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1.
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   

2.
Lanthanum silicated apatites with nominal composition La9.33+x(SiO4)6O2+3x/2 (−0.2 < x < 0.27) have been successfully synthesized by solid state reaction using a new reagent La2O2CO3 and amorphous SiO2 precursors. The formation mechanism of La2O2CO3 reagent, which cannot be purchased, has been followed by in-situ temperature depend XRD of La2O3 under CO2 atmosphere. The stability of this reagent during the synthesis step allowed to limit the formation of secondary phase La2Si2O7 and made the weighting of the reagent easier. High purity powders could be synthesized at the temperature of 1400 °C. Dense pellets (more than 98.5%) were obtained by isostatic pressing of powders calcined at 1200 °C and then sintered at 1550 °C. Traces of La2SiO5 secondary phase present in synthesized powder disappeared after densification and pure oxyapatite materials were obtained for all the compositions. Electrical measurements confirmed that conductivity behaviors of the sintered pellets were dependent to the oxygen over-stoichiometry. Indeed, a relatively high conductivity of 1 × 10−2 S cm−1 was exhibited at 800 °C for the nominal composition La9.60(SiO4)6O2.405 with low activation energy around 0.79 eV. The ionic conductivity properties were comparable with that of the earlier obtained materials.  相似文献   

3.
Cathode materials LiNi0.5Mn1.5O4 and LiNi0.5 ? x/2La x Mn1.5 ? x/2O4 (x = 0.04, 0.1, 0.14) were successfully prepared by the sol-gel self-combustion reaction (SCR) method. The X-ray diffraction (XRD) patterns indicated that, a few of doping La ions did not change the structure of LiNi0.5Mn1.5O4 material. The scanning electronic microscopy (SEM) showed that the sample heated at 800°C for 12 h and then annealed at 600°C for 10 h exhibited excellent geometry appearance. A novel electrolyte system, 0.7 mol L?1 lithium bis(oxalate)borate (LiBOB)-propylene carbonate (PC)/dimethyl carbonate (DMC) (1: 1, v/v), was used in the cycle performance test of the cell. The results showed that the cell with this novel electrolyte system performed better than the one with traditional electrolyte system, 1.0 mol L?1 LiPF6-ethylene carbonate (EC)/DMC (1: 1, v/v). And the electrochemical properties tests showed that LiNi0.45La0.1Mn1.45O4/Li cell performed better than LiNi0.5Mn1.5O4/Li cell at cycle performance, median voltage, and efficiency.  相似文献   

4.
The isomorphous substitution of smaller RE elements (Ln = Nd, Eu, Gd, Ho, Tm, and Yb) for lanthanum in the apatite silicate solid solutions La9−xLnx(SiO4)6O1.5 was studied by X-ray powder diffraction and the Rietveld structure refinement, scanning electron microscopy and energy-dispersive X-ray microanalysis. Single-phase samples were prepared by solid-state synthesis at a moderate temperature of 1200 °C using an amorphous SiO2 nanopowder (10–40 nm) as a reactant. As the atomic number of Ln increases, the complete solubility, 0 ≤ x ≤ 9, found in the systems with Ln = Nd, Eu, Gd, and Ho changes to a limited one for Ln = Tm (0 ≤ x < 1.5) and Yb (0 ≤ x < 1). The distribution of La and smaller Ln over two structurally independent cationic sites is close to statistical. In both cationic polyhedra, Ln(1)O9 and Ln(2)O7, the bond lengths Ln – O decrease with x, except the longest bonds Ln(1) – O(3) and Ln(2) – O(1) which increase slightly. The experimental results on the substitution limits agree with the values of the mixing energy, and critical temperature of miscibility calculated in the approximation of a regular solid solution.  相似文献   

5.
Perovskite-type compounds, Li x La(1− x )/3NbO3 and (Li0.25La0.25)1− x Sr0.5 x NbO3 as lithium ionic conductors, were synthesized by a solid-state reaction. From powder X-ray diffraction, the solid solution ranges of the two compounds were determined to be 0≤x≤0.25 and 0≤x≤0.125, respectively. In the Li x La(1− x )/3NbO3 system, the ionic conductivity of lithium at room temperature, σ25, exhibited a maximum value of 4.7 × 10−5 S · cm−1 at x = 0.10. However, because of the decrease in the lattice parameters with increasing Li concentration , σ25 of the samples decreased with increasing x from 0.10 to 0.25. Also, in the (Li0.25La0.25)1− x Sr0.5 x NbO3 system, the lattice parameter increased with the increase of Sr concentration and the σ25 achieved a maximum (7.3 × 10−5 S · cm−1 at 25 °C) at x = 0.125. Received: 12 September 1997 / Accepted: 15 November 1997  相似文献   

6.
The structure of fine crystalline borogermanate La12GdEuB6Ge2O34 has been studied by NMR and IR spectroscopy. It has been demonstrated that this compound is isostructural to the homonuclear Ln14B6Ge2O34 compounds (Ln = Pr-Gd) and crystallizes in space group P31. The rare-earth elements have been distributed over the LnO n polyhedra in La12GdEuB6Ge2O34 by analogy with the known structures. Lanthanum can occupy positions with CN 7–10, and the symmetry of these LnO n coordination polyhedra is not higher than C 2v . In the La12GdEuB6Ge2O34 structure, the LnO n coordination polyhedra are formed by oxygen atoms of oxo groups and anions, some of the oxygen atoms being shared by LnO n polyhedra. The BO3 and GeO4 groups in the structure are also bridging, i.e., are involved in bonding of LnO n polyhedra. One of the B-O bonds in La12EuGd(BO3)6(GeO4)2O8 is elongated as compared with the B-O bond lengths in homonuclear compounds Pr14(BO3)6(GeO4)2O8 and Nd14(BO3)6(GeO4)2O8. In the La12GdEuB6Ge2O34 structure, germanium is located in isolated GeO4 tetrahedra with distorted T d symmetry. The local symmetry of lanthanum in fine crystalline La12GdEuB6Ge2O34 have been assessed using 139La NMR (B 0 = 7.04 T, room temperature). For comparison, binary lanthanum compounds with a simpler structure— LaBO3, La(BO2)3, and La2GeO5—have been used. The spectra of all compounds are rather broad (ν1/2 = 180–240 kHz). The 139La NMR spectra of the LaBO3, La(BO2)3, and La12GdEu(BO3)6(GeO4)2O8 borates show a signal at (1080 ± 40) ppm, which is absent in the spectrum of La2GeO5. The shape of the 139La NMR spectra of La12GdEu(BO3)6(GeO4)2O8 and LaBO3 is characterized by the second-order quadrupole splitting with a downfield shoulder. The similarity of these spectra points to close 139La NMR chemical shifts of La12GdEu(BO3)6(GeO4)2O8 and LaBO3. No quadrupole splitting was observed in the spectra of La(BO2)3 and La2GeO5.  相似文献   

7.
The preparatory conditions for the oxide compositions La1?xCaxCoO3?δ have been determined along with their crystallographic, thermochemical, and electrical properties. Single phase solid solutions of the perovskite structure form atx < 0.6. It has been established that the compounds obtained in the open air atmosphere are oxygen deficient, the deficit increasing withx and temperature. The specific resistivity atx = 0.2–0.6 is (1–2)·10?3 ohm·cm; it increases with the concentration of oxygen vacancies. At 0.3 ≤ x ≤ 0.6 thep-type conductivity is metallic in character with low temperature resistivity coefficients of the order (1–5)·10?4 K?1 in the interval 20–700°C.  相似文献   

8.
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   

9.
A modified low temperature solid state process has been proposed to systematically synthesize europium-doped yttrium phosphate-vanadates with general formula Y0.48Li1.5V1 ? x P x O4:Eu3+ (x = 0.2, 0.4, 0.6). All the Y0.48Li1.5V1 ? x P x O4:Eu3+ products were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The excitation and emission spectra were measured at room temperature. Y0.48Li1.5V1 ? x P x O4:Eu3+ show the characteristic missions of Eu3+ (5 D 0?7 F 1, 2, 3, 4 transitions dominated by 5 D 0?7 F 2), intensities of the products were sensitive to the x value, and the x value had an obvious influence on the (5 D 0?7 F 2)/(5 D)0?7 F 1) intensity ratio of Eu3+. In addition, incorporation of Li+ ions in the phosphors reduce the amount of Y2O3, lower the cost of production, and cause a new phase Li3VO4.  相似文献   

10.
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   

11.
I‐Type La2Si2O7: According to La6[Si4O13][SiO4]2 not a Real Lanthanum Disilicate In attempts to synthesize lanthanum telluride silicate La2Te[SiO4] (from La, TeO2, SiO2 and CsCl, molar ratio: 1 : 1: 1 : 20, 950 °C, 7 d) or fluoride‐rich lanthanum fluoride silicates (from LaF3, La2O3, SiO2 and CsCl, molar ratio: 5 : 2 : 3 : 17, 700 °C, 7 d) in evacuated silica tubes, colourless lath‐shaped single crystals of hitherto unknown I‐type La2Si2O7 (monoclinic, P21/c; a = 726.14(5), b = 2353.2(2), c = 1013.11(8) pm, β = 90.159(7)°) were found in the CsCl‐flux melts. Nevertheless, this new modification of lanthanum disilicate does not contain any discrete disilicate groups [Si2O7]6‐ but formally three of them are dismutated into one catena‐tetrasilicate ([Si4O13]10‐ unit of four vertex‐linked [SiO4]4‐ tetrahedra) and two ortho‐silicate anions (isolated [SiO4]4‐ tetrahedra) according to La6[Si4O13][SiO4]2. This compound can be described as built up of alternating layers of these [SiO4]4‐ and the horseshoe‐shaped [Si4O13]10‐ anions along [010]. Between and within the layers the high‐coordinated La 3+ cations (CN = 9 ‐ 11) are localized. The close structural relationship to the borosilicates M3[BSiO6][SiO4](M = Ce ‐ Eu) is discussed and structural comparisons with other catena‐tetrasilicates are presented.  相似文献   

12.
Solid lithium electrolytes in the Li4-3x Fe x GeO4 system were synthesized. Their phase composition, thermal behavior, and electrical conductivity were studied in the temperature interval 300–750°C. Introduction of Fe3+ ions into lithium orthogermanate leads to the formation of a γ-Li3PO4-type structure and to a sharp increase in the conductivity, with a maximum reached at x = 0.075–0.15: about 10?1 S cm?1 at 300°C and more than 1 S cm?1 at 700°C. The main current carriers are interstitial Li+ cations weakly bound with the rigid framework. Owing to high conductivity, the electrolytes studied are of interest for use in high-temperature electrochemical devices.  相似文献   

13.
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   

14.
Two original compounds, Ln4?2xBa2+2xZn2?xO10?2x, were isolated for Ln = La, Nd and 0 ≤ x ≤ 0.25. These oxides are tetragonal with a and c parameters close to 6.91 and 11.59 Å, respectively, for lanthanum, and 6.75 and 11.54 Å for neodymium. The structure of these phases was determined from X-ray powder patterns in the most symmetric space group, I4mcm, using Patterson and Fourier functions for x = 0. The structure should be compared to that of copper oxides La4?2xBa2+2xCu2?xO10?2x: it is built up of identical Ln2O5 layers formed from face- and edge-sharing LnO8 polyhedra, between which Ba2+ and Zn2+ ions are inserted. Contrary to the copper compounds, two successive Ln2O5 layers are rotated by 90°, involving a doubling of c. The result for Zn2+ is tetrahedral coordination, while the coordination of Ba2+ becomes a bicapped antiprism.  相似文献   

15.
CO2 在高分散 Ni/La2O3 催化剂上的甲烷化   总被引:1,自引:0,他引:1  
 以 La2O3 为载体, 采用浸渍法制备了 10%Ni/La2O3 催化剂, 考察了该催化剂的 CO2 甲烷化反应性能. 结果表明, 在较低的温度 (350 oC) 和高空速 (约 30000 h–1) 下, 甲烷时空收率可大于 3000 g/(kg•h), 无论转化率高低, 甲烷选择性始终保持在 100%. X 射线衍射和 H2-程序升温还原等表征结果表明, CO2 在 Ni/La2O3 催化剂上的加氢机理可能与 Ni/γ-Al2O3 上不同, 并且 La2O2CO3 的形成有利于提高催化剂活性.  相似文献   

16.
On the H‐ and A‐Type Structure of La2[Si2O7] By thermal decomposition of La3F3[Si3O9] at 700 °C in a CsCl flux single crystals of a new form of La2[Si2O7] have been found which is called H type (triclinic, P1; a = 681.13(4), b = 686.64(4), c = 1250.23(8) pm, α = 82.529(7), β = 88.027(6), γ = 88.959(6)°; Vm = 87.223(9) cm3/mol, Dx = 5.113(8) g/cm3, Z = 4) continuing Felsche's nomenclature. It crystallizes isotypically to the triclinic K2[Cr2O7] in a structure closely related to that of A–La2[Si2O7] (tetragonal, P41; a = 683.83(7), c = 2473.6(4) pm; Vm = 87.072(9) cm3/mol, Dx = 5.122(8) g/cm3, Z = 8). For comparison, the latter has been refined from single crystal data, too. Both the structures can be described as sequence of layers of each of two crystallographically different [Si2O7]6– anions always built up of two corner‐linked [SiO4] tetrahedra in eclipsed conformation with non‐linear Si–O–Si bridges (∢(Si–O–Si) = 128–132°) piled up in [001] direction and aligned almost parallel to the c axis. They differ only in layer sequence: Whereas the double tetrahedra of the disilicate units are tilted alternating to the left and in view direction ([010]; stacking sequence: AB) in H–La2[Si2O7], after layer B there follow due to the 41 screw axis layers with anions tilted to the right and tilted against view direction ([010]; stacking sequence: ABA′B′) in A–La2[Si2O7]. The extremely irregular coordination polyhedra around each of the four crystallographically independent La3+ cations in both forms (H and A type) consist of eight to ten oxygen atoms in spacing intervals of 239 to 330 pm. The possibility of more or less ordered intermediate forms will be discussed.  相似文献   

17.
The results of study of the thermal reactivity and1H NMR spectroscopy of solid polyvanadates of general formula Sr1?x H2x V6O16 · aq are presented. Compounds withx=0 (a),x ∈ (0.3–0.6) (b) andx=1 (c) were studied. The protons are bonded in V - OH (b, c) and V - O ... H (a, b, c) groups, in H2O molecules (a, b, c) and in H2O ... H2O systems (a, b, c). Dehydration of the studied compounds proceeds stepwise. Total dehydration causes decomposition of the original structures and Sr(VO3)2, SrV12O30 and V2O5 are formed. The results confirm the role of crystal water in stabilizing the structures of the studied compounds.  相似文献   

18.
La4Ni3O10 oxide was synthesized as a cathode material for intermediate-temperature solid oxide fuel cells by a facile sol–gel method using a nonionic surfactant (EO)106(PO)70(EO)106 tri-block copolymer (F127) as the chelating agent. The crystal structure, electrical conductivity, and electrochemical properties of La4Ni3O10 were investigated by X-ray diffraction, DC four-probe method, electrochemical impedance spectra, and I–V measurements. The La4Ni3O10 cathode showed a significantly low polarization resistance (0.26 Ω cm2) and cathodic overpotential value (0.037 V at the current density of 0.1 A cm?2) at 750 °C. The results measured suggest that the diffusion process was the rate-limiting step for the oxygen reduction reaction. The La4Ni3O10 cathode revealed a high exchange current density value of 62.4 mA cm?2 at 750 °C. Furthermore, an anode-supported single cell with La4Ni3O10 cathode was fabricated and tested from 650 to 800 °C with humidified hydrogen (~3 vol% H2O) as the fuel and the static air as the oxidant. The maximum power density of 900 mW cm?2 was achieved at 750 °C.  相似文献   

19.
Ordered Occupation of Octahedra in Ba6La2Al1,5Fe2,5O15 Ba6La2Al1.5Fe2.5O15 was prepared and investigated by X-ray single crystal technique. It crystallizes in the space group C – P63mc; a = 11.814, c = 7.1003 Å; Z = 2. The M3+O6 octahedra are occupied exclusively by Fe3+ ions, the M3+O4 tetrahedra in contrast are statistically filled by Fe3+ and Al3+ ions. Ba6La2Al1.5Fe2.5O15 is a partially ordered mixed crystal of the pure iron and aluminium compounds.  相似文献   

20.
Substituted lanthanum manganites with the general composition La1–x Bi x Mn1–y Fe(Ni,Cu)yO3 + δ and unit cells in rhombohedral (space group (sp. gr.) R-3c) and/or orthorhombic (sp. gr. Pnma) symmetry are synthesized and attested. They are characterized by permanent excessive oxygen nonstoichiometry within a single structure type at room temperature, independent of the dopant concentration. These materials are adequately mechanically compatible with bismuth niobates. The interval of their chemical compatibility with bismuth-containing compounds is limited by 700–800°C. In this region, the conductivity of composites of substituted lanthanum manganites and bismuth-containing electrolytes is higher as compared with individual compounds. The use of individual manganites or their composites as the electrodes in cells with bismuthcontaining electrolytes increases the total conductivity of the cells.  相似文献   

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