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1.
Here we report the synthesis, chemical stability, and electrical conductivity of Ti-doped perovskite-type BaCe0.8-x
Ti
x
Y0.2O3-δ
(x = 0.05, 0.1, 0.2, and 0.3; BCTY). Samples were synthesized by conventional solid state (ceramic) reaction from corresponding
metal salts and oxides at elevated temperature of 1,300–1,500 °C in air. The powder X-ray diffraction confirmed the formation
of a simple cubic perovskite-type structure with a lattice constant of a = 4.374(1), 4.377(1), and 4.332(1) ? for x = 0.05, 0.1, and 0.2 members of BCTY, respectively. Like BaCe0.8Y0.2O3-δ
(BCY), Ti substituted BCTY was found to be chemically not stable in 100% CO2 and form BaCO3 at elevated temperature. The bulk electrical conductivity of BCTY decreased with increasing Ti content and the x = 0.05 member exhibited the highest conductivity of 2.3 × 10−3 S cm−1 at 650 °C in air, while a slight increase in the conductivity, especially at low temperatures (below 600 °C), was observed
in humidified atmospheres. 相似文献
2.
We report the synthesis, structure, microstructure, chemical stability in H2O and CO2, and electrical transport properties of an oxide ion-conducting perovskite-related structure Ba3In2MO8 (M = Zr, Ce, Zr0.5Ce0.5). Powder X-ray diffraction confirmed the formation of a simple cubic perovskite-like structure for Ba3In2ZrO8 (a = 4.205(9) ?), Ba3In2CeO8 (a = 4.234(1) ?), and Ba3In2Zr0.5Ce0.5O8 (a = 4.285(8) ?). The increase in lattice constant is consistent with the Shannon’s ionic radius trend. Among the three samples
investigated, Ba3In2ZrO8 was found to be stable against reaction with pure CO2 at elevated temperature, while the Ce and 1:1 Zr and Ce compounds were unstable at 600 °C. Ba3In2ZrO8, Ba3In2CeO8, and Ba3In2Zr0.5Ce0.5O8 were found to be chemically unstable in H2O at about 50 °C. The bulk electrical conductivity of the samples prepared at different temperatures was found to be nearly
the same; the total conductivity (bulk + grain–boundary + electrode) seems to change with sintering temperature. Both Ba3In2ZrO8 and Ba3In2CeO8, prepared at 1,400 °C, exhibited comparable electrical conductivity of about 6 × 10−3 S cm−1 at 800 °C, which is comparable to that of conventional Y2O3-doped ZrO2 electrolyte. These compounds are very promising electroltes, provided that their chemical and mechnical stabitities are improved
without losing any ionic conductivity. 相似文献
3.
The stoichiometry range and lithium ion conductivity of Li5+x
Ba
x
La3−x
Ta2O12 (x = 0, 0.25, 0.50, 1.00, 1.25, 1.50, 1.75, 2.00) with garnet-like structure were studied. The powder X-ray diffraction data
of Li5+x
Ba
x
La3−x
Ta2O12 indicated that single phase oxides with garnet-like structure exist over the compositional range 0 ≤ x ≤ 1.25; while for x = 1.5, 1.75 and 2.00, the presence of second phase in addition to the major garnet like phase was observed. The cubic lattice
parameter increases with increasing x and reaches a maximum at x = 1.25 then decreases slightly with further increase in x in Li5+x
Ba
x
La3−x
Ta2O12. The impedance plots of Li5+x
Ba
x
La3−x
Ta2O12 samples obtained at 33 °C indicated a minimum grain-boundary resistance (R
gb) contribution to the total resistance (R
b + R
gb) at x = 1.0. The total (bulk + grain boundary) ionic conductivity increases with increasing lithium and barium content and reaches
a maximum at x = 1.25 and then decreases with further increase in x in Li5+x
Ba
x
La3−x
Ta2O12. Scanning electron microscope investigations revealed that Li6.25Ba1.25La1.75Ta2O12 is much more dense, and the grains are more regular in shape. Among the investigated compounds, Li6.25Ba1.25La1.75Ta2O12 exhibits the highest total (bulk + grain boundary) and bulk ionic conductivity of 5.0 × 10−5 and 7.4 × 10−5 S/cm at 33 °C, respectively. 相似文献
4.
Bi4V2O11 exists in three phases viz. α, β, and γ. High temperature γ-phase can be stabilized to room temperature owing to its higher
conductivity by the partial substitution of metallic cations for vanadium in Bi4V2O11. Phase transitions from α → β and β → γ are composition and temperature-dependent. Mn2+-doped compounds Bi4V2−x
Mn
x
O11−
δ
(0 ≤ x ≤ 0.4) have been synthesized by solid state reaction technique and investigated by X-ray diffraction and ionic conductivity
measurement. High ionic conducting γ-phase is stabilized for x ≥ 0.2. The ionic conductivity of the series of Bi4V2−x
Mn
x
O11−
δ
samples has been measured by using ac impedance spectroscopy technique. The conductivity data do show departure from its
simple Arrhenius behavior for all of the compositions. The highest conductivity observed for x = 0.2 sample can be attributed to lower activation energy. 相似文献
5.
The Ba(Ce0.8Zr0.2)0.95Yb0.05O2.975 ceramics electrolyte was prepared via a Pechini method using metal nitrate salts as starting materials. An optimum annealing
temperature of 1,400 °C was needed to obtain a pure perovskite-like phase with orthorhombic structure. Particle size distribution
showed a bimodal distribution that corresponds to the loose powders and agglomerates size. Scanning electron micrograph revealed
that the loose powders were in the nanosize range (70–200 nm). These ultrafine loose powders enhanced the densification of
a pellet with relative density ∼95% obtained at 1,400 °C. The sample formed clear and compact grains with submicron sizes.
Impedance results showed that the impedance semicircle of the grain was observed only at T ≤ 250 °C. The introduction of 20 mol% Zr improved the chemical stability of BaCe0.95Yb0.05O2.975 sample in atmosphere containing carbon dioxide at 600 °C. The sample also exhibited high proton conductivity in wet hydrogen. 相似文献
6.
《Current Applied Physics》2010,10(2):574-579
BaBi4Ti4−xZrxO15 with x = 0.1, 0.2, 0.3 and 0.5, has been synthesized via modified solid state reaction route. X-ray diffraction studies confirmed the formation of single phase Zr4+ substituted BaBi4Ti4O15 up to x = 0.2. ZrO2 and Bi2O3 based impurity phases were found at x = 0.3 and 0.5 substitutions. However, Rietveld refinement showed the increase in lattice parameters of BaBi4Ti4O15 up to x = 0.5 substitutions. A broad dielectric peak associated with frequency dependence dielectric maximum temperature was observed at low substitutions. Relaxor behavior was suppressed at x = 0.5 substitution. A broadening and shifting of permittivity-temperature peak was found for the substitution. The high temperature slopes of dielectric peaks were analyzed by quadratic law for relaxors. The degree of relaxation and phase transformation diffusiveness were investigated at different substitutions. 相似文献
7.
Multiple ion-doped lithium manganese oxides LiCrxNixMn2-2xO4-zFz (0 < x ≤ 0.25, z = 0.05, 0.1) with a spinel structure and space group Fd m were prepared by using the co-precipitation procedure carried out in water–alcohol solvent using adipic acid as the chelating
agent. The electrochemical measurements indicated that the charge/discharge capacities of the samples prepared at 600 °C are
higher than that of the treatment at 800 °C or microwave heating. The capacitance-voltage (CV) curves of LiCrxNixMn2-2xO4-zFz (0 < x ≤ 0.25, z = 0.05, 0.1) showed that when x ≤ 0.1, the samples had two reduction–oxidation peaks at 4.0 to 4.2-V region, whereas when x > 0.1, the samples had only one reduction–oxidation peak at 4.0- to 4.2-V region in CV measurements and could offer more
stable voltage plateau in a 4-V region and also had stable electrical conductivity after 20 cycles. Another reduction–oxidation
peak appeared in 4.6-4.8-V region (Ni2+–Ni4+ reduction–oxidation peaks); this suggests that the LiCrxNixMn2-2xO4-zFz (0.1 < x≤ 0.25, z = 0.05, 0.1) cathode material could offer 4.6 to 4.8-V charge/discharge plateaus, and its specific capacity increases with
increasing Ni2+. The impedance measurements of the cell proved that the F− anion doped can not only prevent Mn3+ from disproportion but also can prevent the passivation film from forming and can help keep stable the cell’s electrical
properties. The LiCr0.05Ni0.05Mn1.9O3.9F0.1 sintered at 600 °C shows the best cycle performance and the largest capacity in all prepared samples; its first discharge
capacity is 120 mAh/g, and the discharge capacity loses only 1.78% after 20 cycles. After 100 cycles, it still remains in
the spinel structure. 相似文献
8.
Paramjyot Kumar Jha Jasmeet Kaur Gill Gourav Singla K. Singh O. P. Pandey 《Ionics》2012,18(8):759-767
Composition (100?x) ZrO2 (x) Bi2O3 (x?=?15, 20, 25) is synthesized by solid-state reaction method to study the effect of Bi2O3 doping on ZrO2. The as-prepared samples are characterized by various methods. The X-ray diffraction pattern of all these samples exhibits three phases, namely, m-ZrO2, ??III-Bi2O3, and ??-Bi2O3. The differential thermal analysis curves do not show any phase transition/decomposition, which clearly indicated the stabilization of ??-Bi2O3 phase. The conductivity changes in all the samples are discussed in terms of different phase formations and their volume fractions. The microstructural and energy dispersive analyses indicate the presence of different phases. A maximum conductivity at high temperature (800?°C) was observed for the x?=?25 composition, i.e., ???=?4.21?×?10?2 S/cm. 相似文献
9.
Ma?gorzata A. Ma?ecka Ulrich Burkhardt Dariusz Kaczorowski Marcus P. Schmidt Daniel Goran Leszek K?piński 《Journal of nanoparticle research》2009,11(8):2113-2124
The structure and phase evolution of nanocrystalline Ce1−
x
Ln
x
O2−
x/2−δ (Ln = Yb, Lu, x = 0 − 1) oxides upon heating in H2 was studied for the first time. Up to 950 °C the samples were single-phase, with structure changing smoothly with x from fluorite type (F) to bixbyite type (C). For the Lu-doped samples heated at 1100 °C in the air and H2, phase separation into coexisting F- and C-type structures was observed for ~0.40 < x < ~0.70 and ~0.25 < x < ~0.70, respectively. It was found also that addition of Lu3+ and Yb3+ strongly hinders the crystallite growth of ceria during heat treatment at 800 and 950 °C in both atmospheres. Valency of
Ce and Yb in Ce0.1Lu0.9O1.55−δ and Ce0.95Yb0.05O1.975−δ samples heated at 1100 °C was studied by XANES and magnetic measurements. In the former Ce was dominated by Ce4+, with small contribution of Ce3+ after heating in H2. In the latter, Yb existed exclusively as 3+ in both O2 and H2. 相似文献
10.
Zhang Qingfeng Jiang Shenglin Zeng Yike Fan Maoyan Wang Qingping Zhang Guangzu Zhang Yangyang Yu Yan Wang Jing 《Applied Physics A: Materials Science & Processing》2011,103(4):1159-1163
(Pb0.87La0.02Ba0.1)(Zr0.7Sn0.3−x
Ti
x
)O3 (PLBZST, 0.06≤x≤0.09) antiferroelectric ceramics were fabricated by conventional solid state reaction process, and their ferroelectric, dielectric,
and pyroelectric properties were systemically investigated. PLBZST with different Ti content were all confirmed to be in an
antiferroelectric phase at T=50°C, which is close to the lowest phase transition temperature. Compared with conventional FE ceramics, PLBZST antiferroelectric
ceramics exhibited higher electric field induced pyroelectric coefficient (p). As the content of Ti increased from 0.06 to 0.09, the pyroelectric coefficient increased from 1000 to 6500 μC/m2K under a 500 V/mm DC bias field. The maximum pyroelectric coefficient of 8400 μC/m2K was obtained at x=0.09 when an 850 V/mm DC bias field was applied, which is far larger than that of conventional phase transition pyroelectric
materials. Large pyroelectric response is beneficial for the development of infrared detectors and thermal imaging sensors. 相似文献
11.
M. P. Volkov B. T. Melekh V. I. Bakharev N. F. Kartenko N. V. Matykin Yu. N. Filin 《Physics of the Solid State》1999,41(1):15-17
A study has been made of the glass-forming ability, structure, and superconducting properties of Bi2.2Sr1.8Ca1.05Cu2.15LixOy and Bi2.2Sr1.8Ca1.05Cu2.15−x
LixOy (x=0;0.3;0.5;0.7). The compounds were melted by rf at T=1300–1500 °C. Rapid quenching produces glassy alloys whose glass-forming ability is the highest when lithium is substituted
for copper. Glass annealing at 700–800 °C results in the formation of the HTSC phase 2212 with a critical temperature of up
to 91 K. In lithium-doped samples the HTSC phase forms at lower temperatures and shorter anneals and it depends on the cooling
rate following the anneal. The composition and properties of the 2212 phase depend nonmonotonically on the anneal time. The
lattice parameter C of the 2212 phase increases with increasing lithium content.
Fiz. Tverd. Tela (St. Petersburg) 41, 18–21 (January 1999) 相似文献
12.
I. Ruiz de Larramendi R. López-Antón J. I. Ruiz de Larramendi T. Rojo 《Applied Physics A: Materials Science & Processing》2008,93(3):655-661
Polycrystalline samples of Pr1−x
Sr
x
Fe0.8Co0.2 O3−δ
(x=0.1, 0.2, 0.3) (PSFC) were prepared by the combustion synthesis route at 1200°C. The structure of the polycrystalline powders
was analysed with X-ray powder diffraction data. The X-ray diffraction (XRD) patterns were indexed as the orthoferrite similar
to that of PrFeO3 having a single-phase orthorhombic perovskite structure (Pbnm). Pr1−x
Sr
x
Fe0.8Co0.2O3−δ
(x=0.1, 0.2, 0.3) films have been deposited on yttria-stabilized zirconia (YSZ) single-crystal substrates at 700°C by pulsed
laser deposition (PLD) for application to thin film solid oxide fuel cell cathodes. The structure of the films was analysed
by XRD, scanning electron microscopy (SEM) and atomic force microscopy (AFM). All films are polycrystalline with a marked
texture and present pyramidal grains in the surface with different size distributions. Electrochemical impedance spectroscopy
(EIS) measurements of PSFC/YSZ single crystal/PSFC test cells were conducted. The Pr0.7Sr0.3Fe0.8Co0.2O3−δ
film at 850°C presents a lower area specific resistance (ASR) value, 1.65 Ω cm2, followed by the Pr0.8Sr0.2Fe0.8Co0.2O3−δ
(2.29 Ω cm2 at 850°C) and the Pr0.9Sr0.1Fe0.8Co0.2O3−δ
films (5.45 Ω cm2 at 850°C). 相似文献
13.
Cubic-stabilized ((DyO1.5)
x
–(WO3)
y
–(BiO1.5)1 − x − y
) electrolytes (DWSB) with much higher conductivity than (ErO1.5)0.2(BiO1.5)0.8, 20ESB, were developed through a double-doping strategy. (DyO1.5)0.08–(WO3)0.04–(BiO1.5)0.88, 8D4WSB, is the highest conductivity composition but underwent the greatest conductivity degradation at 500 °C due to its
low total dopant concentration. The effect of dopant composition on conductivity behavior with time at 500 °C demonstrates
that there is a trade-off between initial conductivity and long-term stability at this temperature. Therefore, it is necessary
to find an optimal total and relative concentration of dopants to provide the enhanced long-term stability needed to make
this DWSB electrolyte system feasible for 500 °C operation. To this end, it was found that (DyO1.5)0.25–(WO3)0.05–(BiO1.5)0.70, 25D5WSB, maintained a conductivity of 0.0068 S/cm without appreciable degradation after annealing at 500 °C for 500 h. Moreover,
since bismuth oxide-based electrolytes do not exhibit any grain boundary impedance, the total conductivity of 25D5WSB is significantly
higher than that of alternate electrolytes (e.g., GDC: Gd0.1Ce0.9O1.95) at this temperature. 相似文献
14.
Lead-free (Bi0.98−x
La0.02Na1−x
)0.5Ba
x
TiO3 ceramics have been prepared by an ordinary sintering technique and their structure, ferroelectric and piezoelectric properties
have been studied. The results of X-ray diffraction show that La2+ and Ba2+ diffuse into the Bi0.5Na0.5TiO3 lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) exists at
0.04<x<0.10. Compared with pure Bi0.5Na0.5TiO3 ceramics, the (Bi0.98−x
La0.02Na1−x
)0.5Ba
x
TiO3 ceramics possess much smaller coercive field E
c and larger remanent polarization P
r. Because of the low E
c (3.38 kV/mm), large P
r (46.2 μC/cm2) and the formation of the MPB of rhombohedral and tetragonal phases, the piezoelectric properties of the ceramics are significantly
enhanced at x=0.06: d
33=181 pC/N and k
p=36.3%. The depolarization temperature T
d reaches a minimum value near the MPB. The ceramics exhibit relaxor characteristic, which is probably a result from the cation
disordering in the 12-fold coordination sites. The temperature dependences of the ferroelectric and dielectric properties
suggest that the ceramics may contain both polar and non-polar regions at the temperatures above T
d. 相似文献
15.
The crystallization and glass transition kinetics using differential scanning calorimetry (DSC) in 50AgI–33.33Ag2O–16.67[(V2O5)1−x
–(MoO3)
x
] superionic glassy system is discussed. Thermal stability of glass, studied using various criteria, does not vary significantly
with glass former variation. However, the activation energies for structural relaxation (E
s) at glass transition temperature and crystallization (E
c) obtained using Moynihan and Kissinger, Matusita-Sakka formulations found to exhibit interesting trends with MoO3 substitution in the glass matrix. It is noticed that the electrical conductivity (σ)–temperature (T) cycles obtained at a typical heating rate of 1 °C/min do exhibit significant thermal events. The conductivity after first
heating cycle at room temperature is found to be increasing with MoO3 content and maximum for x = 0.3 (~10−3 Ω−1 cm−1 at 30 °C) which is comparable to that of the host 50AgI–33.33Ag2O–16.67V2O5 glassy system. The parameters obtained from σ–T plots and DSC scans do complement each other in a particular range of composition. 相似文献
16.
M. Barré F. Le Berre M-P. Crosnier-Lopez C. Galven O. Bohnké J-L. Fourquet 《Ionics》2009,15(6):681-687
The Li1−x
La
x
/3Zr2(PO4)3 NASICON-type compounds (0 ≤ x ≤ 1) have been synthesized in powder form by a sol-gel method and sintered for ionic conductivity measurements. In order
to improve the compactness of the ceramic without decomposition of the compound, several sintering processes have been tested
for one member of the solid solution (x = 0.6): the use of sintering aids (ZnO, B2O3, TiO2 and LiNO3), a ball-milling of the synthesized powder, a flash heating, high isostatic pressure, and spark plasma sintering. Finally,
a satisfactory compactness of 85% is obtained compared to the referenced value (63%) obtained by uniaxial and isostatic pressing.
The ionic conductivity study was performed by impedance spectroscopy. It shows that, despite the formation of vacancies, the
substitution Li+→ 1/3 La3+ + 2/3 □ has unfortunately no influence on the conduction for 0 ≤ x ≤ 0.7 since the ionic conductivity remains identical to the LiZr2(PO4)3 one. For higher x values, the ionic conductivity strongly decreases. 相似文献
17.
Xiangqian Shen Mingquan Liu Fuzhan Song Yongwei Zhu 《Applied Physics A: Materials Science & Processing》2011,104(1):109-116
Sr1−x
La
x
Zn
x
Fe12−x
O19/poly(vinylpyrrolidone) (PVP) (0.0≤x≤0.5) precursor nanofibers were prepared by the sol–gel assisted electrospinning method from starting reagents of metal salts
and PVP. Subsequently, the Sr1−x
La
x
Zn
x
Fe12−x
O19 nanofibers with diameters of around 100 nm were obtained by calcination of the precursor at 800 to 1000°C for 2 h. The precursor
and resultant Sr1−x
La
x
Zn
x
Fe12−x
O19 nanofibers were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer and
vibrating sample magnetometer. The grain sizes of Sr0.8La0.2Zn0.2Fe11.8O19 nanofibers are in a nanoscale from 40 to 48 nm corresponding to the calcination temperature from 800 to 1000°C. With La–Zn
substitution content increase from 0 to 0.5, the grain size and lattice constants for the Sr1−x
La
x
Zn
x
Fe12−x
O19 nanofibers obtained at 900°C show a steady reduction trend. With variations of the ferrite particle size arising from the
La–Zn substitution, the nanofiber morphology changes from the necklace-like structure linking by single elongated plate-like
particles to the structure building of multi-particles on the nanofiber cross-section. The specific saturation magnetization
of Sr1−x
La
x
Zn
x
Fe12−x
O19 nanofibers initially increases with the La–Zn content, reaching a maximum value 72 A m2 kg−1 at x=0.2, and then decreases with a further La–Zn content increase up to x=0.5, while the coercivity exhibits a continuous reduction from 413 (x=0) to 219 kA m−1 (x=0.5). The mechanism for the La–Zn substitution and the nanofiber magnetic property are analyzed. 相似文献
18.
BaCe0.7Ta0.1Y0.2O3−
δ
(BCTY) and BaCe0.8Y0.2O3−
δ
(BCY) were synthesized by solid-state reaction method at 1,300 °C for 20 h. After being exposed in 3% CO2 + 3% H2O + 94% N2 at 700 °C for 20 h, the BCTY exhibited adequate chemical stability against carbonations while BCY decomposed into BaCO3 and CeO2. The BCTY showed the similar thermal expansion behavior to BCY from room temperature to 1,000 °C in air. The BCTY displayed
a conductivity of 0.007 S/cm at 700 °C in humid hydrogen, lower than that of BCY (0.009 S/cm). A fuel cell with 10-μm thick
BCTY membrane prepared through an all-solid-state process exhibited 1.004 V for OCV, 330 mW/cm2 for maximum output at 700 °C, respectively. Short-term test shows that the fuel cell performance does not degrade after 20 h. 相似文献
19.
Doubly substitution of vanadium by Cu and Co in the limit of 10% in Bi4V2O11, has led to the formation of the Bi4V1.8Cu0.2−xCoxO10.7 solid solution. X-ray diffraction shows that all the compositions present a tetragonal symmetry. The thermal analysis has
revealed that the polymorph γ' phase, which is formed by a partial ordering of oxygen ions in the γ high temperature form,
is stabilized at room temperature. The influence of sintering temperature on the microstructure of the samples was investigated
by the scanning electron microscopy (SEM). The ceramics sintered at 820 °C for more than 3 hours present micro-craks. The
evolution of the electrical conductivity with temperature and the degree of substitution has been investigated by impedance
spectroscopy. The sample with x=0.1 presents the highest value of the conductivity ≈4.6×10−2 S·cm−1 at 600 °C. 相似文献
20.
Ce(1−x)Gd/Sm
x
O2−δ
(x = 0.05–0.2, GDC/SDC) nanometric powder was prepared by glycine-nitrates combustion synthesis, by strictly following uniformity in the preparation route. The thermochemical properties of the obtained precursor were studied by TGA/DTA. Crystallization of the fluorite phase occurred on heating at 800 °C or higher temperature. The grain size of calcined powder was found to be about 15 nm. Densification was studied as a function of dopant content. SDC was found more sinterable than GDC. Crystal structure and microstructure were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). Electrical characterization was carried out using the impedance spectroscopy method in the frequency range of 50 Hz–13 MHz. The bulk conductivity of SDC is higher than GDC pellet for all concentration ranges. The results were analyzed by using the concept of change of the chemical bond ionicity due to the replacement of the host by dopant. Guest/host ionic size, valence mismatch ratio and their consequences are counted semiquantitatively into the configurational and thermal entropy. 相似文献