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 30 毫秒
1.
《Solid State Ionics》2006,177(19-25):1799-1802
Manganese-doped ceria-based oxides, Ce1−xMnxO2−δ (0.05  x  0.3) and Ce1−xyGdxMnyO2−δ˙ (0.05  x 0.2, 0.05  y  0.25) were synthesized, and crystal phase analysis by XRD and measurements of electrical properties were performed. Solubility limit of Mn in Ce1−xMnxO2−δ˙ seemed to be between 5 mol% and 10 mol% and Mn3O4 was the main by-product above the solubility limit in the case of heat treatment at 1300 °C. Judging from the oxygen partial pressure dependence of total conductivity and emf measurements, Ce1−xMnxO2−δ˙ is a single-phase mixed conductor within the composition below the solubility limit, and when the composition of Mn exceeds the solubility limit, it becomes the dual-phase mixed conductor of Ce1−xMnxO2−δ˙ and Mn3O4. The doing of Mn in gadlia-doped ceria, Ce1−xyGdxMnyO2−δ˙ (0.05  x  0.2, 0.05  y  0.25), was more difficult than that in CeO2 presumably due to the preferential reaction between Gd and Mn to give GdMnO3 to the GDC solid solution formation, and the Mn doping seems not to be so effective in preparing the mixed ionic–electronic conductor based on GDC.  相似文献   

2.
《Solid State Ionics》2006,177(9-10):863-868
Layered Li(Ni0.5Co0.5)1−yFeyO2 cathodes with 0  y  0.2 have been synthesized by firing the coprecipitated hydroxides of the transition metals and lithium hydroxide at 700 °C and characterized as cathode materials for lithium ion batteries to various cutoff charge voltages (up to 4.5 V). While the y = 0.05 sample shows an improvement in capacity, cyclability, and rate capability, those with y = 0.1 and 0.2 exhibit a decline in electrochemical performance compared to the y = 0 sample. Structural characterization of the chemically delithiated Li1−x(Ni0.5Co0.5)1−yFeyO2 samples indicates that the initial O3 structure is maintained down to a lithium content (1  x)  0.3. For (1  x) < 0.3, while a P3 type phase is formed for the y = 0 sample, an O1 type phase is formed for the y = 0.05, 0.1 and 0.2 samples. Monitoring the average oxidation state of the transition metal ions with lithium contents (1  x) reveals that the system is chemically more stable down to a lower lithium content (1  x)  0.3 compared to the Li1−xCoO2 system. The improved structural and chemical stabilities appear to lead to better cyclability to higher cutoff charge voltages compared to that found before with the LiCoO2 system.  相似文献   

3.
《Solid State Ionics》2006,177(7-8):733-739
Different from a conventional solid state reaction, a hydrothermal reaction mechanism is very difficult to illuminate and sometimes it remains undisclosed. Making an attempt to understand the hydrothermal phase formation process of o-LiMnO2 obtained between the reaction of spinel type Mn3O4 precursor and LiOH aqueous solution, the possible reaction route was postulated and experimentally testified. Firstly, the selective dissolution of Mn2+ from the tetrahedral site of [MnII]tet4a[MnIII2]oct8dO4, which is considered as to be an ionic exchange reaction with Li+, and an additional Li+ intercalation into the host structure of precursor would give rise to the formation of meta-stable Li2Mn2O4 ([LiI]tet4a[LiI]oct8c[MnIII2]oct8dO4). Secondly, the phase would be simultaneously transformed to thermodynamically stable o-LiMnO2 phase under hydrothermal state during hydrothermal reaction. Through the above reaction process, the solid solution range of o-LiCoxMn1−xO2 was as large as x  0.14, and that of o-LiFexMn1−xO2 was x  0.05. Co doped o-LiMnO2 has higher capacity and good cyclability upon cycling, being substantially more stable to cycle than the unsubstituted and Fe doped materials.  相似文献   

4.
《Solid State Ionics》2006,177(19-25):1807-1810
The crystal chemistry and mixed conductor properties of the n = 2 member of the Ruddlesden–Popper (R–P) phases Sr3−xLaxFe2−yNiyO7−δ with 0  x  0.3 and 0  y  1.0 have been studied at high temperature. High-temperature X-ray diffraction and thermogravimetric measurements of the equilibrium pO2 (10 5  pO2  1 atm) in the temperature range 400  T  1000 °C indicate that the Sr3FeNiO7−δ phase is able to accommodate a large oxygen non-stoichiometry (δ  1.5) without structural transformations. The electrical conductivity and oxygen permeability increase with the substitution of Ni for Fe in the range 550  T  1000 °C. The electrical transport of the Sr3FeNiO7−δ phase is thermally activated and the activation energy decreases with the substitution of Ni for Fe for a given oxygen content. The increase in the oxygen permeation flux with increasing Ni content is due to an increasing oxygen non-stoichiometry and a lower activation energy for permeation.  相似文献   

5.
《Solid State Ionics》2006,177(13-14):1199-1204
Perovskite oxides of the composition BaxSr1−xCo1−yFeyO3−δ(BSCF) were synthesized via a modified Pechini method and characterized by X-ray diffraction, dilatometry and thermogravimetry. Investigations revealed that single-phase perovskites with cubic structure can be obtained for x  0.6 and 0.2  y  1.0. The as-synthesized BSCF powders can be sintered in several hours to nearly full density at temperatures of over 1180 °C. Thermal expansion curves of dense BSCF samples show nonlinear behavior with sudden increase in thermal expansion rate between about 500 °C and 650 °C, due mainly to the loss of lattice oxygen caused by the reduction of Co4+ and Fe4+ to lower valence states. Thermal expansion coefficients (TECs) of BSCF were measured to be 19.2–22.9 × 10 6 K 1 between 25 °C and 850 °C. Investigations showed further that Ba0.5Sr0.5Co0.8Fe0.2O3−δ is chemically compatible with 8YSZ and 20GDC for temperatures up to 800 °C, above which severe reactions were detected. After being heat-treated with 8YSZ or 20GDC for 5 h above 1000 °C, Ba0.5Sr0.5Co0.8Fe0.2O3−δ was completely converted to phases like SrCoO3−δ, BaCeO3, BaZrO3, etc.  相似文献   

6.
《Solid State Ionics》2006,177(1-2):105-112
Five compositions of Li[Co1 −2x(Li1 / 3Mn2 / 3)x(Ni1 / 2Mn1 / 2)x]O2 solid solutions ( x = 0.1, 0.2, 0.3, 0.4, and 0.5) were synthesized using a sol–gel method with three end members of LiCoO2, Li2MnO3(Li[Li1 / 3Mn2 / 3]O2), and Li[Ni0.5Mn0.5]O2. The compositions of metals in transition metal sites were changed to see the effect of them on electrochemical behavior of the solid solutions. All the samples were nano-sized semi-spherical shaped particles with a layered structure. The reduction of cobalt content (the increase of other metals) in the sites increases the lattice parameters, a and c, resulting in the shift of Raman and XRD peak positions. The discharge capacity fading turned serious at higher Co contents, but it was significantly diminished with the decrease of Co content. At lower Co contents, the capacity increased with cycle numbers. The most stable voltage profile was obtained from the composition of Li[Li1 / 15Co3 / 5Ni1 / 10Mn7 / 30]O2 (x = 0.2).  相似文献   

7.
《Solid State Ionics》2006,177(1-2):29-35
Microstructure and local structure of spinel LiNixMn2  xO4 (x = 0, 0.1 and 0.2) were studied using X-ray diffraction (XRD) and a combination of X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge spectroscopy (XANES) and Raman scattering with the aim of getting a clear picture of the local structure of the materials responsible for the structural stability of LiNixMn2  xO4. XRD study showed that Ni substitution caused the changes of the materials’ microstructure from the view of the lattice parameter, mean crystallite size, and microstrain. XPS and XANES studies showed the Ni oxidation state in LiNixMn2  xO4 was larger than + 2, and the Mn oxidation state increased with Ni substitution. The decrease of the intensity of the 1s → 4pz shakedown transition on the XANES spectra indicated that Ni substitution suppressed the tetragonal distortion of the [MnO6] octahedron. The Mn(Ni)–O bond in LiNixMn2  xO4, which is stronger than the Mn–O bond in LiMn2O4 was responsible for the blue shift of the A1g Raman mode and could enhance the structural stability of the [Mn(Ni)O6] octahedron.  相似文献   

8.
《Solid State Ionics》2006,177(17-18):1509-1516
The structural and thermal properties of the delithiated LixNi1/3Co1/3Mn1/3O2 (0 < x  1) material have been investigated by using diffraction and thermoanalytical techniques such as XRD and TG-DSC methods. XRD result shows that the delithiated materials maintain the O3-type structure with defined stoichiometric number at the range of 0.24 < x  1, exhibiting good crystal structural stability. The cobalt and nickel ions in the delithiated materials change their valence state (i.e. Co3+ to Co4+ and Ni3+ to Ni4+) when x < 0.49; the irreversible changes of the transformation may affect the first cycle of charge–discharge efficiency of the materials. A comparison of the results of TG-DSC with TPD-MS shows that the irreversible change of oxygen species during the delithiation process of LixNi1/3Co1/3Mn1/3O2 have great influence on the structural and thermal stability and reversibility of the materials.  相似文献   

9.
《Solid State Ionics》2006,177(35-36):3109-3115
The oxygen nonstoichiometry δ of La1−xSrxCo1−yFeyO3−δ (x = 0.6 and y = 0.2, 0.4) was investigated by thermogravimetry in the range 703  T/°C  903 and 1E−5 < pO2/atm < 1. The oxygen deficit increases with increasing T and decreasing pO2. Electronic conductivities σ were measured as a function of pO2 in the range 1E−5 < pO2/atm < 1 at 700  T/°C  900. At constant T, a p-type pO2-dependence of σ is observed. Oxygen nonstoichiometry data are analyzed with regard to the enthalpy and entropy of oxidation ΔHoxθ and ΔSoxθ, as well as to the partial molar enthalpy and entropy of oxygen with respect to the standard state of oxygen (pO2θ = 1 atm), (hO  HOθ) and (sO  SOθ), respectively. For 2.67  (3  δ)  2.79, (hO  HOθ) decreases with increasing δ, while (sO  SOθ) is constant within the limits of error. Defect chemical modelling was performed by an ideal solution model under consideration of three different valence states for B-site ions (Co or Fe). The dependence of σ on δ is modelled, using calculated defect concentrations as functions of δ. Deviations from the ideal behaviour suggest an immobilization of n-type charge carriers by oxygen vacancies.  相似文献   

10.
《Solid State Ionics》2006,177(35-36):3199-3203
A co-dopant strategy is used to investigate the effect that the elastic strain in the lattice has on the grain ionic conductivity of doped ceria electrolytes. Based on critical dopant ionic radius (rc), different compositions in the LuxNdyCe1−xyO2−δ (x + y = 0.05, 0.10, 0.15, and 0.20) system are studied. Dopants are added such that the weighted average dopant ionic radius matches rc for all the compositions. Dense ceramic discs are prepared using conventional solid oxide route and sintering methods. Precise lattice parameter measurements are used to calculate the lattice strain. The ionic conductivity of the samples is measured in the temperature range of 250 °C to 700 °C using two-probe electrochemical impedance spectroscopy technique. The elastic strain present in LuxNdyCe1−xyO2−δ system is found to be negligible when compared to LuxCe1−xO2−δ (negative) and NdxCe1−xO2−δ (positive) systems. Grain ionic conductivity of LuxNdyCe1−xyO2−δ (where x + y = 0.05) at 500 °C is observed to be 1.9 × 10 3 S/cm which is twice as high as that of Lu0.05Ce0.95O2−δ. These results extend the validity of the rc concept as a strategy for co-doping ceria electrolytes and open new designing avenues for solid oxide electrolytes with enhanced ionic conductivity.  相似文献   

11.
《Solid State Ionics》2006,177(11-12):1059-1069
Lanthanum–aluminate-based oxides, (La0.8Sr0.2)1−yAl1−xMnxO3−δ (x = 0, 0.3, 0.5; y = 0 or 0.06) (LSAM), were synthesized and evaluated in detail as potential anode materials for solid oxide fuel cells (SOFCs). The electrical conductivity of LSAM (Mn  30 mol%) is dominated by p-type electronic conduction and can be treated as a diluted system of lanthanum manganites, (La,Sr)MnO3. At 810 °C, the electrical conductivity of (La0.8Sr0.2)0.94Al0.5Mn0.5O3−δ (LSAM8255b) reaches 12 S/cm in air and 2.7 S/cm in humidified Ar/4% H2 (p(O2)  10 18 bar). The thermal expansion coefficients of LSAM8255a and LSAM8255b match YSZ very well and no chemical reaction was observed between these two perovskite materials and YSZ up to at least 1400 °C. Fairly good electrochemical performance was observed for an LSAM8255b–YSZ composite anode. At 850 °C, the polarization resistances are only 0.34 and 0.50 Ω cm2 in wet (∼3% H2O) Ar/20% H2 and wet Ar/20% CH4, respectively. In addition, an exposure to Ar/20% CH4/3% H2O for 35 h did not cause any apparent carbon deposition on the electrode. However, the chemical stability of LSAM8255a and LSAM8255b in a typical anode environment under open circuit conditions does not seem sufficient, leading to performance degradation with time in wet Ar/20% H2 or wet Ar/20% CH4. Furthermore, relatively large chemical expansion (0.3–0.5%) was observed when the atmosphere was switched from air to wet Ar/4% H2, which might cause intolerable stress on the thin film electrolyte layer for a large-area anode-supported planar SOFC, but which might be tolerable for small geometries or electrolyte-supported SOFCs.  相似文献   

12.
《Solid State Ionics》2006,177(35-36):3147-3150
Glassy materials are promising intercalation compounds, due to their open network structure and absence of grain boundaries. Some glasses containing alkali ions and a high concentration of transition metal ions can present mixed ionic-electronic conductivity and are therefore potential candidates for application as cathode material in Li-ion batteries. The present work is devoted to the ternary system xLi2O–(1  x)[0.3V2O5–0.7TeO2] with 0  x  0.4. These compounds were prepared by heat treatment in air at 800 °C followed by traditional quenching. Raman spectroscopy and 51V nuclear magnetic resonance measurements were performed in order to highlight the structural short range order modifications induced by the introduction of the Li2O network modifier. These structural effects can be related to the electrical behaviour, as studied by complex impedance spectroscopy measurements.  相似文献   

13.
《Solid State Ionics》2006,177(19-25):1849-1853
Single phase materials of the La(2−x)SrxMnOδ (0.6  x  2.0) solid solution series were prepared via solid state reaction. The structure of each material was examined at room temperature and determined to be tetragonal for all phases examined. An expansion in lattice volume was observed on increasing lanthanum content. The stability and thermal expansion of each member of the solid solution series was determined via the use of in situ high temperature X-ray diffraction. It was found that all materials remained stable up to a temperature of 800 °C. Thermal expansion coefficients were found to be in the region of 15 × 10 6 K 1 for La(2−x)SrxMnOδ compounds where x > 1.4. The electrical conductivity of each phase was also determined over a similar temperature range with a maximum value of ∼6 Scm 1 at 900 °C for the x = 1.8 phase.  相似文献   

14.
《Solid State Ionics》2009,180(40):1702-1709
Nanopowders of Ca1  xEuxMnO3 (0.1  x  0.4) manganites were synthesized as a single phase using the auto gel-combustion method. The citrate method shows to be simple and appropriate to obtain single phases avoiding segregation or contamination. The Ca1  xEuxMnO3 system has been synthesized at 800 °C during 18 h, against the conventional method of mixing oxides used to obtain these materials at higher temperatures of synthesis. The formation reaction was monitored by X-ray diffraction (XRD) analysis and an infrared absorption technique (FTIR). The polycrystalline powders are characterised by nanometric particle size, ∼ 48 nm as determined from X-ray line broadening analysis using the Scherrer equation. Morphological analysis of the powders, using the scanning electron microscope (SEM), revealed that all phases are homogeneous and the europium-substituted samples exhibit a significant decrease in the grain size when compared with the undoped samples. The structure refinement by using the Rietveld method indicates that the partial calcium substitution by europium (for x  0.3) modifies the orthorhombic structure of the CaMnO3 perovskite towards a monoclinic phase. All manganites show two active IR vibrational modes around 400 and 600 cm 1. The high temperature dependence of electrical resistivity (between 25 and 600 °C) allows us to conclude that all the samples exhibit a semiconductor behaviour and the europium causes a decrease in the electrical resistivity by more than one order of magnitude. The results can be well attributed to the Mn4+/Mn3+ ratio.  相似文献   

15.
《Solid State Ionics》2006,177(19-25):1779-1783
Ceramic perovskite solid solutions (La0.9Sr0.1)[(Ga1−xMx)0.8Mg0.2]O3−y, 0  x  0.5, M = Fe, Ni, Cr (systems I–III) and brownmillerite solid solutions (La0.2Sr1.8)[Ga(Fe1−xMgx)]O5−z, 0  x  0.5, (system IV) have been prepared. The samples have been studied by X-ray diffraction and electron microscopy methods, dielectric spectroscopy and permeability measurements. The correlation between the composition, unit cell parameter changes, electrical transport and oxygen permeation properties has been revealed. Introduction of transition metals (Fe, Ni, or Cr), substituting for gallium, ensures the enhancement of the electronic constituent of the conductivity in the perovskite systems I–III. Stabilization of the transition metal high valence states 4+ or 5+ has been suggested for compositions I and III. This leads to a unit cell volume contraction and provides a decrease in the concentration of oxygen vacancies. The oxygen permeability reaches its maximum values in compositions I–III with x  0.3. On the contrary, increasing concentration of the doping element with lower valence state (magnesium), substituting for iron, determines the expansion of the brownmillerite unit cell volume and provides an increase of the oxygen vacancy concentration, which in turn, favors the enhancement of oxygen permeability of composition IV.  相似文献   

16.
《Solid State Ionics》2006,177(7-8):669-676
The electrical conductivity of sintered samples of Ce1−xNdxO2−x / 2 (0.01  x  0.2) was investigated in air as a function of temperature between 150 and 600 °C using AC impedance spectroscopy. The individual contribution of the bulk and grain boundary conductivities has been discussed in detail. In the low temperature range (< 350 °C), the activation enthalpy for bulk conductivity exhibited a shallow minimum at 3 mol% Nd, with a value of 0.68 eV. The activation enthalpy also produced a shallow minimum at 5 mol% Nd in the high temperature range (> 350 °C), with a value of 0.56 eV. It was shown that Ce1−xNdxO2−x / 2 is an electrolyte that obeys the Meyer Neldel rule. The bulk conductivity data measured by others for the same system has also been recalculated and re-evaluated to facilitate easier comparison with our own data.  相似文献   

17.
《Solid State Ionics》2006,177(26-32):2657-2660
The compounds Li(4−x)/3Mn2(1−x)/3CoxO2 (0 < x < 0.5) were prepared by the sol–gel technique. X-ray diffraction patterns of these compounds were identified as α-NaFeO2 type layered structure, though some super-structure lines, related to the ordered array of Li and transition metal ions in the transition metal layer, were observed. The magnetic susceptibility exhibited an antiferromagnetic transition around 40 K for x < 0.2, however the specimens with x > 0.3 had no magnetic transition. The magnetic percolation may explain these magnetic variations. The electrochemical performances were evaluated for the compound of x = 0.5, and it was seen that the electrochemical properties were sensitive to the potential window. Additionally, it was also found that the discharge capacity strongly depended on the preparation temperature; it took a maximum value at the preparation temperature of 900 °C. The discharge capacity is sensitive not only to the cation mixing degree but also to the particle size.  相似文献   

18.
《Solid State Ionics》2006,177(19-25):2005-2008
Electronic conductivity in the potential SOFC anode material La1−xSrxCr0.5Mn0.5Oδ has been investigated in the range 0.2 < x < 0.3. log(σT) vs. 1/T plots indicate conduction via thermally activated polaron hopping. At 900 °C, conductivity in air increases with Sr2+ via an increase in [BB] holes (B—transition metal). X-ray absorption spectroscopy (XAS) studies indicate that compensation for A-site Sr substitution and oxygen vacancy formation is via the Mn cation only; Cr maintains a 3+ oxidation state and 6-fold oxygen coordination. Electronic transport occurs by percolation between Mn cations in a disordered B-site sub-lattice. Conductivity decreases with p(O2), which is indicative of p-type conduction behaviour, but the relationship cannot be explained by a simple redox equilibrium involving Mn3+, Mn4+ and oxygen, possibly due to co-existence of Mn2+, Mn3+ and Mn4+ via disproportionation as with La1−xSrxMnOδ.  相似文献   

19.
《Solid State Ionics》2006,177(1-2):77-87
The incorporation of alkali cations into the tunneled structure of Ga4TiO8 was investigated and compared to predictions based on atomistic computer simulations. Samples were prepared as AxGa4−xTi1−xO8, A=Li, Na, and K, x  0.7, and as NaxGa4+xTi2−xO10 (x = 0.7, 0.85, and 1.0) using solid-state reactions at 1050–1350 °C. The sodium-containing tunneled structure, NaxGa4−xTi1−xO8, formed via solid-state reaction, but the potassium and lithium analogs did not. Instead, these systems formed mixed-phase assemblages, which are discussed in reference to compatibility triangles in the Li2O–Ga2O3–TiO2 and K2O–Ga2O3–TiO2 systems. Experimental results were compared to the results of energy minimization calculations using the General Utility Lattice Program (GULP). For the lithium-containing system, the computer simulations correctly predicted the formation of a mixed-phase assemblage containing LiGa5O8, Ga2O3, and TiO2. For the sodium- and potassium-containing system, the computer simulations suggested that mixtures of the single-cation oxide components should be the stable phase assemblages, in contradiction with experimentally observed results. Energy minimization calculations conducted on structurally different NaxGa4+xTi2−xO10 and NaxGa4+xTi3−xO12 phases indicated that those based on the n = 6 and n = 7 β-gallia rutile intergrowth structures have lower lattice energies than the experimentally observed sodium titanogallate structures reported previously in literature.  相似文献   

20.
《Solid State Ionics》2006,177(13-14):1149-1155
The Lu2+xTi2−xO7−x/2 (x = 0; 0.052; 0.096; 0.286; 0.44; 0.63; 33.3–49 mol% Lu2O3) nanoceramics with partly disordered pyrochlore-type structure are prepared by sintering freeze-dried powders obtained by a co-precipitation technique with 1600 °C annealing. Similar to pyrochlore-like compositions in the zirconate system, some of the new titanates are good oxide-ion conductors in air. The new solid-state electrolytes have oxide-ion conductivity in the interval of 1.0 × 10 3  2.5 × 10 S/cm at 740 °C in air. This value of conductivity is comparable with that of ZrO2/Y2O3 ceramics. The conductivity of Lu2+xTi2−xO7−x/2 depends on the chemical composition. The highest ionic conductivity is exhibited by nearly stoichiometric Lu2+xTi2−xO7−x/2 (x = 0.096; 35.5 mol% Lu2O3) material containing ∼ 4.8 at.% LuTi anti-site defects.  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