni_0.5O_3±δ is the most suitable for the fabrication of oxide electrodes and wiring, though La_1−xSr_xCoO_3±δ and La_1−xSr_xMnO_3±δ also exhibit high electronic conductivity at R.T., with maximum electrical conductivities of 4.4 × 10³ S cm⁻¹ for La_0.5Sr_0.5CoO_3±δ and 1.5 × 10³ S cm⁻¹ for La_0.6Sr_0.4MnO_3±δ because oxygen release occurs in La_1−xSr_xCoO_3±δ as elevating temperature and the electrical conductivity of La_0.6Sr_0.4MnO_3±δ slightly decreases at temperatures above 400 K.     

Electrical conductivity of LaxSr2−xFe1−yRuyO4±δ

Materials of the K₂NiF₄ structure type have been prepared and the electrical conductivity in air determined for a number of compositions in the La_xSr_2−xFe_1−yRu_yO_4±δ solid solution series including three with Ru substituted for Fe on the B site: La_0.2Sr_1.8Fe_0.6Ru_0.4O_4±δ, La_0.4Sr_1.6Fe_0.7Ru_0.3O_4±δ, and La_0.6Sr_1.4Fe_0.8Ru_0.2O_4±δ. Overall the total conductivity values measured were lower than expected for the Ru-doped materials, with a peak conductivity of ≈2 S cm⁻¹ at 700 °C. In the undoped La_xSr_2−xFeO_4±δ materials, a significant jump in conductivity was observed between the x = 0.7 and 0.8 compositions and was related to the bonding in the materials and the Fe³⁺/Fe⁴⁺ redox behaviour. In all materials, the conduction behaviour was found to follow a semi-conducting trend.     

A new route to synthesize La1?xSrxMnO3

Self-Propagating High-temperature Synthesis (SHS) was used to producecomplex oxides (La_1–x Sr _x MnO₃ with x = 0, 0.1 and 0.2), which are used as the cathode in solid oxide fuel cells (SOFCs). Thermodynamic predications and experiments show that La_1–x Sr _x MnO₃ can be prepared via SHS under moderate conditions from a mixture of La₂O₃ + SrO₂ + Mn, using either gaseous oxygen or solid NaClO₄ as the oxidant. Partial melting at the high combustion temperature increased product homogeneity. The electrical conductivity of the product was 180 S·cm^–1 at 1000°C in air, matching that of sample made by other synthesis processes. SHS enables a more economical production of La_1–x Sr _x MnO₃ than existing commercial processes.     

Structures and properties of La1−x,Sr x CoO3−y,prepared by freeze drying

Several samples of La_1–x Sr _x CoO_3–y (x = 1, 0.8, 0.5, 0.2) were prepared by calcining freezedried, stoichiometric mixtures of nitrates at different temperatures and for different lengths of time. Selected samples were characterized by powder X-ray diffraction, conductivity measurements, Brunauer-Emmett-Teller surface area measurement, and by electrochemical cyclic voltammetry in alkaline solutions and alkaline solutions containing methanol. The structures of each composition were complex and varied with composition and preparation conditions. There is evidence for non-stoichiometry caused by oxygen anion vacancies. For La_0.5Sr_0.5CoO_3–y the electrochemical activity towards the oxidation of methanol is a maximum at the fully formed cubic perovskite. The oxidation currents at La_0.8Sr_0.2CoO_3–y and La_0.2Sr_0.8CoO_3–y go through maxima at more distorted structures.     

A Porous Perovskite Nanofiber with Reinforced Aerophobicity for High-Performance Anion Exchange Membrane Water Splitting

Perovskite oxides stand out as emerging oxygen evolution reaction (OER) catalysts on account of their effective electrocatalytic performance and low costs. Nevertheless, perovskite oxides suffer from severe bubble overpotential and inhibited electrochemical performance in large current densities due to their small specific surface areas and structural compactness. Herein, the study highlights the electrospun nickel-substituted La_0.5Sr_0.5FeO_3-δ (LSF) porous perovskite nanofibers, that is, La_0.5Sr_0.5Fe_1-xNi_xO_3-δ (denoted as ES-LSFN-x, x = 0, 0.1, 0.3, and 0.5), as high-performance OER electrocatalysts. The most effective La_0.5Sr_0.5Fe_0.5Ni_0.5O_3-δ (ES-LSFN-0.5) nanofibers suggest a larger specific surface area, higher porosity, and faster mass transfer than the counterpart sample prepared by conventional sol–gel method (SG-LSFN-0.5), showing notably increased geometric and intrinsic activities. The bubble visualization results demonstrate that the enriched and nano-sized porosity of ES-LSFN-0.5 enables reinforced aerophobicity and rapid detachment of oxygen bubbles, thereby reducing the bubble overpotential and enhancing the electrochemical performance. As a result, the ES-LSFN-0.5-based anion exchange membrane water electrolysis delivers a superior stability of 100 h while the SG-LSFN-0.5 counterpart degrades rapidly within 20 h under a current density of 100 mA cm⁻². The results highlight the advantage of porous electrocatalysts in optimizing the performance of large current density water electrolysis devices by reducing the bubble overpotential.     

Magnetic susceptibility, spin transition, and electrical conductivity of LaCo1 + xO3 and NdCo1 + xO3

The magnetic susceptibility of Nd₂O₃, NdCo_{1 + x} O₃, and LaCo_{1 + x} O₃ (x = 0, 0.05, 0.1, 0.15) has been measured at temperatures from 80 to 950 K, and the electrical conductivity of the neodymium and lanthanum cobaltites (enriched in cobalt relative to neodymium or lanthanum) with the general formulas Nd(La)Co_{1 + x} O_{3 + 1.5x} , or Nd_{1/(1 + x)}(La)_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)}, has been measured between 300 and 1050 K. The effective magnetic moments of paramagnetic ions have been determined in the temperature ranges of CurieWeiss behavior and have been used to evaluate the fractions of low-, intermediate-, and high-spin Co³⁺ ions. Raising the temperature from 320 to 660 K (non-Curie—Weiss behavior) increases the fraction of high-spin Co³⁺ ions in LaCo_{1 + x} O_{3 + 1.5x} (La_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)} from 27–43 to 56–61%. Moreover, in this temperature range the conductivity of the lanthanum cobaltites rises most steeply. In the range 660–950 K, no spin transition occurs in LaCo_{1 + x} O_{3 + 1.5x} , the slope of the conductivity versus temperature curves gradually decreases, and the conductivity gradually saturates. The conductivity of NdCo_{1 + x} O_{3 + 1.5x} (Nd_{1/(1 + x)}CoO_{(3 + 1.5x)/(1 + x)}) varies considerably in the range 550–950 K, and the spin transition in these cobaltites takes place between 260 and 760 K. Above 760 K, the NdCo_{1 + x} O_{3 + 1.5x} cobaltites with x = 0.05 and 0.10 contain, respectively, 72 and 83% high-spin Co³⁺ ions and 28 and 17% high-spin Co⁴⁺ ions, whereas neodymium cobaltite with x = 0.15 contains 83% high-spin and 17% intermediate-spin Co³⁺ ions. Original Russian Text ? S.V. Shevchenko, L.A. Bashkirov, G.S. Petrov, S.S. Dorofeichik, N.N. Lubinskii, 2008, published in Neorganicheskie Materialy, 2008, Vol. 44, No. 1, pp. 88–94.     

Observation of Higher Suppression of Superconducting Transition Temperature in YBa2Cu3O7??? /La0.5Sr0.5CoO3 as?Compared?to?YBa2Cu3O7??? /La0.7Sr0.3MnO3 Bilayers

We report the experimental investigations of the suppression of superconductivity due to the pair breaking effect induced by ferromagnetic layer in YBa₂Cu₃O_7??? /La_0.5Sr_0.5CoO₃ and YBa₂Cu₃O_7??? /La_0.7Sr_0.3MnO₃ bi-layers fabricated by pulsed laser deposition. The current dependent electrical transport studies in the bilayers exhibit a significant reduction in the superconducting transition temperature in accord to I ^2/3 law as compared to single YBa₂Cu₃O_7??? layer, and moreover the superconducting transition temperature in YBa₂Cu₃O_7??? /La_0.7Sr_0.3MnO₃ bilayer is surprisingly found to be much larger than the YBa₂Cu₃O_7??? /La_0.5Sr_0.5CoO₃. It appears that the current driven from a low spin polarization (?11%) material like La_0.5Sr_0.5CoO₃ can also suppress the superconductivity to a larger extent. This indicates that the degree of spin polarization of the ferromagnetic electrode is not the only criteria to determine the suppression of superconductivity by pair breaking effect in superconductor/ferromagnet hybrid structures; rather the transparency of the interface for the spin polarization, the formation of vortex state due to the stray field of ferromagnetic layer and the ferromagnetic domain patterns might play significant roles to determine such effect.     

Structural, magnetic, infrared and Raman studies of La0.8Sr x Ca0.2-x MnO3 (0 ≤ x ≤ 0.2)

We report the results of magnetic, X-ray powder diffraction, infrared and temperature dependent Raman spectra of the La_0.8Sr _x Ca_0.2-x MnO₃ (0 ≤ x ≤ 0.2) manganite. The structure refinement using the Rietveld method indicates that the partial substitution of strontium for calcium (for x ≥ 0.15) modifies the orthorhombic structure of the CaMnO₃ perovskite towards a rhombohedral phase. Magnetic measurement confirms the increase in the Curie temperature from 180 K for La_0.8Ca_0.2MnO₃ to 307 K for La_0.8Sr_0.2MnO₃, respectively. It is argued that the substitution with the larger Sr²⁺ ion strengthens the double-exchange interaction and gives rise to the observed increase of transition temperatures. All manganites show two IR active vibrational modes around 400 and 600 cm^?1. Moreover, when x ≤ 0.1, the absorption band around 400 cm^?1 splits into two peaks. In addition, we have analyzed the frequencies and widths of the observed Raman modes as a function of temperature for all samples with various Sr content. The mode splitting is attributed to both magnetic ordering and large orthorhombic distortion in doped rhombohedral manganites.     

Structural,Thermal, and Electrical Study of Bi0.5Sr0.5MnO3

Solid oxide fuel cell (SOFC) is considered as a potential candidate for clean and efficient alternate energy source. Efforts are being made to reduce their operating temperature for SOFCs commercialization. However, the reduction in operating temperature increases the polarization effect in the existing cathodes. In the present study, Bi_0.5Sr_0.5MnO₃ was synthesized and studied for its structural, thermal, and electrical properties. Bi_0.5Sr_0.5MnO₃ was synthesized by conventional solid state reaction method. The as-prepared sample was characterized by x-ray diffraction, scanning electron microscope, thermogravimetric analysis, dilatometer and impedance spectroscopy. The Rietveld refinement results confirm that Bi_0.50Sr_0.50MnO₃ shows the tetragonal symmetry with p4 mm space group. Scanning electron microscopy study shows that the distribution of grains is uniform and the grains are well connected to each other due to better sinterability of the samples. The dilatometric curve shows linear behavior up to 600°C and after that becomes steeper. This can be due to the loss of lattice oxygen at higher temperatures and creation of oxygen vacancies. The thermal expansion coefficient of the system is ～8.9 × 10^?6 °C^?1 and total conductivity of the sample is ～4.78 × 10^?3 S/cm.     

Preparation and properties of thick LaMnO3-based films

Thick (50 ±10 μm) La_1-xSr_xMnO₃ (x = 0.2, 0.4) and La_0.7Ca_0.3Mn0₃ films were prepared by screen printing, and their electrical properties were studied. The films were found to be close in magnetoresistance and resistivity to bulk materials     

Itinerant electron behaviour and long-range ordering in La1−x Sr x CoO3

Electrical resistivity of La_1?x Sr _x CoO₃ is reduced significantly by the substitution of Ni³⁺ ions in place of the cobalt ions. In the La_1?x Sr _x Co_1?y Ni _y O₃ system, for small values ofx(x=0·05) superparamagnetic clusters seem to be formed at lower temperatures (<300 K). The formation of such clusters is not affected by the presence of nickel ions. Whenx is large, the occurrence of long-range ordering seems to depend on the itinerancy of charge carriers.     

Structural, thermal, and electrical properties of La0.7Sr0.3Mn1−y FeyO3±δ

The crystal structure, thermal expansion, and electrical conductivity of the doped manganites La_0.7Sr_0.3Mn_1?y Fe_yO_3±δ (y = 0, 0.1, 0.2, 0.3) are studied. The manganites are shown to crystallize in rhombohedral symmetry (sp. gr. $R\bar 3c$ ). Their lattice parameters are determined, and their thermal expansion coefficients are measured in the range 600–1223 K in air. The conductivity of the manganites is measured in broad ranges of oxygen partial pressures (p _{O 2} = 0.1 to 10^?15 MPa) and temperatures (T = 1073–1273 K). The effects of Fe content, temperature, and p _{O 2} on the dominant defect species and the nature of electrical transport in La_0.7Sr_0.3Mn_1?y Fe_yO_3±δ are analyzed.     

Combined platinum/perovskite catalyst for an efficient nanostructured air electrode

This work shows the stepwise improvement of air electrodes by the right combination of catalysts. In all electrodes carbon nanotubes serve as carbon support. The electrodes are produced by ultrasonic mixing of the carbon nanotubes and the catalysts. Their catalytic activity towards oxygen reduction in alkaline solution is evaluated by polarisation curves and electrochemical impedance spectroscopy. In a first step La_1?xSr_xMnO₃ perovskites are investigated, as well as La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃ are compared. It is found that La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃ have a positive impact on different parts of the current–potential curve. In a second step the influence of small amounts of platinum as an additional catalyst besides the perovskite is analyzed with the result that platinum lowers significantly the activation polarisation. Finally, the optimum composition of the electrode is found by using the synergetic effect of platinum, La_0.65Sr_0.35MnO₃ and La_0.6Sr_0.4CoO₃.     

Comparison of Pb(Zr,Ti)O3 capacitors sandwiched with conductive La0.5Sr0.5CoO3 and non-conductive Bi3.25La0.75Ti3O12 layers

Ferroelectric capacitors of Bi_3.25La_0.75Ti₃O₁₂/PbZr_0.4Ti_0.6O₃/Bi_3.25La_0.75Ti₃O₁₂ (BLT/PZT/BLT) and La_0.5Sr_0.5CoO₃/PbZr_0.4Ti_0.6O₃/La_0.5Sr_0.5CoO₃ (LSCO/PZT/LSCO) are fabricated, respectively, on Si substrates in order to study the properties of PZT film sandwiched by conductive oxide and non-conductive oxide layers. It is found that the crystallinity of PZT film grown on LSCO electrode is much better than that on BLT film although the growth temperature of BLT/PZT/BLT is 100 °C higher than that of LSCO/PZT/LSCO. Remanent polarization of LSCO/PZT/LSCO capacitors measured at 10 V is 31.1 μC/cm², which is much higher than the value of 19.8 μC/cm² for BLT/PZT/BLT. Both kinds of the capacitors are fatigue-free up to 10¹⁰ switching cycles. The leakage current density measured at 5 V is about 4.7 × 10^− 6 A/cm² and 1.9 × 10^− 5 A/cm² for BLT/PZT/BLT and LSCO/PZT/LSCO, respectively. The differences for the two kinds of capacitors are discussed in the article.     

Influence of Ag-doping in La0.5Sr0.5CoO3 on Its Structural and Magnetic Properties

The structural and magnetic properties of the mixed valent cobaltites La_0.5Sr_0.5?x Ag _x CoO₃ (0≤x≤0.15) with perovskite structure have been investigated. X-ray diffraction (XRD) analysis using Rietveld refinement shows that all our samples crystallize in the orthorhombic structure with $R\overline{3}c$ space group. Although the unit cell volume remains almost constant, the Co–O bond length and the Co–O–Co bond angle are sensitive to the Ag addition. All our studied samples undergo a paramagnetic-ferromagnetic transition with decreasing temperature. The zero field cooled (ZFC) and field cooled (FC) magnetization curves at 50 mT of La_0.5Sr_0.5CoO₃ (x=0) sample exhibits thermomagnetic irreversibility indicating frustration and competition of both antiferromagnetic and ferromagnetic interactions. It is suggested that Co³⁺ ions are in the intermediate spin state but Co⁴⁺ ions stay in a mixture of intermediate and high spin states. Ag addition leads to dramatic changes in magnetic properties. An interesting result has been obtained for La_0.5Sr_0.4Ag_0.1CoO₃, where the ZFC and FC curves coincide. For La_0.5Sr_0.35Ag_0.15CoO₃ (x=0.15) sample, the observed thermomagnetic irreversibility is much higher than that observed in x=0 sample. Hysteresis loops were recorded for x=0, 0.05, 0.1, and 0.15. The coercitive field is found to increase with Ag content reaching 0.26 T for x=0.15 whereas the remanent magnetization decreases.     

Dielectric properties of La2O3-doped Ba0.8Sr0.2TiO3 ceramics

La₂O₃-doped Ba_0.8Sr_0.2TiO₃ dielectric ceramics were prepared by conventional solid state ceramic route. Scanning electron microscope was employed to observe the surface morphologies. The capacitance C and dielectric loss factor D of the samples were measured with automatic LCR Meter 4225 at 10 kHz respectively. The results show that: ε _r of the samples decreases and tgδ first decreases then increases with increasing amount of La₂O₃ doping. ε _r reaches better value, tgδ obtains the minimum value at 0.5 mol% La₂O₃. ε _r increases and tgδ decreases when sintering temperature increases. The samples doped with 0.5 mol% La₂O₃ sintered at 1,350 °C for 10 h exhibited attractive properties, including high relative dielectric constant (>4,000), low dielectric loss (16.8 × 10^?4), low temperature coefficient of relative dielectric constant(<±21 %) in the temperature range of +25 to +85 °C.     

New cathode compositions based on La0.84Sr0.16Mn1−xMxO3, where M = Al, Ga for solid oxide fuel cell

In order to identify new cathode compositions for the high temperature solid oxide fuel cell, we have investigated the effect of the trivalent cations Al and Ga at the Mn site of the well-studied cathode composition La_0.84Sr_0.16MnO₃. All the compositions have been prepared by the low temperature citrate-nitrate auto-ignition process and sintered within the temperature range of 1150-1350 °C for 4 h. In order to understand the compatibility of the prepared samples as alternative cathode materials, we compared their electrical conductivity and thermal expansion coefficient with those of La_0.84Sr_0.16MnO₃ and yttria-stabilized zirconia. A 10 mol% Al doped La_0.84Sr_0.16MnO₃ composition exhibited a conductivity of around 122 S cm⁻¹ at 950 °C and a thermal expansion coefficient of 11.04 × 10⁻⁶ K with a minimum reactivity towards yttria-stabilized zirconia. Though the conductivity of the new composition is lower than that of La_0.84Sr_0.16MnO₃ (169 S cm⁻¹ at 950 °C), it is still high enough for use as a cathode material.     

Fabrication of (La1−x Gd x )2/3Sr1/3MnO3 Manganite Perovskite Nanorods by Sonication-Assisted Coprecipation

(La_1?x Gd _x )_2/3Sr_1/3MnO₃ manganite perovskite nanorods were synthesized by sonication-assisted coprecipitation. Lower sintering temperatures were required for all the samples to crystallize. The fully crystallize samples of (La_0.5Gd_0.5)_2/3Sr_1/3MnO₃ and (La_0.4Gd_0.6)_2/3Sr_1/3MnO₃ show the formation of nanorods upon their synthesis with an average length and width of 160 nm and 20 nm, respectively. The structural, electrical, and magnetic transport properties were investigated.     

Synthesis of Ni-doped LaSrMnO3 nanopowders by hydrothermal method for SOFC interconnect applications

Ni-doped lanthanum strontium manganite (LSMN) nanopowders, La_0.7Sr_0.3Mn_1?xNi_xO₃ (0.05?≤?x?≤?0.3) were synthesized at 150?°C for 8?h by hydrothermal reaction as a function of Ni doping concentration. The SEM analyses suggested that the calcination treatment influenced the morphology of the nanopowders. The calcined nanopowders at 1300?°C had agglomerated spherical structure of 44–77?nm. Meanwhile, the XRD studies revealed that the nanopowders have single crystalline phase over the range x?=?0.05–0.2. In addition, the LSMN nanopowders were sintered at elevated temperatures, 1250–1350?°C to examine their electrical conductivity for solid oxide fuel cell (SOFC) interconnect applications under actual SOFC working condition. Their electrical conductivity gradually increased to 90.05?S/cm with Ni doping concentration x?=?0.2, which were sintered at 1300?°C. These results suggest La_0.7Sr_0.3Mn_0.8Ni_0.2O₃ displays a good performance as an optimal composition of the LSMN.     

Novel Multifunctional Properties Induced by Interface Effects in Perovskite Oxide Heterostructures

Multilayer structures have emerged as a leading research topic and researchers expect that multilayers may lead to interesting artificial materials with novel properties. In this Research News we show that the introduction of interfaces into perovskite oxides can induce a series of novel properties including an unusual positive magnetoresistance, great enhancement of lateral photovoltage in La_0.9Sr_0.1MnO₃/SrNb_0.01Ti_0.99O₃, and an electrical modulation of the magnetoresistance in multi‐p‐n heterostructures of SrTiO_3?δ/La_0.9Sr_0.1MnO₃/SrTiO_3?δ/La_0.9Sr_0.1MnO₃/Si. This novel positive magnetoresistance is attributed to the creation of a space charge region at the interface where the spin of the carriers is anti‐parallel to that of the carriers in the region far from the interface of manganese oxide in the heterostructures.