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1.
A series of ZnxMg1 − xGa2O4:Co2+ spinels (x = 0, 0.25, 0.5, 0.75, and 1.0) was successfully produced through low-temperature burning method by using Mg(NO3)2·4H2O, Zn(NO3)2·6H2O, Ga(NO3)3·6H2O, CO(NH2)2, NH4NO3, and Co(NO3)2·6H2O as raw materials. The product was characterized by X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The product was not merely a simple mixture of MgGa2O4 and ZnGa2O4; rather, it formed a solid solution. The lattice constant of ZnxMg1 − xGa2O4:Co2+ (0 ≤ x ≤ 1.0) crystals has a good linear relationship with the doping density, x. The synthesized products have high crystallinities with neat arrays. Based on an analysis of the form and position of the emission spectrum, the strong emission peak around the visible region (670 nm) can be attributed to the energy level transition [4T1(4P) → 4A2(4F)] of Co2+ in the tetrahedron. The weak emission peak in the near-infrared region can be attributed to the energy level transition [4T1(4P) → 4T2(4F)] of Co2+ in the tetrahedron.  相似文献   

2.
Bo Gao 《Electrochimica acta》2010,55(11):3681-11258
Amorphous RuO2·xH2O was well coated on the benzenesulfonic functionalized multi-wall carbon nanotubes (f-MWCNTs) successfully via hydrothermal method. The decorated benzenesulfonic groups served as a bifunctional role both for solubilizing and dispersing MWCNTs into aqueous solution and for tethering Ru3+ precursor to facilitate the following uniform chemical deposition of RuO2·xH2O. The electrochemical performance of RuO2/f-MWCNTs and utilization of RuO2·xH2O were evidenced by cyclic voltammetry and galvanostatic charge/discharge tests. The specific capacitance of 1143 Fg−1 for RuO2·xH2O was obtained from RuO2/f-MWCNTs with 32 wt.% RuO2·xH2O, which was much higher than that of just 798 Fg−1 for the RuO2/p-MWCNTs. Even though the RuO2·xH2O loading increases to 45 wt.%, the utilization of RuO2·xH2O still possesses as high as 844.4 Fg−1, indicating a good energy capacity in the case of high loading.  相似文献   

3.
Hydrous ruthenium dioxide (RuO2·xH2O) prepared in a modified sol-gel process was subjected to annealing in air and water at various temperatures for supercapacitor applications. The textural and pseudocapacitive characteristics of RuO2·xH2O annealed in air and water were systematically compared to show the benefits of annealing in water (denoted as hydrothermal annealing). An important concept that hydrothermal annealing effectively restricts condensation of hydroxyl groups within nanoparticles, inhibits crystal growth, and maintains high water content of RuO2·xH2O is demonstrated in this work. The unique textural characteristics of hydrothermally annealed RuO2·xH2O are attributable to the high-pressured, water-enriched surroundings which restrain coalescence of RuO2·xH2O nanocrystallites. The crystalline, hydrous nature of hydrothermally annealed RuO2·xH2O favors the utilization of active species in addition to a merit of minor dependence of specific capacitance on the scan rate of CV for pseudocapacitors. As a result, RuO2·xH2O with hydrothermal annealing at 225 °C for 24 h exhibits 16 wt.% water, an average particle size of about 7 nm, and specific capacitance of ca. 390 F g−1.  相似文献   

4.
Yang Liu 《Electrochimica acta》2008,53(8):3296-3304
Co3O4/RuO2·xH2O composites with various Ru content (molar content of Ru = 5%, 10%, 20%, 50%) were synthesized by one-step co-precipitation method. The precursors were prepared via adjusting pH of the mixed aqueous solutions of Co(NO3)2·6H2O and RuCl3·0.5H2O by using Pluronic123 as a soft template. For the composite with molar ratio of Co:Ru = 1:1 annealed at 200 °C, Brunauer-Emmet-Teller (BET) results indicated that the composite showed mesoporous structure, and the specific surface area of the composite was as high as 107 m2 g−1. The electrochemical performances of these composites were measured in 1 M KOH electrolyte. Compared with the composite prepared without template, the composite with P123 exhibited a higher specific capacitance. When the molar content of Ru was rising, the specific capacitance of the composites increased significantly. It was also observed that the crystalline structures as well as the electrochemical activities were strongly dependent on the annealing temperature. A capacitance of 642 F/g was obtained for the composite (Co:Ru = 1:1) annealed at 150 °C. Meanwhile, the composites also exhibited good cycle stability. Besides, the morphologies and textural characteristic of the samples were also investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM).  相似文献   

5.
In this study, ultra-thin nanobelts of Ag2V4O11/Ag were successfully synthesized. The synthesized ultra-thin nanobelts of Ag2V4O11/Ag are highly crystalline and the thickness is found to be about 5 nm. A lithium battery using ultra-thin nanobelts of Ag2V4O11/Ag as the active materials of the positive electrode exhibits a high initial discharge capacity of 276 mAh g−1, corresponding to the formation of LixAg2V4O11 (x = 6). With increased cycling, the electrode made of ultra-thin nanobelts of Ag2V4O11/Ag tends to loose electrochemical activity due to Ag+ ions in the ultra-thin nanobelts of Ag2V4O11 were reduced and new phase was formed.  相似文献   

6.
Lithium vanadium oxides have been prepared by the new solution processing in an aqueous hydrogen peroxide solution with lithium and vanadium alkoxides, LiO-n-C3H7 and VO(O-i-C3H7)3, at low temperature, compared with conventional high temperature solid state reaction. Oxides having a layered structure isomorphic to that of γ-phase LixV2O5 were obtained. This “γ-like phase” oxide can be obtained at the nominal Li/V ratio of 1.5 almost as a single phase. However, formation of ω phase cannot be confirmed. The γ-like phase oxide contained water and organic compounds, and the water content n in LixV2O5·nH2O was found to be about 2.4 for the γ-like phase oxide. Further as the result of the atomic absorption spectrometric method, the lithium content x in LixV2O5·nH2O was estimated to be 2.2, and water molecules presumably exist in the interlayer space.Water content of the γ-like phase oxides, affects charge and discharge behaviours markedly. The lithium extraction-insertion capacity of the γ-like phase oxides were smaller, but the oxides had higher average potential compared with those of γ-phase oxide. As water content of γ-like phase oxides decreased, the lithium extraction-insertion capacity increased. Moreover, it should be noted that the average potential of γ-like phase oxides is at least 1 V higher than that of γ-LiV2O5.  相似文献   

7.
Grass blade-like microparticle MnPO4·H2O was synthesized by a simple precipitation at room temperature using a mixture of manganese sulphate monohydrate, phosphoric acid and water at pH = 7. The thermogravimetric study indicates that the synthesized compound is stable below 500 °C and its final decomposed product is Mn2P2O7. The pure monoclinic phases of the synthesized MnPO4·H2O and its final decomposed product Mn2P2O7 are verified by XRD data. FTIR spectra indicate the presences of the PO43− ion and water molecules in the MnPO4·H2O structure and the P2O74− ion in the Mn2P2O7 structure. The thermal stability, crystallite size, and grass blade-like microparticle of MnPO4·H2O in this work are different from previous reports, which may be caused by the starting reagents and reaction condition for the precipitation.  相似文献   

8.
A two-step hydrothermal process was developed to synthesize hydrous 30RuO2-70SnO2 composites with much better capacitive performances than those fabricated through the normal hydrothermal process, co-annealing method, or modified sol-gel procedure. A very high specific capacitance of RuO2 (CS,Ru), ca. 1150 F g−1, was obtained when this composite was synthesized via this two-step hydrothermal process with annealing in air at 150 °C for 2 h. The voltammetric currents of this annealed composite were found to be quasi-linearly proportional to the scan rate of CV (up to 500 mV s−1), demonstrating its excellent power property. From Raman, UV-vis spectroscopic and TEM analyses, the reduction in mean particulate size is clearly found for this two-step oxide composite, attributable to the co-precipitation of (RuδSn1−δ)O2·xH2O onto partially dissolved SnO2·xH2O and the formation of (RuδSn1−δ)O2·xH2O crystallites in the second step. This effect significantly promotes the utilization of RuO2 (i.e., very high CS,Ru). The excellent capacitive performances, very similar to that of RuO2·xH2O, suggest the deposition of RuO2-enriched (RuδSn1−δ)O2·xH2O onto SnO2·xH2O seeds as well as the individual formation of (RuδSn1−δ)O2·xH2O crystallites in the second hydrothermal step.  相似文献   

9.
G.Q. Liu  Qilu  W. Li 《Electrochimica acta》2005,50(9):1965-1968
Spinel compound LiNi0.5Mn1.5O4 was synthesized by a chemical wet method. Mn(NO3)2, Ni(NO3)2·6H2O, NH4HCO3 and LiOH·H2O were used as the starting materials. At first, Mn(NO3)2 and Ni(NO3)2·6H2O reacted with NH4HCO3 to produce a precursor, then the precursor reacted with LiOH·H2O to synthesize product LiNi0.5Mn1.5O4. The product showed a single spinel phase under appropriate calcination conditions, and exhibited a high voltage plateau at about 4.6-4.8 V in the charge/discharge process. The LiNi0.5Mn1.5O4 had a discharge specific capacity of 118 mAh/g at about 4.6 V and 126 mAh/g in total in the first cycle at a discharge current density of 2 mA/cm2. After 50 cycles, the total discharge capacity was above 118 mAh/g.  相似文献   

10.
The electrochemical energy storage and delivery on the electrodes composed of hydrous ruthenium oxide (RuOx·nH2O) or activated carbon-hydrous ruthenium oxide (AC-RuOx) composites are found to strongly depend on the substrate employed. The contact resistance at the active material-graphite interface is much lower than that at the active material-stainless steel (SS) mesh interface. Thin films of gold plus RuOx·nH2O deposited on SS meshes (RuOx/Au/SS) are found to greatly improve the poor contact between SS meshes and electrode materials. The maximum specific capacitance (CS,RuOx) of RuOx·nH2O, 1580 F g−1 (measured at 1 mV s−1), very close to the theoretic value, was obtained from an AC-RuOx/RuOx/Au/SS electrode with 10 wt.% sol-gel-derived RuOx·nH2O annealed in air at 200 °C for 2 h. The highly electrochemical reversibility, high-power characteristics, good stability, and improved frequency response of this AC-RuOx/RuOx/Au/SS electrode demonstrate its promising application potential in supercapacitors. The ultrahigh specific capacitance of RuOx·nH2O probably results from the uniform size distribution of RuOx·nH2O nanoparticles, ranged from 1.5 to 3 nm which is clearly observed from the high-resolution transmission electron microscopy (HRTEM).  相似文献   

11.
RuO2·xH2O/NiO composites having RuO2 contents in the range 0-100 wt.% have been prepared by a co-precipitation method. Structural, microstructural and textural transformations after heating the as-prepared composites at 200 and 600 °C have been followed by X-ray diffraction, scanning electron microscopy (SEM) and nitrogen adsorption/desorption isotherms. At 200 °C the composites are made of micrometric particles in which nanometric crystallites of the two oxides are aggregated. The composites show microporosity (0.02-0.10 cm3/g), mesoporosity (0.07-0.12 cm3/g) and relatively high specific surface area (62-309 m2/g). At 600 °C the composites are fully dehydrated and RuO2 has crystallized and segregated. Microporosity and mesoporosity as well as specific surface area are strongly decreased. Specific capacitance and specific surface area of the composites heated at 200 and 600 °C have been measured and discussed on the basis of the RuO2 content. For comparison the specific capacitance and specific surface area of mixtures of NiO and RuO2·xH2O (or RuO2) have been taken as references. The higher specific capacitance of the 200 °C-heated composites compared to the 600 °C-heated ones is due to the higher specific surface area of the former and the higher pseudocapacitance of RuO2·xH2O compared to RuO2. The discussion reported in this work can be applied to other composites such as RuO2·xH2O/carbon and RuO2·xH2O/other oxides.  相似文献   

12.
Hydrous, crystalline, binary (Ru-Ti)O2·nH2O with compositions equal to the ratios of metallic ions in the precursor solutions are successfully synthesized by a mild hydrothermal process. The maximum utilization of RuO2·nH2O (ca. 793 F/g) occurs at the composition of 60 M% TiO2·nH2O although phase separation is clearly found for this TiO2-enriched binary oxides. The nano-structured architecture with a high BET surface area (ca. 253 m2/g) of the hydrothermal-derived (Ru-Ti)O2·nH2O with annealing at 200 °C favors the physical adsorption of water and maintains a high water content which is novel and never found before. Due to this novel nanostructure, the annealed (Ru-Ti)O2·nH2O synthesized by means of the hydrothermal process exhibits excellent performances (i.e., high utilization of RuO2, high power property, and long cycle life) for supercapacitors.  相似文献   

13.
This work demonstrates that anodic deposition of vanadium oxide (denoted as VOx·nH2O) can be considered as the chemical co-precipitation of V5+ and V4+ oxy-/hydroxyl species and the accumulation of V5+ species at the vicinity of electrode surface is the key factor for the successful anodic deposition of VOx·nH2O at a potential much more negative than the equilibrium potential of the oxygen evolution reaction (OER). The results of in situ UV-vis spectra show that the V4+/V5+ ratio near the electrode surface can be controlled by varying the applied potential, leading to different, three-dimensional (3D) nanostructures of VOx·nH2O. The accumulation of V5+ species due to V4+ oxidation at potentials ≥0.4 V (vs. Ag/AgCl) has been found to be very similar to the phenomenon by adding H2O2 in the deposition solution. The X-ray photoelectron spectroscopic (XPS) results show that all VOx·nH2O deposits can be considered as aggregates consisting of mixed V5+ and V4+ oxy-/hydroxyl species with the mean oxidation state significantly increasing with the applied electrode potential.  相似文献   

14.
Lifeng Zhang 《Fuel》2009,88(3):511-24
Nickel-based catalysts supported on Al2O3 · SiO2 were prepared with modification of the second metal involving La, Co, Cu, Zr or Y, of which the catalytic behaviors were assessed in the ethanol steam reforming reaction. Activity test indicated that addition of La resulted in higher selectivity of hydrogen and lower selectivity of carbon monoxide, compared with Co-doped nickel catalyst. Influences of lanthanum amounts on catalytic performance were studied over 30NixLa/Al2O3 · SiO2 (x = 5, 10, 15), and characterizations by XRD, TPR and XPS indicated that low amount of lanthanum additives (5%) was superior to inhibit the crystal growth of nickel as well as beneficial to the reduction of nickel oxide. Finally 100 h test for the optimal catalyst 30Ni5La/Al2O3 · SiO2 indicated its good long-term stability to provide high hydrogen selectivity and low carbon monoxide formation, as well as good resistance to coke deposition at low temperature.  相似文献   

15.
Co-doped Li3V2−xCox(PO4)3/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li3V2−xCox(PO4)3/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li3V2−xCox(PO4)3. XPS studies also revealed that V4+ and V3+ ions were present in the Co2+-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li3V2−xCox(PO4)3/C compounds showed that the voltage peaks associated with the extraction of three Li+ ions shifted to higher voltages with an increase in Co content, and when the Co2+-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li3V2(PO4)3 phase. For the Li3V1.85Co0.15(PO4)3/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li3V2(PO4)3) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co2+into V sites should be favorable for the structural stability of Li3V2−xCox(PO4)3/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li+ extraction/insertion, thus resulting in the improvement of cell cycling ability.  相似文献   

16.
This paper reports the synthesis, structure, chemical stability and electrical transport properties of Ti substituted Ba3CaNb2O9 (BCN) to develop electrolytes for proton conducting solid oxide fuel cells (H-SOFCs). The powder X-ray diffraction (PXRD) of Ba3CaNb2−xTixO9−δ (x = 0.1, 0.15, 0.2, 0.25 and 0.3) and Ba3Ca1.18Nb1.82−xTixO9−δ (x = 0.15 and 0.25) showed formation of double perovskite-like structure with lattice constant comparable to that of Ba3Ca1.18Nb1.82O9−δ (BCN18). Scanning electron microscopy (SEM) showed dense and pore-free microstructure for Ba3CaNb1.75Ti0.25O8.875. PXRD and Fourier transform infrared (FTIR) spectroscopy data confirmed long-term stability of Ba3CaNb2−xTixO9−δ and Ba3Ca1.18Nb1.82−xTixO9−δ in boiling H2O and in CO2 at elevated temperatures. The AC impedance investigation showed contribution due to bulk, grain-boundary and electrode effect at low temperatures. The electrical conductivity of studied materials were measured in different medium including dry air, dry H2, wet H2, wet N2 and D2O. Increase in conductivity in wet N2 and decrease in conductivity in D2O confirmed the proton conduction in Ba3CaNb1.75Ti0.25O9-δ. Among Ti-substituted compounds investigated in this study, Ba3Ca1.18Nb1.57Ti0.25O8.605 showed the highest conductivity of 3.5 × 10−4 S cm−1 at 400 °C in wet N2 (3%H2O), which is comparable to reported values of Ba2Ca0.79Nb0.66Ta0.55O6−δ and BCN18.  相似文献   

17.
A carbon coated Li3V2(PO4)3 cathode material for lithium ion batteries was synthesized by a sol-gel method using V2O5, H2O2, NH4H2PO4, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P21/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li3V2(PO4)3 electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g−1 was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li3V2(PO4)3 formula unit (133 mAh g−1). It was found that the increase in total carbon content can improve the discharge performance of the Li3V2(PO4)3 electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li3V2(PO4)3 host are almost reversible, exhibiting a reversible capacity of 177 mAh g−1 and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material were also discussed.  相似文献   

18.
Layered metastable lithium manganese oxides, Li2/3[Ni1/3−xMn2/3−yMx+y]O2 (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na2/3[Ni1/3−xMn2/3−yMx+y]O2 precursors. The Al and Co doping produced the T#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni1/3−xMn2/3−yMx+yO2 slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T#2-Li2/3[Ni1/3Mn2/3]O2 were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g−1 in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g−1 along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T#2 into the O2 structure was observed during the initial lithium deintercalation.  相似文献   

19.
Several compositions of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb1−xGdxZr2O7 ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb1−xGdxZr2O7 (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb1−xGdxZr2O7 (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb0.5Gd0.5Zr2O7 composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb1−xGdxZr2O7 ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb1−xGdxZr2O7 ceramics are oxide-ion conductor 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 1.79 × 10−2 S cm−1 at 1173 K for NdYb0.3Gd0.7Zr2O7 composition.  相似文献   

20.
A new series of rare earth solid solutions Sc2−xYxW3O12 was successfully synthesized by the conventional solid-state method. Effects of doping ion yttrium on the crystal structure, morphology and thermal expansion property of as-prepared Sc2−xYxW3O12 ceramics were investigated by X-ray diffraction (XRD), thermogravimetric analysis (TG), field emission scanning electron microscope (FE-SEM) and thermal mechanical analyzer (TMA). Results indicate that the obtained Sc2−xYxW3O12 samples with Y doping of 0≤x≤0.5 are in the form of orthorhombic Sc2W3O12-structure and show negative thermal expansion (NTE) from room temperature to 600 °C; while as-synthesized materials with Y doping of 1.5≤x≤2 take hygroscopic Y2W3O12·nH2O-structure at room temperature and exhibit NTE only after losing water molecules. It is suggested that the obvious difference in crystal structure leads to different thermal expansion behaviors in Sc2−xYxW3O12. Thus it is proposed that thermal expansion properties of Sc2−xYxW3O12 can be adjusted by the employment of Y dopant; the obtained Sc1.5Y0.5W3O12 ceramic shows almost zero thermal expansion and its average linear thermal expansion coefficient is −0.00683×10−6 °C−1 in the 25–250 °C range.  相似文献   

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