Preparation and electrical behavior study of the ceramic interconnect La0.7Ca0.3CrO3−δ with CeO2-based electrolyte Ce0.8Sm0.2O1.9

Based on the conventional interconnect La_0.7Ca_0.3CrO_3−δ, a novel ceramic interconnect for intermediate temperature solid oxide fuel cells was developed. In the air, the electrical conductivities of La_0.7Ca_0.3CrO_3−δ + 5%Ce_0.8Sm_0.2O_1.9 at 600, 700 and 800 °C were 96.7, 146.3 and 687.8 S cm⁻¹, respectively, which increased significantly as compared with La_0.7Ca_0.3CrO_3−δ under the same conditions. Similarly, in pure hydrogen, La_0.7Ca_0.3CrO_3−δ + 3%Ce_0.8Sm_0.2O_1.9 possessed the maximal electrical conductivities which were 4.2, 5.3 and 7.1 S cm⁻¹, respectively at 600, 700 and 800 °C. The crystal structures of La_0.7Ca_0.3CrO_3−δ, La_0.7Ca_0.3CrO_3−δ + 5%Ce_0.8Sm_0.2O_1.9 and La_0.7Ca_0.3CrO_3−δ + 10%Ce_0.8Sm_0.2O_1.9 were single phase with hexagonal symmetry, cubic phase plus some doped ceria impurity and orthorhombic phase plus some doped ceria impurity, respectively. The difference between the crystal structures may account for the difference between the electrical conductivities. The electrical conductivities and sinterability of La_0.7Ca_0.3CrO_3−δ were increased by introducing Ce_0.8Sm_0.2O_1.9, whereas the other properties were not influenced.     

Novel composite interconnecting ceramics La0.7Ca0.3CrO3−δ/Ce0.8Sm0.2O1.9 for solid oxide fuel cells

In this paper, an interconnecting ceramic for solid oxide fuel cells was developed, based on the modification from La_0.7Ca_0.3CrO_3−δ by addition of Ce_0.8Sm_0.2O_1.9. It is found that addition of small amount Ce_0.8Sm_0.2O_1.9 into La_0.7Ca_0.3CrO_3−δ dramatically increased the electrical conductivity. For the best system, La_0.7Ca_0.3CrO_3−δ + 5 wt.% Ce_0.8Sm_0.2O_1.9, the electrical conductivity reached 687.8 S cm⁻¹ at 800 °C in air. In H₂ at 800 °C, the specimen with 3 wt.% Ce_0.8Sm_0.2O_1.9 had the maximal electrical conductivity of 7.1 S cm⁻¹. With the increase of Ce_0.8Sm_0.2O_1.9 content the relative density increased, reaching 98.7% when the Ce_0.8Sm_0.2O_1.9 content was 10 wt.%. The average coefficient of thermal expansion at 30-1000 °C in air increased with Ce_0.8Sm_0.2O_1.9 content, ranging from 11.12 × 10⁻⁶ to 12.46 × 10⁻⁶ K⁻¹. The oxygen permeation measurement illustrated a negligible oxygen ionic conduction, indicating it is still an electronically conducting ceramic. Therefore, this material system will be a very promising interconnect for solid oxide fuel cells.     

Thermal expansion properties of Ln2−xCrxMo3O12 (Ln = Er and Y)

Structures and thermal expansion properties of Ln_2−xCr_xMo₃O₁₂ (Ln = Er and Y) have been investigated by X-ray powder diffraction. Rietveld analysis results of Ln_2−xCr_xMo₃O₁₂ indicate that compounds Er_2−xCr_xMo₃O₁₂ (0 ≤ x ≤ 0.3) and Y_2−xCr_xMo₃O₁₂ (0 ≤ x ≤ 0.2) crystallize in orthorhombic structure and exhibit negative thermal expansion, while both monoclinic and orthorhombic compounds Er_2−xCr_xMo₃O₁₂ (1.7 ≤ x ≤ 2.0) and Y_2−xCr_xMo₃O₁₂ (1.8 ≤ x ≤ 2.0) possess positive coefficient of thermal expansion. The coefficients of linear thermal expansion of orthorhombic Ln_2−xCr_xMo₃O₁₂ change from negative to positive with increasing chromium content. Thermogravimetric and differential scanning calorimetry have been used to study the hygroscopicity and the phase transition temperature.     

Phase formation mechanism and kinetics in solid-state synthesis of undoped and calcium-doped lanthanum manganite

LaMnO_3+δ and La_0.7Ca_0.3MnO₃ were synthesized from La₂O₃(La(OH)₃), CaCO₃ and MnO₂ powder mixture with solid-state reaction technique. X-ray diffraction and thermal analysis were employed in the present study on the process of synthesizing of the two compound powders. The kinetic study on solid-state reaction between La₂O₃ and MnO₂ in the powder mixture was isothermally carried out for LaMnO_3+δ formation. The result showed that the reaction process was controlled by three-dimensional solid-ionic diffusion. Both Jander and Ginstling-Brounstein model can be used to describe the reaction kinetics satisfactorily. The relevant apparent activation energy values obtained were as great as 205 ± 11 and 189 ± 8 kJ/mol. The reaction process of La_0.7Ca_0.3MnO₃ preparation from La₂O₃, SrCO₃ and MnO₂ powder mixture was also studied using X-ray diffraction and thermal analysis. The result indicated that the following steps composed the overall reaction: the decomposition of the reactant; the formation of La_1−xCa_xMnO_3+δ; La₂O₃ and Mn₃O₄ reacted with La_1−xCa_xMnO₃ to form final La_0.7Ca_0.3MnO₃ phase. The latest step was the most time-consuming one among others in the overall reaction.     

Magnetic properties and magnetocaloric effect in La1.4?xCexCa1.6Mn2O7 perovskites synthesized by sol–gel method

The magnetic properties and magnetocaloric effect near the critical phase transition temperatures of La_1.4−x Ce _x Ca_1.6Mn₂O₇ (x = 0, 0.2) double layered manganites are analyzed. Polycrystalline nanopowders of La_1.4Ca_1.6Mn₂O₇ and La_1.2Ce_0.2Ca_1.6Mn2O₇ were successfully synthesized by a sol–gel method. The magnetic measurements suggest an antiferromagnetic alignment of the Ce and Mn moments in La_1.2Ce_0.2Ca_1.6Mn₂O₇. Both Ce³⁺ and Ce⁴⁺ ions are present in the doped sample, as indicated by the XPS spectra. A moderate magnetocaloric effect was found for both samples, with the maximum entropy change located at temperatures near the magnetic transition ones. The high RCP(S) values together with the broadened magnetic entropy curves suggest the possibility to use these materials for magnetic refrigeration devices.     

Electrochemical characteristics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ–Sm0.2Ce0.8O1.9 composite materials for low-temperature solid oxide fuel cell cathodes

In this paper, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ–xSm_0.2Ce_0.8O_1.9 (BSCF–xSDC, x = 0–60 wt.%) composite cathodes were prepared by soft chemical methods, and then examined for potential applications in lower temperature solid oxide fuel cells. Both DC polarization and AC impedance spectroscopy measurements indicated that the addition of SDC electrolyte into BSCF remarkably improved the electrochemical properties. The optimum composition was found to be BSCF–30SDC, which exhibited 5.5 times higher polarization current density and 15.1% polarization resistance, compared with the pure-phase BSCF cathode at 550 °C.     

High temperature mechanical properties of La1−x Sr x Cr1−y Co y O3 for SOFC interconnect

Solid oxide fuel cells (SOFC) require an interconnect for fabrication into stacked cells. This is typically La(Sr, Ca)CrO₃, of which much data on the electrical and physical properties already exists. However, very little information exists on the high temperature mechanical properties of the material, which is a necessity for future design improvements. La_1–x Sr _x Cr_1–y Co _y O₃ samples were fabricated into green dry-pressed bars and pellets, and sintered under various heating and cooling regimes. The sinterability and high temperature mechanical properties of the material was then investigated as a function of the dopant concentration. It was observed, for example, that the modulus of rupture of the dry pressed La_0.7Sr_0.3Cr_1–yCo_yO₃ (y 0.3) gave a value of over 110 MPa at 1000 °C. This paper will provide data on the high temperature mechanical properties of the material and its application to the SOFC system.     

Synthesis of layered Li1.2+x[Ni0.25Mn0.75]0.8−xO2 materials (0 ≤ x ≤ 4/55) via a new simple microwave heating method and their electrochemical properties

Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) was prepared by a new simple microwave heating method and the effect of extra Li⁺ content on electrochemistry of Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) was firstly revealed. X-ray diffraction identified that they had layered α-NaFeO₂ structure (space group R-3m). Linear variation of lattice constant as a function of x value supported the formation of solid solution, that is, extra Li⁺ is possibly incorporated in structure of layered Li_1.2Ni_0.2Mn_0.6O₂ (x = 0), accompanying oxidization of Ni²⁺ to Ni³⁺ to form Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55). This was confirmed by X-ray photoelectron spectroscopy that Ni³⁺ appeared and increased in content with increasing x value. Charge–discharge tests showed that Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂ (0 ≤ x ≤ 4/55) truly displayed different electrochemical properties (different initial charge–discharge plots, capacities and cycleability). Li_1.2Ni_0.2Mn_0.6O₂ (x = 0) in this work delivered the highest discharge capacity of 219 mAh g⁻¹ between 4.8 and 2.0 V. Increasing Li content (x value in Li_1.2+x[Ni_0.25Mn_0.75]_0.8−xO₂) reduced charge–discharge capacities, but significantly enhancing cycleability.     

Symmetry breaking and electrical conductivity of La0.7Sr0.3Cr0.4Mn0.6O3−δ perovskite as SOFC anode material

This work is focused on nanocrystalline solid oxide fuel cell synthesis and characterization (SOFC) anodes of La_0.7Sr_0.3Cr_0.4Mn_0.6O_3−δ (perovskite-type) with Nickel. Perovskite-type oxide chemical reactivity, nucleation kinetics and phase composition related with La_0.7Sr_0.3Cr_0.4Mn_0.6O_3−δ–NiO to La_0.7Sr_0.3Cr_0.4Mn_0.6O_3−δ–Ni transformation have been analyzed. SOFC anode powders were obtained by sol–gel synthesis, using polyvinyl alcohol as an organic precursor to get a porous cermet electrode after sintering at 1365 °C and oxide reduction by hydrogen at 800 °C/1050 °C for 8 h in a horizontal tubular reactor furnace under 10% H₂/N₂ atmosphere. Composite powders were compressed into 10-mm diameter discs with 25–75 wt% Ni.     

Sinterability and electrical conductivity of calcium-doped lanthanum chromites

Calcium-doped lanthanum chromites, (La_1–x Ca _x ) (Cr_1– y Ca_y O₃, have been synthesized to investigate effects of calcium doping on sinterability and electrical conductivity. X-ray diffractometric results have revealed that in addition to normal perovskites (La_1– xCa _x CrO₃), chromium-deficient perovskites can exist as a single phase in the composition region 0.1 <x < 0.3, although the deficit of chromium is small. These chromium-deficient perovskites show a good sinterability even in air at 1873 K. Electrical conductivity of these perovskites has been measured as functions of temperature and oxygen potential. It has been found that electrical conductivity of the chromium-deficient perovskites increases almost linearly with total calcium content. The magnitudes of electrical conductivity are comparable to those of strontium-doped lanthanum chromites.     

Ca4REO(BO3)3 crystals for green and blue microchip laser generation: from crystal growth to laser and nonlinear optical properties

We have taken advantage of congruent melting behavior of the nonlinear rare-earth oxoborate Ca₄REO(BO₃)₃ family to perfect a process of collective fabrication of self-frequency doubling microchip laser based on Nd:GdCOB (Ca₄Gd_1−xNd_xO(BO₃)₃) crystals. The process goes from Czochralski boule to 1 × 3 mm² chips perfectly oriented (better than 0.1°) to the phase matching direction (θ=90°, φ=46°) in the XY principal plane, with dielectric mirrors directly deposited on both faces of the chips. 20 mW of self-frequency doubling output power at 530 nm was performed under 800 mW of diode laser as incident pump power at 812 nm. In addition, new compositions from the solid solution Ca₄Gd_1−xY_xO(BO₃)₃ (Gd_1−xY_xCOB) (x=0.13, 0.16, 0.44) have been grown by the Czochralski pulling method, in order to achieve noncritical phase matching (NCPM) second harmonic generation of ⁴F_3/2 → ⁴I_9/2 Nd³⁺ doped laser hosts. Three types of laser wavelengths have been chosen: Nd:YAP (YAlO₃) at 930 nm, Nd:YAG (Y₃Al₅O₁₂) at 946 nm, and Nd:ASL (Nd_ySr_1−x La_x−yMg_x Al_12−xO₁₉) at 900 nm. Angular acceptance measurements of these three types of compositions present very large values, compared to pure GdCOB or YCOB oriented in critical phase matching configurations.     

Preparation of double-doped BaCeO3 and its application in the synthesis of ammonia at atmospheric pressure

Perovskite-type oxides BaCe_0.90Sm_0.10O_3−δ (BCS) and BaCe_0.80Gd_0.10Sm_0.10O_3−δ (BCGS) were synthesized by the sol–gel method and characterized by thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Using the sintered samples as solid electrolytes and silver–palladium alloy as electrodes, ammonia was synthesized from nitrogen and hydrogen at atmospheric pressure in a solid-state proton-conducting cell reactor. The maximum rate of production of ammonia was 5.82×10⁻⁹ mol s⁻¹ cm⁻².     

Effect of Ca doping on the performance of CeO<Subscript>2</Subscript>–NiO catalysts for CH<Subscript>4</Subscript> catalytic combustion

Methane catalytic combustion was carried out over the Ce_0.9–xNi_0.1Ca_xO_δ (0 < x ≤ 0.3) catalysts prepared by a citric acid complexation–combustion method. When x ≤ 0.1, the presence of Ca can enhance the surface area and reduce the crystalline size, and improve the reduction of the dispersed NiO species in catalyst, resulting in an improvement of the catalytic activity of Ce_0.9–xNi_0.1Ca_xO_δ. The XRD and Raman results show that Ce_0.9–xNi_0.1Ca_xO_δ (x ≤ 0.1) solid solution can form by Ni and Ca incorporation in the CeO₂ lattices. TEM and etching results reveal that part of Ni disperses well on the surface of Ca-doped sample. FT-IR testing shows that with an increase in Ca amount (x > 0.1), more carbonate species (mainly carbonate calcium) can form on the catalyst surface, which would severely debase the catalytic activity of Ce_0.9–xNi_0.1Ca_xO_δ.     

Properties and performance of La1.6Sr0.4NiO4+δ-Ce0.8Sm0.2O1.9 composite cathodes for intermediate temperature solid oxide fuel cells

La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 composite cathodes were prepared successfully using combustion synthesis method for intermediate temperature solid oxide fuel cells. The chemical compatibility, thermal expansion behavior, electrical conductivity and electrode performance were studied. The X-ray diffraction of La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 composite result proved a slight reaction between La_1.6Sr_0.4NiO_4+δ and Ce_0.8Sm_0.2O_1.9. Both the thermal expansion coefficient and the electrical conductivity of La_1.6Sr_0.4NiO_4+δ-Ce_0.8Sm_0.2O_1.9 decreased with increasing Ce_0.8Sm_0.2O_1.9 content. AC impedance spectroscopy measurements indicated that the addition of 30 wt% Ce_0.8Sm_0.2O_1.9 to La_1.6Sr_0.4NiO_4+δ exhibited the lowest polarization resistance (0.238 Ωcm²) at 800 °C in air, which was only one fourth of the La_1.6Sr_0.4NiO_4+δ electrode measured at the same temperature.     

Self-rising approach to synthesize hierarchically porous metal oxides

Hierarchically porous metal oxides are prepared using a novel self-rising approach. The method is ‘hard-template’ free and relatively easy to perform, utilizes inexpensive precursors and processing conditions, and is versatile, thus offering tremendous opportunities with a wide variety of conditions to explore to synthesize single or mixed metal oxides with hierarchically porous structures. Fe₂O₃, Sm_0.2Ce_0.8O_1.9, LaFeO₃, LaCoO₃, and La_0.5Sr_0.5Co_0.5Fe_0.5O₃ have been successfully synthesized while Fe₂O₃ and La_0.5Sr_0.5Co_0.5Fe_0.5O₃ as examples for single and mixed metal oxides have been studied in detail. Sm_0.2Ce_0.8O_1.9 has been applied as electrolyte for solid oxide fuel cells, showing good sinterability and high conductivity. A tentative scheme is provided to illustrate the pore formation mechanism using the self-rising approach.     

Phase Equilibria and Crystal Structures of Mixed Oxides in the La-Mn-Ni-O System

The phase equilibria and crystal structures of mixed oxides in the ternary system La₂O₃-Mn₃O₄-NiO are studied at 1100°C in air. The projection of the La-Mn-Ni-O phase diagram at 1100°C and = 0.21 × 10⁵ Pa onto the metal-composition triangle is found to comprise 12 phase fields. The lattice parameters of La₂NiO₄ (sp. gr. I4/mmm), La₃Ni₂O₇ (sp. gr. Cmcm), La₄Ni₃O₁₀ (sp. gr. Cmca), and La_{1 + x} Mn_{1 − x − y} Ni_yO₃ solid solutions (sp. gr. Pnma, −0.04 ≤ x ≤ 0.05, 0 ≤ y ≤ 0.4) are determined. The composition stability limits of La₄Ni_{3 − y} Mn_yO₁₀ solid solutions are 0 < y ≤ 0.05. With increasing Ni concentration in La_{1 + x} Mn_{1 − x − y} Ni_yO₃, the metal nonstoichiometry decreases from −0.04 ≤ x ≤ 0.05 at y = 0 to x = 0 at y = 0.4.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 7, 2005, pp. 841–848.Original Russian Text Copyright © 2005 by Demina, Cherepanov, Petrov, Klokova.     

High-temperature oxygen non-stoichiometry, conductivity and structure in strontium-rich nickelates La2−xSrxNiO4−δ (x = 1 and 1.4)

Oxygen non-stoichiometry, electrical conductivity and thermal expansion of La_2−xSr_xNiO_4−δ phases with high levels of strontium-substitution (1 ≤ x ≤ 1.4) have been investigated in air and oxygen atmosphere in the temperature range 20–1050 °C. These phases retain the K₂NiF₄-type structure of La₂NiO₄ (tetragonal, space group I4/mmm). The oxygen vacancy fraction was determined independently from thermogravimetric and neutron diffraction experiments, and is found to increase considerably on heating. The electrical resistivity, thermal expansion and cell parameters with temperature show peculiar variations with temperature, and differ notably from La₂NiO_4±δ in this respect. These variations are tentatively correlated with the evolution of nickel oxidation state, which crosses from a Ni³⁺/Ni⁴⁺ to a Ni²⁺/Ni³⁺ equilibrium on heating.     

Structure, conductivity and redox stability of solid solution Ce1?xCaxVO4 (0?≤?x?≤?0.4125)

A-site-substituted cerium orthovanadates, Ce_1−x Ca _x VO₄, were synthesised by solid-state reactions. At room temperature, the solid solution limit in Ce_1−x Ca _x VO₄ series is at x = 0.4125. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I4₁/amd with a = 7.4004 (1) and c = 6.4983 (6) ? for CeVO₄. The UV–Visible absorption spectra indicated that the compounds have band gaps at room temperature in the range of 4.2–4.5 eV. Conductivity measurements were performed for the first time up to the calcium solid solution limit in both air and dry 5% H₂/Ar with conductivity values at 600 °C ranging from 0.3 to 20 mS cm⁻¹ in air to 3 to 30 mS cm⁻¹ in reducing atmosphere. In general, the conductivity of Ca-doped CeVO₄ is higher in air but lower in a reducing atmosphere comparing to pure CeVO₄. The H₂/air electrochemical cell measurement indicates that the conduction of sample Ce_0.7Ca_0.3VO₄ is electronic dominant. Samples Ce_0.9Ca_0.1VO₄ and Ce_0.8Ca_0.2VO₄ are redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.     

Emission (Gd3+ and Sm3+) and ESR (Gd3+) studies of La1−xLnxB3O6 (Ln = Gd,Sm; 0 ≤ x ≤ 0.2 for Gd; 0 ≤ x ≤ 0.1 for Sm) phosphors

Polycrystalline powders of rare-earth doped La_1?xGd_xB₃O₆ (0?≤?x?≤?0.2) and La_1?xSm_xB₃O₆ (0.0?≤?x?≤?0.1) phosphors were successfully prepared by a B₂O₃ flux method. All the phosphor samples are well characterized by powder X-ray diffraction (XRD), infrared (IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) methods and fluorescence lifetime of Sm³⁺ ion. The XRD patterns show that La_1?xM_xB₃O₆ (M?=?Gd and Sm) adopt monoclinic with the I2/a space group. The SEM–EDS results confirmed the doping of Gd and Sm into LaB₃O₆ lattice. The IR and Raman spectra of these solid solutions gave distinctive bands corresponding to planar BO₃ and tetrahedral BO₄ groups. The photoluminescence (PL) spectra of La_1?xGd_xB₃O₆ gave a strong emission band, ⁶P_J?→?⁸S_7/2, at 310 nm. The PL spectra of La_1?xSm_xB₃O₆ phosphor showed orange-red emission at 598 nm when excited using light of wavelength of 402 nm. The results were obtained by the transition ⁴G_5/2?→?⁶H_7/2 of Sm³⁺ ions. The influence of dopant concentration on the emission profiles was studied. The ESR spectra of La_1?xGd_xB₃O₆ (x?=?0.02) gave a typical U-spectrum and spin-Hamiltonian parameters are deduced.

     

Synthesis and characterization of LiCo0.3−xGaxNi0.7O2 (x = 0, 0.05) as a cathode material for lithium ion battery

The single phase of LiCo_0.3−xGa_xNi_0.7O₂ (x = 0, 0.05) was synthesized by a sol–gel method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical performance. The powders are homogeneous and have a good-layered structure. The synthesized LiCo_0.25Ga_0.05Ni_0.7O₂ exhibits better electrochemical performance with an initial discharge capacity of 180.0 mAh g⁻¹ and a capacity retention of 95.2% after 50 cycles between 2.8 and 4.4 V at 0.2C rate. The study on the structural evolution of the material during the cycling shows that Ga-doping improves the structure stability of LiCo_0.3Ni_0.7O₂ at ambient temperature and 55 °C. Meanwhile, Ga-doping not only suppresses the alternating current (AC) impedance of LiCo_0.3Ni_0.7O₂ but also promotes the Li⁺ diffusion in LiCo_0.3Ni_0.7O₂. Furthermore, thermal stability of the charged LiCo_0.25Ga_0.05Ni_0.7O₂ is improved, which may be attributed to the retard of O₂ evolution in LiCo_0.3Ni_0.7O₂ and the suppression of electrolyte oxidation during cycling by Ga-doping_.