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1.
Lanthanum strontium manganite (La1−xSrxMnO3, LSM) powders were synthesized by polymerizable complex method, based on complexation of metal ions (MI) with citric acid (CA) and polyesterification between CA and ethylene glycol (EG). Firstly, the effect of the molar ratio of CA:MI (=1–3) was investigated on the synthesis of La0.7Sr0.3MnO3 powders, which were characterized by thermal analysis (TGA/DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The results indicated that the molar ratio CA:MI = 3 is adequate for a good crystallization of pure perovskite phase after calcination, with nanometric crystallite sizes and porous microstructure. For the La0.7Sr0.3MnO3 sample synthesized with CA:MI ratio of 3, it was investigated the effect of calcination temperature, showing that the perovskite structure is better crystallized at 900 °C, without secondary phase formation. Using this same CA:MI ratio and calcination temperature, powders with different Sr content (x = 0.2–0.4) were synthesized, with surface areas of 4–10 m2 g−1. These powders were sintered at 1100 °C to produce porous pellets. The porosity of the sintered pellets and the electrical conductivity, measured by two-probe technique, increased with increasing Sr content.  相似文献   

2.
Composite G/PPy/PPy(La1−xSrxMnO3)/PPy electrodes made of the perovskite La1−xSrxMnO3 embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La1−xSrxMnO3) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm−3 pyrrole (Py) plus 0.05 mol dm−3 K2SO4 with and without containing a suspension of 8.33 g L−1 oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm−3 K2SO4 plus 5 mmol dm−3 KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.  相似文献   

3.
Eu-doped perovskites La0.65−xEuxSr0.35MnO3 (0.05 ≤ x ≤ 0.30) were synthesized by sol–gel method using citric acid and characterized by X-ray diffraction, magnetization, resistivity and magnetoresistance (MR) experiments. All samples had a single hexagonal perovskite structure. As x increased from 0.05 to 0.30, the Curie temperature TC for the samples decreased from 352 to 242 K. It was found that two transition points appeared when the resistivity changed with increasing temperature, and upon an application of a magnetic field of 20 kOe the maximum magnetoresistivity of 18% for the La0.65−xEuxSr0.35MnO3 with x = 0.20 was obtained at room temperature 300 K. The mechanism of the transitions for the samples was explored.  相似文献   

4.
Yan Cui 《Electrochimica acta》2010,55(3):922-7735
Carbon coated LiFePO4 particles were first synthesized by sol-gel and freeze-drying method. These particles were then coated with La0.7Sr0.3MnO3 nanolayer by a suspension mixing process. The La0.7Sr0.3MnO3 and carbon co-coated LiFePO4 particles were calcined at 400 °C for 2 h in a reducing atmosphere (5% of hydrogen in nitrogen). Nanolayer structured La0.7Sr0.3MnO3 together with the amorphous carbon layer forms an integrate network arranged on the bare surface of LiFePO4 as corroborated by high-resolution transmission electron microscopy. X-ray diffraction results proved that the co-coated composite still retained the structure of the LiFePO4 substrate. The twin coatings can remarkably improve the electrochemical performance at high charge/discharge rates. This improvement may be attributed to the lower charge transfer resistance and higher electronic conductivity resulted from the twin nanolayer coatings compared with the carbon coated LiFePO4.  相似文献   

5.
《Ceramics International》2015,41(4):5821-5829
We report improvement in the magnetocaloric properties of Ce-doped lanthanum manganites. Polycrystalline La0.7−xCexSr0.30MnO3 (0≤x≥0.3) samples were prepared using the conventional solid-state reaction method with phase purity and structure confirmed using X-ray diffraction. Temperature dependent magnetization measurements and Arrott analysis reveal second order ferromagnetic transition in parent sample and as well as in doped sample with Curie temperature decreasing progressively with increasing Ce-concentration from ~370 K for x=0.0 to 310 K for x=0.30. Magnetic entropy change (ΔSM) was calculated by applying the thermodynamic Maxwell equation to a series of isothermal field dependent magnetization curves. A large ΔSM associated with the ferromagnetic–paramagnetic transition in La0.7−xCexSr0.30MnO3 samples has been observed. The value of ΔSM was found to increase with Ce-doping up to x=0.15 and the highest value of 2.12 J kg−1 K−1 (at ΔH=2 T) was observed for La0.55Ce0.15Sr0.30MnO3 sample near the Curie temperature of 356 K. Also, improved relative cooling power of ~122 J kg−1 was observed for the same sample. Due to the large magnetic entropy change and high Curie temperature, the La0.55Ce0.15Sr0.30MnO3 sample is suggested to be used as potential magnetic refrigerants for magnetic refrigeration technology above room temperature.  相似文献   

6.
From the perspectives of scientific researches and practical applications, it is desirable to explore high operating temperature ferromagnetic films. The effect of biaxial strain on magnetic properties of (110)-oriented La0.7Sr0.3MnO3 films was studied. High quality La0.7Sr0.3MnO3 films were grown on (110)-oriented perovskite single crystal substrates using pulsed laser deposition, varying substrate-induced misfit strains from ??2.27–0.75%. A remarkable enhancement of Curie temperature has been achieved for (110)-oriented La0.7Sr0.3MnO3 films clamped with small misfit strains (i.e., grown on LAST (110)). The enhanced Curie temperature of (110)-oriented La0.7Sr0.3MnO3 films could be attributed to the misfit strain between the films and the underlying substrates and may have technological implication for applications at high temperature environments.  相似文献   

7.
The electrochemical properties of Sr1−xCexMnO3 (SCM, 0.1≤x≤0.4)–Gd0.2Ce0.8O2−x (GDC) composite cathodes were determined by impedance spectroscopy. The study focused on the doping effect of Ce in the composite cathodes. Single-phase perovskite was obtained for 0.1≤x≤0.3 in SCM. No reaction occurred between the Sr0.7Ce0.3MnO3 electrode and the GDC electrolyte at an operating temperature of 800 °C for 100 h. In the single phase perovskite region, lattice expansion occurred due to the reduction of Mn4+ to Mn3+ at B-sites, and this was attributed to an increase in Ce content. Ce doping enhanced the electrode performance of SCM–GDC composite cathodes, and best electrode performance was achieved for the Sr0.7Ce0.3MnO3–GDC composite cathode (0.93 Ω cm2 and 0.47 Ω cm2 at 750 °C and 800 °C, respectively). The improvement in electrode performance was attributed to increases in charge carriers induced by a shift of some Mn from +4 to +3 and to the formation of surface oxygen vacancies caused by Mn4+ to Mn3+ conversion at high temperatures.  相似文献   

8.
(LaxSr1−x)MnO3 (LSMO) and (LaxSr1−x)FeO3 (LSFO) (x = 0.2–0.4) ceramics prepared by a simple and effective reaction-sintering process were investigated. Without any calcination involved, La2O3 and SrCO3 were mixed with MnO2 (LSMO) or Fe2O3 (LSFO) then pressed and sintered directly. LSMO and LSFO ceramics were obtained after 2 and 4 h sintering at 1350–1400 and 1200–1280 °C, respectively. Grain size decreased as La content increased in LSMO and LSFO ceramics.  相似文献   

9.
Ca0.9Gd0.1MnO3 nanopowders with perovskite type crystal structure were synthesized by modified glycine nitrate procedure. Nanopowders were prepared by combining glycine with metal nitrates and/or metal acetates in their appropriate stoichiometric ratios. Modification of the procedure was performed by partial replacement of nitrates by acetates, in order to control the burn-up reaction. Obtained Ca0.9Gd0.1MnO3 powders were calcinated in the temperature interval from 850 °C to 950 °C for 10 min. Properties such as phase evolution, lattice parameters, chemical composition and magnetic properties were monitored by DTA, X-ray diffraction, SEM/EDS and magnetic measurements. Magnetic measurements performed at the sample with the smallest crystallite size showed that a 10% of Gd3+ substituted Ca2+ ions changes antiferromagnetic properties of CaMnO3 by the introduction of ferromagnetic interaction due to a double exchange between Mn3+ and Mn4+ ions. Presence of competing interactions and their randomness lead to a formation of a spin glass state below Neel temperature TN = 110 K. From the high temperature magnetic susceptibility measurements effective magnetic moment of manganese ions is determined which lies between the values for Mn3+ and Mn4+ ions.  相似文献   

10.
A. Evdou  L. Nalbandian 《Fuel》2010,89(6):1265-1273
This work reports on the preparation and characterization of perovskitic materials with the general formula La1−xSrxFeO3 (x = 0, 0.3, 0.7, 1) for application in a dense mixed conducting membrane reactor process for simultaneous production of synthesis gas and pure hydrogen. Thermogravimetric experiments indicated that the materials are able to loose and uptake reversibly oxygen from their lattice up to 0.2 oxygen atoms per “mole” for SrFeO3 with x = 1 at 1000 °C. The capability of the prepared powders to convert CH4 during the reduction step, in order to produce synthesis gas, as well as their capability to dissociate water during the oxidation step, in order to produce hydrogen were evaluated by pulse reaction experiments in a fixed bed pulse reactor. The high sintering temperatures (1100-1300 °C) required for the densification of the membrane materials result in decreased methane conversion and H2 yields during the reduction step compared to the corresponding values obtained with the perovskite powders calcined at 1000 °C. Addition of small quantities of NiO, by simple mechanical mixing, to the perovskites after their sintering at high temperatures, increases substantially both their methane decomposition reactivity, their selectivity towards CO and H2 and their water splitting activity. Maximum H2 yield during the reduction step is achieved with the La0.7Sr0.3FeO3 sample mixed with 5% NiO and is 80% of the theoretically expected H2, based on complete methane decomposition. In the oxidation - water splitting step, 912 μmol H2 per gr solid are produced with the La0.3Sr0.7FeO3 sample mixed with 5% NiO. The experimental results of this work can be equally well applied for the “chemical-looping reforming” process since they concern using the lattice oxygen of the perovskite oxides for methane partial oxidation to syngas, in the absence of molecular oxygen, and subsequent oxidation of the solid.  相似文献   

11.
The La2−xAxMo2O9−δ (A = Ca2+, Sr2+, Ba2+ and K+) series has been synthesised as nanocrystalline materials via a modification of the freeze-drying method. The resulting materials have been characterised by X-ray diffraction (XRD), thermal analysis (TG/DTA, DSC), scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). The high-temperature β-polymorph is stabilised for dopant content x > 0.01. The nanocrystalline powders were used to obtain dense ceramic materials with optimised microstructure and relative density >95%. The overall conductivity determined by impedance spectroscopy depends on both the ionic radius and dopant content. The conductivity decreases slightly as the dopant content increases in addition a maximum conductivity value was found for Sr2+ substitution, which show an ionic radii slightly higher than La3+ (e.g. 0.08 S cm−1 for La2Mo2O9 and 0.06 S cm−1 for La1.9Sr0.1Mo2O9−δ at 973 K). The creation of extrinsic vacancies upon substitution results in a wider stability range under reducing conditions and prevents amorphisation, although the stability is not enhanced significantly when compared to samples with higher tungsten content. These materials present high thermal expansion coefficients in the range of (13-16) × 10−6 K−1 between room temperature and 753 K and (18-20) × 10−6 K−1 above 823 K. The ionic transport numbers determined by a modified emf method remain above 0.98 under an oxygen partial pressure gradient of O2/air and decreases substantially under wet 5% H2-Ar/air when approaching to the degradation temperature above 973 K due to an increase of the electronic contribution to the overall conductivity.  相似文献   

12.
A series of perovskite catalysts was investigated for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte and at room temperature, supplied by oxygen or air. A meniscus cell was used to screen-test candidate catalysts for their bifunctionality and assess their activity for ORR at 3 mm depth of immersion (DOI) in the electrolyte. Based on the meniscus data LaNiO3, La0.1Ca0.9MnO3 and La0.6Ca0.4CoO3 were selected for further assessment in microelectrode and half-cell studies. Activity tests for the ORR and OER, Tafel slopes at high current densities and apparent activation energies for the ORR were determined using a microelectrode technique on samples of the selected perovskites, La0.1Ca0.9MnO3, La0.6Ca0.4CoO3 and LaNiO3 with and without graphite support. Tafel slopes of ca. 120 mV per decade and apparent activation energies of approximately 18 kcal mol−1 were measured at high cathodic current densities. Cycle-life and performance of La0.1Ca0.9MnO3, La0.6Ca0.4CoO3 and LaNiO3-based gas-diffusion electrodes in half-cell configurations were tested at a constant current density of 25 mA cm−2 with subsequent and intermittent polarizations. Similar activities resulted in the ORR, while increased numbers of cycles were observed for the La0.1Ca0.9MnO3-based electrode. Furthermore, electrode material compositions, especially PTFE contents were optimized to conform to the establishment of the three phase interactions of the electrode structure. Transmission Electron microscopy (TEM) and BET-surface area analyses were carried out in order to find out the morphological and surface properties of the perovskite materials.  相似文献   

13.
Perovskite solid solutions of (La0.6Sr0.4)(X1−yMgy)O3−δ (X = Ti, Zr, Al) were prepared by a coprecipitation method using corresponding aqueous solutions and ammonium carbonate solution. The freeze-dried powders were sintered in air at 1000-1500 °C for 1-36 h. Single phase solid solutions were produced in the compositions of (La0.6Sr0.4)(Zr0.6Mg0.4)O3−δ and (La0.6Sr0.4)(Al0.9Mg0.1)O3−δ where (3 − δ) < 3. For the compositions of X = Ti and Zr for y = 0.1 where (3 − δ) > 3, two phases including perovskite solid solution were produced at 1400-1500 °C. The stability of perovskite solid solution was closely related to the fraction of lattice oxygen atom (3 − δ). A relatively high conductivity was measured for (La0.6Sr0.4)(Al0.9Mg0.1)O3−δ (σ = 4.15 × 10−4 S/cm at 600 °C, activation energy 113.4 kJ/mol). The influence of fraction of oxide ion vacancy on the activation energy was small for δ = 0.1-0.3 of perovskite solid solution.  相似文献   

14.
La(1−x)SrxFeO3 (x = 0.2,0.4) powders were prepared by a stearic acid combustion method, and their phase structure and electrochemical properties were investigated systematically. X-ray diffraction (XRD) analysis shows that La(1−x)SrxFeO3 perovskite-type oxides consist of single-phase orthorhombic structure (x = 0.2) and rhombohedral one (x = 0.4), respectively. The electrochemical test shows that the reaction at La(1−x)SrxFeO3 oxide electrodes are reversible. The discharge capacities of La(1−x)SrxFeO3 oxide electrodes increase as the temperature rises. With the increase of the temperature from 298 K to 333 K, their initial discharge capacity mounts up from 324.4 mA h g−1 to 543.0 mA h g−1 (when x = 0.2) and from 147.0 mA h g−1 to 501.5 mA h g−1 (when x = 0.4) at the current density of 31.25 mA g−1, respectively. After 20 charge-discharge cycles, they still remain perovskite-type structure. Being similar to the relationship between the discharge capacity and the temperature, the electrochemical kinetic analysis indicates that the exchange current density and proton diffusion coefficient of La(1−x)SrxFeO3 oxide electrodes increase with the increase of the temperature. Compared with La0.8Sr0.2FeO3, La0.6Sr0.4FeO3 electrode is a more promising candidate for electrochemical hydrogen storage because of its higher cycle capacity at various temperatures.  相似文献   

15.
In this work, the physical properties of nanocrystalline samples of La0.7Sr0.3Mn1−xFexO3 (0.0 ≤ x ≤ 0.20) perovskite manganites synthesized by the reverse micelle (RM) technique were explored in detail. The phase purity, crystal structure, and crystallite size of the samples were determined using X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. All the samples had rhombohedral crystal structure and crystallite size increased with increase in Fe content in La0.7Sr0.3MnO3. The scanning electron micrographs (SEMs) exhibited smooth surface morphology and nonuniform shape of the particles. The optical properties studied using UV-visible absorption spectroscopy revealed a decrease in the absorbance and optical band gap with an increase in Fe content in La0.7Sr0.3MnO3 compound. The temperature-dependent resistivity measurements revealed semiconducting nature of x = 0 and 0.1 samples up to the studied temperature range, while a metal-to-insulator transition was observed at higher Fe doping. Magnetic studies revealed weak ferromagnetism in all the samples and a reduction in the maximum magnetization with an increase in Fe content. A close correlation between electrical transport and magnetic properties was observed with the doping of Fe ion in La0.7Sr0.3MnO3 at Mn site. These results advocate strong interactions associated with the double exchange mechanism among Fe3+ and Mn3+ ions.  相似文献   

16.
《Ceramics International》2022,48(8):11094-11102
Based on the analysis of crystal structure, Mn3+/Mn4+ pairs, distortion of MnO6 octahedron, and electrical transport properties of La1-xCaxMnO3 and La1-xSrxMnO3 materials, room-temperature coefficient of resistivity (TCR) of La0.7Ca0.3-xSrxMnO3 (LCSMO) films was optimized by Ca/Sr co-doping at the A-site. LCSMO films are successfully fabricated on LaAlO3 (100) substrates via facile spin coating technology. The microstructure of LCSMO films is characterized by X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, atomic force microscopy and X-ray photoemission spectroscopy. Results reveal that A-site Ca/Sr co-doping significantly influenced crystal structure, formation of Mn3+/Mn4+ pairs, and distortion of MnO6 octahedron. The correlation between microstructure and electrical transport properties was explained through the phenomenological percolation model, double-exchange mechanism and Jahn-Teller effect. Furthermore, the TCR reached 10.2% K-1 at 296.1 K in La0.7Ca0.18Sr0.12MnO3 films.  相似文献   

17.
This work investigates the effect of synthesis parameters (calcination temperature, milling conditions and sintering temperature) on the structural, morphological and electrical properties of La0.7Sr0.3Co0.5Fe0.5O3 (LSCF) powders prepared by the solid state reaction. The thermogravimetric profile showed that the minimum temperature needed for the carbonate decomposition and formation of perovskite phase is 800 °C. SEM analysis revealed the loose and porous structure of the powder materials. The XRD patterns demonstrate that milling parameters such as grinding balls:sample ratio, rotational speed, and milling time influence the structural properties. The results revealed that powders synthesized with grinding balls:sample ratio of 8:1, 500 rpm and 4 h of milling present pure LSCF phase. Porosity of the pellets decreased with increasing sintering temperature from 950 to 1100 °C. Electrical conductivity was measured at 400–1000 °C and correlated with sintering temperature.  相似文献   

18.
Layered perovskite oxides have ordered A-cations localizing oxygen vacancies, and may potentially improve oxygen ion diffusivity and surface exchange coefficient. The A-site-ordered layered perovskite PrBa0.5Sr0.5Co2O5+δ (PBSC) was evaluated as new cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). The material was characterized using electrochemical impedance spectroscopy in a symmetrical cell system (PBSC/Ce0.9Sm0.1O1.9 (SDC)/PBSC), exhibiting excellent performance in the intermediate temperature range of 500-700 °C. An area-specific-resistance (ASR) of 0.23 Ω cm2 was achieved at 650 °C for cathode polarization. The low activation energy (Ea) 124 kJ mol−1 is comparable to that of La0.8Sr0.2CoO3−δ. A laboratory-scaled SDC-based tri-layer cell of Ni-SDC/SDC/PBSC was tested in intermediate temperature conditions of 550 to 700 °C. A maximum power density of 1045 mW cm−2 was achieved at 700 °C. The interfacial polarization resistance is as low as 0.285, 0.145, 0.09 and 0.05 Ω cm2 at 550, 600, 650 and 700 °C, respectively. Layered perovskite PBSC shows promising performance as cathode material for IT-SOFCs.  相似文献   

19.
The effect of spin states on the spin entropy has been studied in La0.7−xYxCa0.3CoO3 (x=0.0, 0.05, 0.1 and 0.15). Magnetothermopower results reveal that Y-doping improves the spin entropy of La0.7Ca0.3CoO3. The magnetic results indicate that the Co3+ ions undergo a transition from an intermediate spin state (t52ge1g; S=1) to a low spin state (t62ge0g; S=0), which results in the enhancement of the spin entropy. A suitable theoretical model is suggested to explain well the enhancement of the spin entropy induced by spin state transition. This investigation gives strong evidence that the enhanced spin entropy contribution to the thermopower is tuned by the spin state transition.  相似文献   

20.
Y2−xLaxW3O12 solid solutions were successfully synthesized by the solid state reaction method. The microstructure, hygroscopicity and thermal expansion property of the resulting samples were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM) and thermal mechanical analysis (TMA). Results indicate that the structural phase transition of the Y2−xLaxW3O12 changes from orthorhombic to monoclinic with increasing substituted content of lanthanum. The pure phase can form for 0≤x≤0.4 with orthorhombic structure and for 1.5≤x≤2 with monoclinic one. High lanthanum content leads to a low relative density of Y2−xLaxW3O12 ceramic. Thermal expansion coefficients of the Y2−xLaxW3O12 (0≤x≤2) ceramics also vary from −9.59×10−6 K−1 to 2.06×10−6 K−1 with increasing substituted content of lanthanum. The obtained Y0.25La1.75W3O12 ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.66×10−6 K−1 from 103 °C to 700 °C.  相似文献   

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