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1.
SmYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics were pressureless-sintered at 1973 K for 10 h in air. The relative density, structure and electrical conductivity of SmYb1−xGdxZr2O7 ceramics were investigated by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance spectroscopy measurements. SmYb1−xGdxZr2O7 (0 ≤ x ≤ 0.5) ceramics exhibit a defect fluorite-type structure, while SmYb1−xGdxZr2O7 (0.7 ≤ x ≤ 1.0) ceramics have a pyrochlore-type structure. The measured values of the electrical conductivities obey the Arrhenius relation. The grain conductivity of each composition in SmYb1−xGdxZr2O7 ceramics increases with increasing temperature from 723 to 1173 K. The grain conductivity of SmYb1−xGdxZr2O7 ceramics gradually increases with increasing gadolinium content at identical temperature levels. An increase of about one order of magnitude in grain conductivity is found at all temperature levels when the gadolinium content increases from 0.5 to 0.7. SmYb1−xGdxZr2O7 ceramics are oxide-ion conductors in the oxygen partial pressure range of 1.0 × 10−4 to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 2.69 × 10−2 S cm−1 at 1173 K for SmGdZr2O7 ceramic.  相似文献   

2.
(Sm1−xCax)2Zr2O7−x (0 ≤ x ≤ 0.100) ceramics were prepared by a solid state reaction process at 1973 K for 10 h in air, and were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). (Sm1−xCax)2Zr2O7−x (0 ≤ x ≤ 0.025) ceramics have a single phase of pyrochlore-type structure; however (Sm1−xCax)2Zr2O7−x (0.050 ≤ x ≤ 0.100) consist of pyrochlore phase and a small amount of perovskite-like CaZrO3. The electrical conductivity of (Sm1−xCax)2Zr2O7−x ceramics was investigated by complex impedance spectroscopy over a frequency range of 0.1 Hz to 20 MHz in the temperature range of 573–873 K. The measured electrical conductivity obeys the Arrhenius relation. Both the activation energy and pre-exponential factor for grain conductivity increase with increasing the CaO content; however, electrical conductivity of (Sm1−xCax)2Zr2O7−x decreases with increasing the CaO content, which is due to the increase in structural disordering at 0 ≤ x ≤ 0.025 and the presence of the poorly conducting CaZrO3 phase at 0.050 ≤ x ≤ 0.100, respectively.  相似文献   

3.
(Nd1−xYbx)2Zr2O7 (0 ≤ x ≤ 1) ceramics were prepared by pressureless-sintering to obtain dense bulk materials. The electrical conductivity of (Nd1−xYbx)2Zr2O7 was investigated by complex impedance spectroscopy over a frequency range of 20 Hz to 2 MHz from 723 to 1173 K in air. A high-temperature dilatometer was used to analyze thermal expansion coefficient of (Nd1−xYbx)2Zr2O7 in the temperature range of 373-1523 K. The measured electrical conductivity obeys the Arrhenius relation. The grain conductivity of each composition in (Nd1−xYbx)2Zr2O7 gradually increases with increasing temperature. A decrease of about one order of magnitude in grain conductivity is found at all temperature levels when the Yb content increases from x = 0.3 to x = 0.5. The highest electrical conductivity value obtained in this work is 9.32 × 10−3 S cm−1 at 1173 K for (Nd0.7Yb0.3)2Zr2O7 ceramic. (Nd1−xYbx)2Zr2O7 ceramics are oxide-ion conductors in the oxygen partial pressure range from 1.0 × 10−4 to 1.0 atm at all test temperature levels. Thermal expansion coefficients of (Nd1−xYbx)2Zr2O7 gradually decrease with increasing ytterbium content at identical temperature levels.  相似文献   

4.
We evaluate in this work the effect of Gd substitution on the dc activation energy, Edc, and ionic conductivity of the pyrochlore-type gadolinium zirconate, P-Gd2Zr2O7. Several compositions with the general formulae Gd2−yLnyZr2O7 (Ln = Er3+, Y3+, Dy3+, Sm3+, Nd3+ and La3+) were prepared by mechanically milling and firing stoichiometric mixtures of the corresponding elemental oxides and their electrical properties analyzed as a function of frequency and temperature by using impedance spectroscopy. Whereas Gd substitution in P-Gd2Zr2O7 by smaller lanthanides induces a pyrochlore to fluorite phase transition, using larger dopant cations yields partially disordered pyrochlores. Despite of higher structural disorder, ionic conductivity values measured for the fluorite-type materials are lower than those observed for pyrochlores whereas activation energies for oxygen migration in the series decrease monotonically as the average size of the A cation increases.  相似文献   

5.
(Sm1−xDyx)2Zr2O7 (0 ≤ x ≤ 1) ceramics are prepared by a solid state reaction process at 1973 K for 10 h in air. (Sm1−xDyx)2Zr2O7 (0 ≤ x ≤ 0.3) ceramics exhibit a single phase of pyrochlore-type structure, while (Sm1−xDyx)2Zr2O7 (0.5 ≤ x ≤ 1.0) possess a defective fluorite-type structure. The full width at half-maxima in the Raman spectra increases with increasing Dy content, which indicates that the degree of structural disorder increases as the Dy content increases. The ionic conductivity of (Sm1−xDyx)2Zr2O7 ceramics is investigated by impedance spectroscopy over a frequency range of 0.2 Hz to 8 MHz in the temperature range of 873-1173 K in air and hydrogen atmospheres, respectively. The ionic conductivity has a maximum near the phase boundary between the pyrochlore- and the defective fluorite-type phases under identical temperature levels. The ionic conductivity is determined by the degree of structural disorder or unit cell free volume, which is depending on the Dy content. As the ionic conductivity in the hydrogen atmosphere is almost the same as that obtained in air, the conduction of (Sm1−xDyx)2Zr2O7 is purely ionic with negligible electronic conduction.  相似文献   

6.
Sr2Fe1−xCoxNbO6 (0.1 ≤ x ≤ 0.9) (SFCN) oxides with perovskite structure have been developed as the cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). These materials are synthesized via solid-state reaction and characterized by XRD, SEM, electrical conductivity, AC impedance spectroscopy and DC polarization measurements. The reactivity tests show that the Sr2Fe1−xCoxNbO6 electrodes are chemically compatible with the Zr0.85Y0.15O1.925 (YSZ) and Ce1.9Gd0.1O1.95 (CGO) electrolytes at 1200 °C, and the electrode forms a good contact with the electrolyte after sintering at 1200 °C for 12 h. The total electrical conductivity that has a considerable effect on the electrode properties is determined in a temperature range from 200 °C to 800 °C. The highest conductivity of 5.7 S cm−1 is found for Sr2Fe0.1Co0.9NbO6 at 800 °C in air. The electrochemical performances of these cathode materials are studied using impedance spectroscopy at various temperatures and oxygen partial pressures. Two different kinds of reaction rate-limiting steps exist on the Sr2Fe0.1Co0.9NbO6 electrode, depending on the temperature. The Sr2Fe0.1Co0.9NbO6 electrode on CGO electrolyte exhibits a polarization resistance of 0.74 Ω cm2 at 750 °C in air, which indicates that the Sr2Fe0.1Co0.9NbO6 electrode is a promising cathode material for IT-SOFCs.  相似文献   

7.
We report the effect of Y substitution for Nb on Li ion conductivity in the well-known garnet-type Li5La3Nb2O12. Garnet-type Li5La3Nb2−xYxO12−δ (0 ≤ x ≤ 1) was prepared by ceramic method using the high purity metal oxides and salts. Powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), 7Li nuclear magnetic resonance (Li NMR) and AC impedance spectroscopy were employed for characterization. PXRD showed formation of single-phase cubic garnet-like structure for x up to 0.25 and above x = 0.25 showed impurity in addition to the garnet-type phases. The cubic lattice constant increases with increasing Y content up to x = 0.25 in Li5La3Nb2xYxO12−δ and is consistent with expected ionic radius trend. 7Li MAS NMR showed single peak, which could be attributed to fast migration of ions between various sites in the garnet structure, close to chemical shift 0 ppm with respect to solid LiCl and which confirmed that Li ions are distributed at an average octahedral coordination in Li5La3Nb2xYxO12δ. Y-doped compounds showed comparable electrical conductivity to that of the parent compound Li5La3Nb2O12. The x = 0.1 member of Li5La3Nb2xYxO12δ showed total (bulk + grain-boundary) ionic conductivity of 1.44 × 10−5 Scm−1 at 23 °C in air.  相似文献   

8.
SmBaCo2O5+x (SBCO), an oxide with double-perovskite structure, has been developed as a novel cathode material for intermediate-temperature solid-oxide fuel cells (IT-SOFCs). The electrical conductivity of an SBCO sample reaches 815–434 S cm−1 in the temperature range 500–800 °C. XRD results show that an SBCO cathode is chemically compatible with the intermediate-temperature electrolyte materials Sm0.2Ce0.8O1.9 (SDC) and La0.9Sr0.1Ga0.8Mg0.2O3−δ (LSGM). The polarization resistances of an SBCO cathode on SDC and LSGM electrolytes are 0.098 and 0.054 Ω cm2 at 750 °C, respectively. The maximum power densities of a single cell with an SBCO cathode on SDC and LSGM electrolytes reach 641 and 777 mW cm−2 at 800 °C, respectively. The results of this study demonstrate that the double-perovskite structure oxide SBCO is a very promising cathode material for use in IT-SOFCs.  相似文献   

9.
A new type of Li1−xFe0.8Ni0.2O2–LixMnO2 (Mn/(Fe + Ni + Mn) = 0.8) material was synthesized at 350 °C in air atmosphere using a solid-state reaction. The material had an XRD pattern that closely resembled that of the original Li1−xFeO2–LixMnO2 (Mn/(Fe + Mn) = 0.8) with much reduced impurity peaks. The Li/Li1−xFe0.8Ni0.2O2–LixMnO2 cell showed a high initial discharge capacity above 192 mAh g−1, which was higher than that of the parent Li/Li1−xFeO2–LixMnO2 (186 mAh g−1). We expected that the increase of initial discharge capacity and the change of shape of discharge curve for the Li/Li1−xFe0.8Ni0.2O2–LixMnO2 cell is the result from the redox reaction from Ni2+ to Ni3+ during charge/discharge process. This cell exhibited not only a typical voltage plateau in the 2.8 V region, but also an excellent cycle retention rate (96%) up to 45 cycles.  相似文献   

10.
LiNi0.6CoxMn0.4−xO2 (x = 0.05, 0.10, 0.15, 0.2) cathode materials are prepared, and their structural and electrochemical properties are investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetric (DSC) and charge–discharge test. The results show that well-ordering layered LiNi0.6CoxMn0.4−xO2 (x = 0.05, 0.10, 0.15, 0.2) cathode materials are successfully prepared in air at 850 °C. The increase of the Co content in LiNi0.6Mn0.4−xCoxO2 leads to the acceleration of the grain growth, the increase of the initial discharge capacity and the deterioration of the cycling performance of LiNi0.6Mn0.4−xCoxO2. It also leads to the enhancement of the ratio Ni3+/Ni2+ in LiNi0.6CoxMn0.4−xO2, which is approved by the XPS analysis, resulting in the increase of the phase transition during cycling. This is speculated to be main reason for the deteriotion of the cycling performance. All synthesized LiNi0.6CoxMn0.4−xO2 samples charged at 4.3 V show exothermic peaks with an onset temperature of larger than 255 °C, and give out less than 400 J g−1 of total heat flow associated with the peaks in DSC analysis profile, exhibiting better thermal stability. LiNi0.6Co0.05Mn0.35O2 with low Co content and good thermal stability presents a capacity of 156.6 mAh g−1 and 98.5% of initial capacity retention after 50 cycles, showing to be a promising cathode materials for Li-ion batteries.  相似文献   

11.
Li7La3Zr2O12 electrolytes doped with different amounts of Al (0, 0.2, 0.7, 1.2, and 2.5 wt.%) were prepared by a polymerized complex (Pechini) method. The influence of aluminum on the structure and conductivity of Li7La3Zr2O12 were investigated by X-ray diffraction (XRD), impedance spectroscopy, scanning electron microscopy (SEM), and thermal dilatometry. It was found that even a small amount of Al (e.g. 0.2 wt.%) added to Li7La3Zr2O12 can greatly accelerate densification during the sintering process. SEM micrographs showed the existence of a liquid phase introduced by Al additions which led to the enhanced sintering rate. The addition of Al also stabilized the higher conductivity cubic form of Li7La3Zr2O12 rather than the less conductive tetragonal form. The combination of these two beneficial effects of Al enabled greatly reduced sintering times for preparation of highly conductive Li7La3Zr2O12 electrolyte. With optimal additions of Al (e.g. 1.2 wt.%), Li7La3Zr2O12 electrolyte sintered at 1200 °C for only 6 h showed an ionic conductivity of 2.0 × 10−4 S cm−1 at room temperature.  相似文献   

12.
Nano-crystalline fluorite-like structure CeO2 and Ca-doped CeO2 compounds were prepared in the temperature range of 220–400 °C using a precursor method which involves coprecipitation of Ca2+ and Ce4+ ions using oxalic acid from the aqueous calcium chloride and ammonium cerium nitrate solutions. The precipitated products were characterized by employing thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD), infrared spectroscopy (IR), laser particle size analysis (LPSA) methods and scanning electron microscopy (SEM). TGA studies show two step weight loss in the temperature range: (i) room temperature to 200 °C and (ii) 200–400 °C for all the investigated precursors. The former loss is attributed to loss of water while the latter is due to decomposition of oxalates. The XRD study reveal a complex pattern for the as-precipitated powders, and surprisingly we see the formation of single-phase fluorite-like structure at about 220 °C for Ce1−xCaxO2−x (0 < x < 0.20). However, XRD peaks were found to be very broad that sharpen with increasing temperature. The cubic fluorite-type lattice constant increases with increasing Ca-content, which is consistent with literature, and also follows the expected trend based on the ionic radii consideration. For purpose of comparison, Ce1−xCaxO2−x (0 < x < 0.25) samples were also prepared by solid-state reaction using CeO2 and CaCO3, and lattice parameter is consistent with precipitation method samples within the experimental error. This result suggesting that doping of Ca is successful by coprecipitation. The particle size of parent and Ca-doped CeO2 samples prepared by precipitated method was found to be in the range 10–85 nm (from PXRD) in the temperature range 400–1000 °C, while about order of higher size was observed for the ceramic method synthesized samples. The presently employed wet chemical method could be used to prepare ceria and doped materials with nano-sized particles for a large scale production at mild temperature.  相似文献   

13.
Brownmillerite oxide Ca2Fe2−xCoxO5 (x = 0.2, 0.4, 0.6) was characterized by XRD, SEM and electrochemical impedance spectrum (EIS), respectively. Ca2Fe2−xCoxO5 has no reaction with Sm0.2Ce0.8O1.9 (SDC) electrolyte at 1100 °C for 10 h in air. The thermal expansion coefficient (TEC) of Ca2Fe2−xCoxO5 increased with increasing Co content, and the TEC value was compatible with SDC. The electrode properties of Ca2Fe2−xCoxO5 were studied under various temperatures and oxygen partial pressures. The polarization resistance (Rp) of Ca2Fe2−xCoxO5 with x = 0.2, 0.4 and 0.6 are 0.23, 0.48 and 1.05 Ω cm2 at 700 °C in air, respectively. The rate-limiting step for oxygen reduction reaction was the charge transfer process. Ca2Fe1.8Co0.2O5 cathode exhibits the lowest overpotential of about 50 mV at a current density of 70 mA cm−2 at 700 °C in air.  相似文献   

14.
Sr2−xLaxMnO4+δ (x = 0.4, 0.5, 0.6) oxides were studied as the cathode material for solid oxide fuel cells (SOFC). The reactivity tests indicated that no reaction occurred between Sr2−xLaxMnO4+δ and CGO at annealing temperature of 1000 °C, and the electrode formed good contact with the electrolyte after being sintered at 1000 °C for 4 h. The total electrical conductivity, which has strong effect on the electrode properties, was determined in a temperature range from 100 to 800 °C. The maximum value of 5.7 S cm−1 was found for the x = 0.6 phase at 800 °C in air. The cathode polarization and AC impedance results showed that Sr1.4La0.6MnO4+δ exhibited the lowest cathode overpotential. The area specific resistance (ASR) was 0.39 Ω cm2 at 800 °C in air. The charge transfer process is the rate-limiting step for oxygen reduction reaction on Sr1.4La0.6MnO4+δ electrode.  相似文献   

15.
Bulk conduction and relaxation of the [(ZrO2)1−x(CeO2)x]0.92(Y2O3)0.08 (0 ≤ x ≤ 1) solid solutions were studied using impedance spectroscopy at intermediate temperatures (200-500 °C). The bulk conductivity as a function of x shows a “V-shape” variation which is a competitive effect of the defect associates and the lattice parameter. In the ZrO2-rich region (x < 0.5) CeO2 doping increases the concentration of defect associates which limits the mobility of the oxygen vacancies; in the CeO2-rich region (x > 0.5) the increase of x increases the lattice parameter which enlarges the free channel for oxygen vacancy migration. Further analysis indicates the ionic radius of the tetravalent dopant determines the composition dependence of the ionic conductivity of the solid solutions. When doping YSZ with other tetravalent dopant with similar ionic radius with Zr4+, e.g., Hf4+, such “V-shape” composition dependence of the bulk conductivity cannot be observed.  相似文献   

16.
Sm1.8Ce0.2CuO4-xCe0.9Gd0.1O1.95 (SCC-xCGO, x = 0-12 vol.%) composite cathodes supported on Ce0.9Gd0.1O1.95 (CGO) electrolyte are studied for applications in IT-SOFCs. Results show that Sm1.8Ce0.2CuO4 material is chemically compatible with Ce0.9Gd0.1O1.95 at 1000 °C. The composite electrode exhibits optimum microstructure and forms good contact with the electrolyte after sintering at 1000 °C for 4 h. The polarization resistance (Rp) reduces to the minimum value of 0.17 Ω cm2 at 750 °C in air for SCC-CGO06 composite cathode. The relationship between Rp and oxygen partial pressure indicates that the reaction rate-limiting step is the surface diffusion of the dissociative adsorbed oxygen on the composite cathode.  相似文献   

17.
Pr2−xSrxNiO4 (PSNO, x = 0.3, 0.5 and 0.8) cathode materials for intermediate-temperature solid oxide fuel cell (IT-SOFC) were synthesized by a glycine-nitrate process using Pr6O11, Ni(NO3)2·6H2O and SrCO3 powders as raw materials. Phase structure of the synthesized powders was characterized by X-ray diffraction analysis (XRD). Microstructure of the sintered PSNO samples was observed and thermal expansion coefficient (TEC) and electrical conductivity were investigated. Electrochemical impedance spectroscopy (EIS) measurement of the PSNO materials on Sm0.2Ce0.8O1.9 (SCO) electrolyte was carried out, and single cells based on the PSNO cathodes were also assembled and their performances were tested. The results show that the synthesized PSNO powders have pure K2NiF4-type structure and the PSNO materials are chemically stable with Sm0.2Ce0.8O1.9 (SCO) electrolyte. The sintered PSNO samples have porous and fine microstructure with pore size smaller than 1 μm. Average thermal expansion coefficient of the PSNO materials is about 12–13 × 10−6 K−1 at 200–800 °C and the electrical conductivity is in the range of 70–120 Scm−1 at 800 °C. Area specific resistance (ASR) of the Pr2−xSrxNiO4 materials on SCO electrolyte is 0.407 Ωcm2, 0.126 Ωcm2 and 0.112 Ωcm2 for x = 0.3, 0.5 and 0.8 at 800 °C, respectively. Maximum open circuit voltage (OCV) and power density of the single NiO-SCO/SCO/PSNO cells are 0.75 V and 298 mWcm−2 at 700 °C, respectively, which indicates that Pr2−xSrxNiO4 may be a potential cathode material for IT-SOFC.  相似文献   

18.
Prospective positive-electrode (cathode) materials for a lithium secondary battery, viz., Li[Li0.2Ni0.2−x/2Mn0.6−x/2Crx]O2 (x = 0, 0.02, 0.04, 0.06, 0.08), were synthesized using a solid-state pyrolysis method. The structural and electrochemical properties were examined by means of X-ray diffraction, cyclic voltammetry, SEM and charge–discharge tests. The results demonstrated that the powders maintain the α-NaFeO2-type layered structure regardless of the chromium content in the range x ≤ 0.08. The Cr doping of x = 0.04 showed improved capacity and rate capability comparing to undoped Li[Li0.2Ni0.2Mn0.6]O2. ac impedance measurement showed that Cr-doped electrode has the lower impedance value during cycling. It is considered that the higher capacity and superior rate capability of Cr-doping samples would be ascribed to the reduced resistance of the electrode during cycling.  相似文献   

19.
A series of cathode materials with molecular notation of xLi[Li1/3Mn2/3]O2·(1 − x)Li[Ni1/3Mn1/3Co1/3]O2 (0 ≤ x ≤ 0.9) were synthesized by combination of co-precipitation and solid state calcination method. The prepared materials were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques, and their electrochemical performances were investigated. The results showed that sample 0.6Li[Li1/3Mn2/3]O2·0.4Li[Ni1/3Mn1/3Co1/3]O2 (x = 0.6) delivers the highest capacity and shows good capacity-retention, which delivers a capacity ∼250 mAh g−1 between 2.0 and 4.8 V at 18 mA g−1.  相似文献   

20.
Cathode materials prepared by a co-precipitation are 0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (0.2 ≤ x ≤ 0.4) cathode materials with a layered-spinel structure. In the voltage range of 2.0-4.6 V, the cathodes show more than one redox reaction peak during its cyclic voltammogram. The Li/0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (x = 0.3, y = 0.2) cell shows the initial discharge capacity of about 200 mAh g−1. However, when x = 0.2 and y = 0.1, the cell exhibits a rapid decrease in discharge capacity and poor cycle life.  相似文献   

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