首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Oxygen-ion conduction in apatite-like compounds based on silicates and germanates of lanthanum La x A6O12 + 1.5x (A = Si, Ge; x = 9.11–10.22) is studied. The compounds are shown to be purely ionic conductors at 600–900°C and partial oxygen pressures 10?16 to 105 Pa. The electroconductivity of the best conducting specimens of La x A6O12 + 1.5x (A = Si, Ge; x = 9.77–10) exceeds that of electrolyte YSZ at moderate temperatures. The electroconductivity of lanthanum germanate is substantially greater than that of lanthanum silicate, specifically, 7.85 × 10?2 and 2.35 × 10?2 S cm?1, respectively, at 800°C. An inflection is discovered at ~750°C in the temperature dependences of electroconductivity of La x Ge6O12 + 1.5x (x = 9.77–10.22). A dilatometric examination points to a second-kind phase transition that may be due to the oxygen sublattice disordering. The behavior of apatite-like electrolytes La x A6O12 + 1.5x (A = Si, Ge) during long exploitation periods in the interval of working temperatures of electrochemical devices is studied for the first time ever. The electrolytes’ aging at 800°C in air for 1000 h was investigated by the electroconductivity method. The electroconductivity of lanthanum germanates decayed with time by 5% and that of lanthanum silicates, by 9.5%. The steady-state values of electroconductivity of all compounds studied is reached after 600–700 h. The compounds studied form a class of materials that hold some promise as solid electrolytes for medium-temperature fuel cells and other electrochemical devices.  相似文献   

2.
The ion-oxygen conductivity of apatite-like compounds based on lanthanum silicates and germanates La10A6O27 (A = Si, Ge), La10?x CaxSi6O27?δ (x = 0.25, 0.5, 1.0), La9.75Ca0.25Ge6O27?δ and La9.33+δSi6?x AlxO26(x=0.4, 0.8, 1.5) is studied in the interval of partial oxygen pressures pO2 extending from 10?16 to 105 Pa, at temperatures of 500–1000°C. The electroconductivity of undoped compounds La10A6O27 (A = Si, Ge) exceeds that of yttria-stabilized zirconia. The electroconductivity of lanthanum germanate (1.7 × 10?2 and 8.5 × 10?2S cm?1 at 700 and 900°C, respectively) is substantially higher than that of lanthanum silicate (9.8 × 10?3 and 3.5 × 10?2 S cm?1 at 700 and 900°C). Doping lanthanum germanate with calcium raises its electroconductivity (2.7 × 10?2 and 1.3 × 10?1 S cm?1 for La9.75Ca0.25Ge6O27?δ at 700 and 900°C). Conversely, doping lanthanum silicate with ions of calcium or aluminum reduces the conductivity. In the pO2 interval studied, the above compounds are ionic conductors and represent a class of solid electrolytes of promise for various electrochemical devices.  相似文献   

3.
Eu3+ ions activated La2Ti2O7 (La2Ti2O7:xEu3+) phosphors have been successfully synthesized by a fractional precipitation method from commercially available La2O3, Eu2O3, HNO3, Ti(SO4)2·9H2O and NH3·H2O as the starting materials. Detailed characterizations of the synthetic products were obtained by fourier transform infrared spectroscopy (FT-IR), X-ray diffractometry (XRD), differential thermal analysis, thermogravimetry and derivative thermogravimetry (DTA-TG-DTG), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy. The results show that the precursor is composed of amorphous particles with quasi-spherical in shape and about 50 nm in size. Moreover, the precursor could be converted into pure La2Ti2O7 phase by calcining at 1000 °C for 2 h in air. The as-synthesized La2Ti2O7 particles are approximate polyhedron in shape and about 100–200 nm in size. PL spectroscopy of La2Ti2O7:xEu3+ phosphors reveals that the strongest emission peak is located at 616 nm under 275 nm ultraviolet (UV) light excitation, which corresponds to the 5D07F2 transition of Eu3+ ions. The quenching concentration of Eu3+ ions is 10.0 mol%, and its corresponding fluorescence lifetime was 1.82 ms according to the linear fitting result. Decay study reveals that the 5D07F2 transition of Eu3+ ions has a single exponential decay behavior.  相似文献   

4.
《Solid State Sciences》2012,14(3):387-393
Partial substitutions of Ho at the La-site of La2Mo1.7W0.3O9−δ were carried out. Compound La2−xHoxMo1.7W0.3O9−δ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5) has been synthesized by solid state reaction technique. The specimens were characterized by XRD, SEM, DSC for crystal structure, surface morphology, phase transition and ac impedance spectroscopy for conductivity and other electrical parameter determination. Partial substitution of Ho at the La-site of La2Mo1.7W0.3O9−δ, increases the conductivity within the substitutional range, x ≤ 0.2. The phase transition of La2Mo2O9 is suppressed in doped compound and a transition from Arrhenius to VTF behavior of temperature dependence of conductivity is observed around 500 °C. The conductivity is found to be high in the intermediate temperature region and at high temperature the conductivity of La2−xHoxMo1.7W0.3O9−δ (0.05 ≤ x ≤ 0.2) is almost similar with that of La2Mo2O9. The decrease in energy barrier enhances the thermally assisted process to start at lower temperature.  相似文献   

5.
The oxidative coupling of methane (OCM) is an attractive route to convert natural gas directly into value-added chemical products (C2+). This work comparatively investigated SiO2- or La2O3-supported Na2WO4-MnxOy (denoted as NWM) catalysts in powder and fiber forms. The powder catalysts were prepared using a co-impregnation method and the fiber catalysts were prepared successfully using an electrospinning technique. The NWM/La2O3 fiber catalysts were activated at low temperature (500 °C) and had a 4.7% C2+ yield, with the maximum C2+ yield of 9.6% at 650 °C, while the NWM/SiO2 fiber catalyst was activated at 650 °C and had a maximum C2+ yield of 20.4% at 700 °C. The XPS results in the O 1s region indicated that NWM/La2O3 had a lower binding energy than NWM/SiO2, suggesting that the lattice oxygen species is easily released from the catalyst surface and creates vacancy sites that enhance performance. The stability test of the catalysts indicated that the La2O3-containing catalysts had excellent activity and high thermal stability, while the SiO2-containing catalysts had a higher C2+ yield when the prepared catalysts were compared at 700 °C. Considering the same component catalysts, the fiber catalysts achieved higher performance because their heat and mass transfer properties were enhanced.  相似文献   

6.
Highly lithium ion conductive composites with Al-doped Li7La3Zr2O12 (LLZ) and amorphous Li3BO3 were prepared from sol–gel derived precursor powders of LLZ and Li3BO3. Precursor LLZ powders with cubic phase were obtained by a heat treatment of the precursor dried gel at 600 °C. Pellets of the mixture of the obtained LLZ and Li3BO3 were first held at 700 °C, and then successively sintered at 900 °C. Density of the sintered pellet with Li3BO3 was larger than that of the pellet without Li3BO3. From the TEM observation, the pellets were found to consist of cubic LLZ and amorphous Li3BO3. Total electrical conductivity of the obtained LLZ–Li3BO3 composite was 1 × 10 4 Scm 1 at 30 °C.  相似文献   

7.
《Solid State Sciences》2004,6(6):523-531
Weakly-agglomerated nanocrystalline (ZrO2)1−x(Yb2O3)x (x=0.02–0.2) powders with high surface area (109–151 m2 g−1) were synthesized by a two-step hydrothermal process in the presence of urea: a stock solution of metal nitrates and urea was heated at 80 °C for 24 h and then at 180 °C for 48 h. For x=0.04–0.2, the as-derived powders were an assembly of uniform nanoparticles with well-defined edges in the size between 6.1–8.4 nm. Before and after calcination at 800 °C, the lattice parameters, microstrain and surface area of the (ZrO2)1−x(Yb2O3)x samples tended to increase with Yb3+ concentration; while, the average crystallite size decreased correspondingly. In the Arrhenius plots over the measurement temperature range of 400–800 °C, the bulk ionic conductivity of the compacts sintered at 1400 °C for 24 h showed a maximum value at the composition of x=0.08 in cubic structure, with an activation energy of 0.89 eV. At 800 °C, σb=0.049 S cm−1 for x=0.08.  相似文献   

8.
Superfine and uniform La2NiO4+δ powder was synthesized by a polyaminocarboxylate complex precursor method. La2NiO4+δ layers were screen-printed on dense Ce0.8Sm0.2O1.9 electrolyte substrates and sintered at 900–1,100 °C. The microstructure and electrochemical properties of the resulting porous electrodes were investigated with respect to sintering temperature. The results indicate a significant effect of sintering temperature on the microstructure and electrode polarization. It was found that elevating sintering temperature was favorable to the charge transfer process whereas undesired for the oxygen surface exchange process due to an increase of the grain size. Sintering at 900 °C was determined to be preferred in terms of the polarization resistance of the electrode. The porous electrode sintered at the temperature showed a fine-grained microstructure (about 200 nm) and a relatively low polarization resistance of 0.28 Ω cm2 at 800 °C. This work suggests that preparing the electrode from superfine starting powder is contributive to modifying the polarization properties.  相似文献   

9.
Nano-sized La0.8Sr0.2MnO3 prepared by the polyethylene glycol assisting sol–gel method was applied as oxygen reduction catalyst in nonaqueous Li/O2 batteries. The as-synthesized La0.8Sr0.2MnO3 was characterized by X-ray diffraction (XRD), scanning electron microscopy, and Brunauer–Emmet–Teller measurements. The XRD results indicate that the sample possesses a pure perovskite-type crystal structure, even sintered at a temperature as low as 600 °C, whereas for solid-state reaction method it can only be synthesized above 1,200 °C. The as-prepared nano-sized La0.8Sr0.2MnO3 has a specific surface area of 32 m2 g−1, which is much larger than the solid-state one (1 m2 g−1), and smaller particle size of about 100 nm. Electrochemical results show that the nano-sized La0.8Sr0.2MnO3 has better catalytic activity for oxygen reduction, higher discharge plateau and specific capacity.  相似文献   

10.
The early stages of crystallization for MgO-Al2O3-SiO2-TiO2-La2O3 glasses with different La2O3 concentrations were studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The glass transition temperature (Tg) of the glass decreases at first and then increases again with increasing La2O3 concentration. This indicates that the structure of the glass becomes weaker at first and then stronger again. Lanthanum acts in glasses as network modifier and will usually decrease the network connectivity of the glass structure. Nevertheless, if the La2O3 concentration is high enough, the oxygen and other ions start to agglomerate around La, resulting in a more closely packed structure. Heat-treatment of the sample with x = 0.1 at 770–810 °C results in the precipitation of a droplet phase with higher mean atomic weight embedded in a matrix with lower mean atomic weight. The initial crystalline phase magnesium aluminum titanate (MAT) precipitates from the droplet phase. Nevertheless, for the sample with x = 0.4, dendrite-like structure could be observed after heat-treatment of the glass at 810 °C. Furthermore, the crystalline phase first precipitated is the lanthanum containing perrierite, which could be attributed to the rearrangement of the glass structure as an effect of La3+ incorporation.  相似文献   

11.
The effects of doping the mixed-conducting (La,Sr)FeO3−δ system with Ce and Nb have been examined for the solid-solution series, La0.5−2xCexSr0.5+xFeO3−δ (x = 0–0.20) and La0.5−2ySr0.5+2yFe1−yNbyO3−δ (y = 0.05–0.10). Mössbauer spectroscopy at 4.1 and 297 K showed that Ce4+ and Nb5+ incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for La0.3Sr0.7Fe0.90Nb0.10O3−δ at 923–1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10−5–0.5 atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe4+ concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 × 10−3 for La0.3Sr0.7Fe0.9Nb0.1O3−δ cf. 1.3 × 10−3 for La0.5Sr0.5FeO3−δ at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0–21.2) × 10−6 K−1 at 780–1080 K.  相似文献   

12.
The complexes M[La(C2O4)3]⋅xH2O (x=10 for M=Cr(III) and x=7 forM=Co(III)) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR, reflectance and powder X-ray diffraction (XRD) studies. Thermal investigations using TG, DTG and DTA techniques in air of chromium(III)tris(oxalato)lanthanum(III)decahydrate, Cr[La(C2O4)3]⋅10H2O showed the complex decomposition pattern in air. The compound released all the ten molecules of water within ∼170°C, followed by decomposition to a mixture of oxides and carbides of chromium and lanthanum, i.e. CrO2, Cr2O3, Cr3O4, Cr3C2, La2O3, La2C3, LaCO, LaCrOx (2<x<3) and C at ∼1000°C through the intermediate formation of several compounds of chromium and lanthanum at ∼374, ∼430 and ∼550°C. Thecobalt(III)tris(oxalato)lanthanum(III)heptahydrate, Co[La(C2O4)3]⋅7H2O becomes anhydrous around 225°C, followed by decomposition to Co3O4, La2(CO3)3 and C at ∼340°C and several other mixture species of cobalt and lanthanum at∼485°C. The end products were identified to be LaCoO3, Co3O4, La2O3, La2C3, Co3C, LaCO and C at ∼ 2>1000°C. DSC studies in nitrogen of both the compounds showed several distinct steps of decomposition along with ΔH and ΔSvalues. IR and powder XRD studies have identified some of the intermediate species. The tentative mechanisms for the decomposition in air are proposed. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

13.
Dense mixed-conducting membranes of La0.6Sr0.4Fe0.9Ga0.1O3−δ (LSFG) with various contents of MgO as second phase particles were prepared to evaluate the influence of magnesia inclusions on LSFG stoechiometry, microstructure and oxygen permeation. XRD and EDS investigations on sintered pellets revealed that magnesia inclusions were quite inert with the LSFG matrix phase, the composition of which remained identical whatever the magnesia content. LSFG pure phase material was synthesized through a solid-state route and sintered between 1250 and 1350 °C. Sintering temperature strongly affected microstructure of the LSFG membrane since rapid grain growth and decreasing density were observed when temperature increased. Small amounts of fine particles of magnesia, from 2 to 10 vol%, were found to significantly reduce grain size of sintered samples and made it possible to obtain a high density on a large sintering temperature range. Average grain size experimental data of LSFG in function of the amount of second phase magnesia were also compared with numerical models from literature. Oxygen permeation rates of pure LSFG and composite LSFG/MgO dense membranes were measured in an air/argon gradient, in a temperature range from 825 to 975 °C and results were discussed to explain the flux improvement of composite membranes.  相似文献   

14.
A-site deficient perovskite La0.57Sr0.15TiO3 (LSTO) materials are synthesized by a modified polyacrylamide gel route. X-ray diffraction pattern of LSTO indicates an orthorhombic structure. The thermal expansion coefficient of LSTO is 10.0 × 10−6 K−1 at 600 °C in 5%H2/Ar. LSTO shows an electrical conductivity of 2 S cm−1 at 600 °C in 3%H2O/H2. A new composite material, containing the porous LSTO backbone impregnated with small amounts of Ce0.9Gd0.1O2−δ (CGO) (3.4–8.3 wt.%) and Ni/Cu (2.0–6.3 wt.%), is investigated as an alternative anode for solid oxide fuel cells (SOFCs). Because of the substantial electro-catalytic activity of the fine and well-dispersed Ni particles on the surface of the ceramic framework, the polarization resistance of 6.3%Ni-8.3%CGO-LSTO anode reaches 0.73 Ω cm2 at 800 °C in 3%H2O/H2. In order to further improve the anodic performance, corn starch and carbon black are used as pore-formers to optimize the microstructure of anodes.  相似文献   

15.
Spinel LiMn2O4 and Sm, La co-substituted LiSm x La0.2-x Mn1.80O4 (x?=?0.05, 0.10 and 0.15) cathode materials were synthesized by sol–gel method using aqueous solutions of metal nitrates and tartaric acid as chelating agent at 600 °C for 10 h. The structure and electrochemical properties of the synthesized materials were characterized by using thermogravimetric/differential thermal analysis, X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, charge/discharge and electrochemical impedance spectroscopy studies. XRD analysis indicated that all the prepared samples were mainly belong to cubic crystal form with Fd3m space group. LiSm0.10La0.10Mn1.80O4 exhibits capacity retention of 90 % and 82 % after 100 cycles at room temperature (30 °C) and at elevated temperature (50 °C) at a rate of 0.5-C, respectively, much higher than those of the pristine LiMn2O4 (74 % and 60 %). Among all the compositions, LiSm0.10La0.10Mn1.80O4 cathode has improved the structural stability, high-capacity retention, better elevated temperature performance and excellent electrochemical performances of the rechargeable lithium-ion batteries.  相似文献   

16.
Solid state reactions at 925°C between the high-T c ceramic superconductor YBa2Cu3O7?δ and La2O3 and SrCO3, respectively, mixed in various molar ratiosr=MeOn/YBa2Cu3O7?δ, were studied using X-ray powder diffraction and scanning electron microscopy. The reaction between YBa2Cu3O7?δ and La2O3 yielded (La1?xBax)2CuO4?δ, withx≈0.075?0.10. La2?xBa1+xCu2O6?δ, withx≈0.2?0.25 and La-doped (Y1?xLax)2BaCuO5, withx≈0.10?0.15. Forr=3.0, Y-doped La2BaCuO5 resulted also. The reaction between YBa2Cu3O7?δ and SrCO3 yielded (Sr1?zBaz)2CuO3, withz≈0.1, Y2(Ba1?zSrz)CuO5, withz=0.1?0.15, and a nonsuperconducting compound with an approximate composition of Y(Ba0.5Sr0.5)5Cu3.5O10±δ. At values ofr≤2.0, unsubstituted YBa2Cu3O7?delta was found in the reaction products.  相似文献   

17.
《Comptes Rendus Chimie》2014,17(9):920-926
Lanthanum phosphosilicate apatites with the chemical formula Sr10–xLax(PO4)6–x(SiO4)xO, where 0  x  6, usually prepared by a solid-state reaction at about 1400 °C, were synthesized via the mechanochemical method at room temperature. The samples were characterized using powder X-ray diffraction, infrared spectroscopy and thermal analysis. The results showed that the prepared products were carbonated apatites and no secondary phase was detected. The realization of the milling under a controlled atmosphere can lead to oxyapatites containing no carbonates. The ionic conductivity of the Sr6La4(PO4)2(SiO4)4O sample was investigated by using impedance spectroscopy. The highest ionic conductivity value of 1.522 × 10−6 S·cm−1 was found at 800 °C. In the investigated temperature range, the activation energy is of 0.85 eV.  相似文献   

18.
The Li4+xMxSi4+xO4‐yLi2O (M=Al, B; x = 0 to 0.6, y = 0 to 0.5) ion conductors were prepared by the Sol‐Gel method and examined in detail. The powder and sintered samples were characterized by DTA‐TG, XRD, SEM, and AC impedance techniques. The experimental results show that the conductivity and sinterability in creased with the amount of excess lithium oxide in the silicate. The Li2O phase acts as a flux to accelerate the sintering process and to obtain high conductivity of grain boundaries. The particle size of the sintered pellets is about 0.25 μm. The maximum conductivity at 200 °C is 5.40 × 10?3s cm?1 for Li4.4Al0.4 Si0.6O4‐0.3Li2O.  相似文献   

19.
High performance La2−xSrxCuO4−δ (x = 0.1, 0.3, 0.5) cathode materials for intermediate temperature solid oxide fuel cell (IT-SOFCs) were prepared and characterized. The investigation of electrical properties indicated that La1.7Sr0.3CuO4 cathode has low area specific resistance (ASR) of 0.16 Ω cm2 at 700 °C and 1.2 Ω cm2 at 500 °C in air. The rate-limiting step for oxygen reduction reaction on La1.7Sr0.3CuO4 electrode changed with oxygen partial pressure and measurement temperature. La1.7Sr0.3CuO4 cathode exhibits the lowest overpotential of about 100 mV at a current density of 150 mA cm−2 at 700 °C in air.  相似文献   

20.
The performance of the SrCo0.8Fe0.2O3−δ(SCF)–La0.45Ce0.55O2−δ(LDC) composite cathodes was studied in this paper. The composite cathodes were prepared by screen-printing, and then sintered at 1200 °C for 2 h. Electrochemical impedance spectroscopy (EIS) and cathodic polarization test were carried out to investigate the electrochemical properties of the composite cathodes. The results showed that the composite cathodes had superior electrochemical performance compared to that of the pure SCF cathodes. Through optimizing the structures of composite cathodes, the cathodic overpotential of triple-layer SCF–LDC composite cathodes was only 23 mV at 0.3 A cm−2. The specific ohmic resistance, charge transfer resistance and gas phase diffusion resistance of the triple-layer SCF–LDC cathodes were the lowest for the SCF–LDC composite cathodes, and they were 0.1 Ω cm2, 0.01 Ω cm2 and 0.1 Ω cm2 respectively at 800 °C. The changes were attributable to the enlargement of triple phases boundary (tpb) and enhancement of the adhesion between electrode and electrolyte by adding LDC to the cathode material.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号