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1.
Single-crystal (100) and (001) TiO2 rutile substrates have been implanted with 40 keV Fe+ at room temperature with high doses in the range of (0.5–1.5) × 1017 ions/cm2. A ferromagnetic resonance (FMR) signal has been observed for all samples with the intensity and the out-of-plane anisotropy increasing with the implantation dose. The FMR signal has been related to the formation of a percolated metal layer consisting of close-packed iron nanoparticles in the implanted region of TiO2 substrate. Electron spin resonance (ESR) signal of paramagnetic Fe3+ ions substituting Ti4+ positions in the TiO2 rutile structure has been also observed. The dependences of FMR resonance fields on the DC magnetic field orientation reveal a strong in-plane anisotropy for both (100) and (001) substrate planes. An origin of the in-plane anisotropy of FMR signal is attributed to the textured growth of the iron nanoparticles. As result of the nanoparticle growth aligned with respect to the structure of the rutile host, the in-plane magnetic anisotropy of the samples reflects the symmetry of the crystal structure of the TiO2 substrates. Crystallographic directions of the preferential growth of iron nanoparticles have been determined by computer modeling of anisotropic ESR signal of substitutional Fe3+ ions.  相似文献   

2.
The sample of Mg0. 5+y (Zr1-y Fey) 2 (PO4) 3 (0.0 ≤y ≤0.5) was synthesized using the sol-gel method. The structures of the samples were investigated using X-ray diffraction and Fourier transform infrared spectroscopy measurement. XRD studies showed that samples had a monoclinic structure which was iso-structured with the parent compound, Mg0.5Zr (PO4) 3. The complex impedance spectroscopy was carried out in the frequency range 1–6 MHz and temperature range 303 to 773 K to study the electrical properties of the electrolytes. The substitutions of Fe3+ with Zr4+ in the Mg0.5Zr (PO4) 3 structure was introduced as an extrainterstitial Mg2+ ion in the modified structured. The compound of Mg0.5+y (Zr1-y Fey)2(PO4)3 with y?=?0.4 gives a maximum conductivity value of 1.25?×?10?5 S cm?1 at room temperature and 7.18?×?10?5 S cm?1 at 773 K. Charge carrier concentration, mobile ion concentration, and ion hopping rate are calculated by fitting the conductance spectra to power law variation, σ ac (ω)?=?σ o ? +?Aω α . The charge carrier concentration and mobile ion concentration increases with increase of Fe3+ inclusion. This implies the increase in conductivity of the compounds was due to extra interstitial Mg2+ ions.  相似文献   

3.
N. Nouiri  K. Jaouadi  T. Mhiri  N. Zouari 《Ionics》2016,22(9):1611-1623
Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs2(HSO4)(H2AsO4). The title compound crystallizes in the monoclinic system with the P21/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm?1and 1200–50 cm?1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs2(HSO4)(H2AsO4) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10?4 Ω?1 cm?1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.  相似文献   

4.
Carbon-coated olivine-structured LiFePO4/C composites are synthesized via an efficient and low-cost carbothermal reduction method using Fe2O3 as iron source at a relative low temperature (600 °C). The effects of two kinds of carbon sources, inorganic (acetylene black) and organic (sucrose), on the structures, morphologies, and lithium storage properties of LiFePO4/C are evaluated in details. The particle size and distribution of the carbon-coated LiFePO4 from sucrose (LiFePO4/SUC) are more uniform than that obtained from acetylene black (LiFePO4/AB). Moreover, the LiFePO4/SUC nanocomposite shows superior electrochemical properties such as high discharge capacity of 156 mAh g?1 at 0.1 C, excellent cyclic stability, and rate capability (78 mAh g?1 at 20 C), as compared to LiFePO4/AB. Cyclic voltammetric test discloses that the Li-ion diffusion, the reversibility of lithium extraction/insertion, and electrical conductivity are significantly improved in LiFePO4/SUC composite. It is believed that olivine-structured LiFePO4 decorated with carbon from organic carbon source (sucrose) using Fe2O3 is a promising cathode for high-power lithium-ion batteries.  相似文献   

5.
Titanium dioxide (TiO2)-based materials have been well studied because of the high safety and excellent cycling performance when employed as anode materials for lithium ion batteries (LIBs), whereas, the relatively low theoretical capacity (only 335 mAh g?1) and serious kinetic problems such as poor electrical conductivity (~?10?13S cm?1) and low lithium diffusion coefficient (~?10?9 to 10?13 cm2 s?1) hinder the development of the TiO2-based anode materials. To overcome these drawbacks, we present a facile strategy to synthesize N/S dual-doping carbon framework anchored with TiO2 nanoparticles (NSC@TiO2) as LIBs anode. Typically, TiO2 nanoparticles are anchored into the porous graphene-based sheets with N, S dual doping feature, which is produced by carbonization and KOH activation process. The as-obtained NSC@TiO2 electrode exhibits a high specific capacity of 250 mAh g?1 with a coulombic efficiency of 99% after 500 cycles at 200 mA g?1 and excellent rate performance, indicating its promising as anode material for LIBs.  相似文献   

6.
Li2Mn4O9 and molybdenum-doped Li2Mn4O9 have been prepared by simple solid-state method. Molybdenum is used as a dopant since it is resistant to both corrosion and high-temperature creep deformation. The structural, morphological, and electrical performances of the samples have been analyzed. The material exhibits a cubic structure with the fd3m space group. Using EDAX, the chemical compositions of the samples have been identified. The dc electrical conductivity of the Mo-doped (LM2) sample is found to be increased to 7.44?×?10?6 S cm?1 at 393 K. The enhanced electrical property of the molybdenum-doped Li2Mn4O9 reveals it as a feasible cathode material for rechargeable Li-ion batteries.  相似文献   

7.
Lithium vanadium-borate glasses with the composition of 0.3Li2O–(0.7-x)B2O3xV2O5 (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V2O5 concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO4] structural units occur at V2O5 concentration of 45 mol%. It is established that the concentration of V4+ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li2O-0.275B2O3-0.475V2O5 shows the highest electrical conductivity that has the value of 7.4?×?10?5 S cm?1 at room temperature.  相似文献   

8.
For over two decades, the high-temperature phase transition (HTPT) at around T p = 180 °C on KH2PO4 (KDP), which involves an ionic conductivity increase, constitutes a controversial subject; while most authors ratify a physical transformation (tetragonal → monoclinic phase transition), others defend the chemical transformation. A careful high-temperature phase behavior examination of this acid salt by means of modulated and conventional differential scanning calorimetry, thermogravimetric analysis, simultaneous thermogravimetric and differential scanning calorimetry, impedance spectroscopy, and temperature evolution of X-ray diffraction was performed to provide a possible solution to this long-standing issue. We found that the structural phase transition does not take place. Instead, a chemical transformation occurs at T p. When KDP is heated through this temperature, the sample initially corresponding to a single phase (tetragonal) transforms to a sample composed of two solid phases: tetragonal KDP, located at its bulk, and monoclinic potassium metaphosphate (KPO3), located at its surface. Most of the water produced evaporates, but a small portion of liquid water bonds to KPO3. Because this is of polymeric nature, it takes the role of a host matrix that contains liquid water regions. Consequently, given that part of the water dissolves a portion of surface salt (providing protons), the surface sample system behaves in a similar manner to a polymer electrolyte membrane where the proton transport mechanism includes the vehicle type, using hydronium (H3O+) as a charge carrier. On further heating, the bulk tetragonal KDP phase reduced to its total decomposition. The metastability of the high-temperature phase below T p is also explained.  相似文献   

9.
La0.5Sr0.5CoO3-yttria-stabilized zirconia (LSCO-YSZ) composite cathode for solid oxide fuel cell (SOFC) has been fabricated by wet impregnation method. Nitrate precursors of La, Sr, and Co have been impregnated into the pre-sintered porous YSZ matrix, which is converted into LSCO phase after calcination at 850 °C in the presence of glycine as confirmed from X-ray diffraction. LSCO of 5, 7, and 10 wt% impregnated porous YSZ have been electrochemically characterized using 2-probe AC conductivity method. Maximum ionic conductivity of 0.27 S/cm at 800 °C and activation energy of 0.15 eV between 600 and 800 °C have been observed for 10 wt% LSCO-YSZ cathode. Area-specific resistance of 1.01 Ω cm2 at 800 °C is estimated for the electrolyte-supported half-cell (10 wt% LSCO-YSZ/YSZ). After testing the LSCO-YSZ cathode matrix, the electrolyte-supported full cell (10 wt% LSCO-YSZ/YSZ/NiO-YSZ) has been tested and produced maximum power density 51.12 mW/cm2 (109.38 mA/cm2) at 800 °C. The electrolyte-supported full cell exhibited 6 Ω cm2 electrode polarization at 800 °C in H2, which is in higher side leading to low performance. LSCO-YSZ/YSZ/NiO-YSZ SOFC found to give stable performance up to 2 h and scanning electron microscopy analysis has been carried out before and after cell testing to assess the morphological changes.  相似文献   

10.
This work examines the effect of lithium trifluoromethanesulfonate (LiCF3SO3) and glycerol on the conductivity and dielectric properties of potato starch-chitosan blend-based electrolytes. The electrolytes are prepared via solution cast technique. From X-ray diffraction (XRD) analysis, the blend of 50 wt.% starch and 50 wt.% chitosan is found to be the most amorphous blend. Fourier transform infrared (FTIR) spectroscopy studies show the interaction between the electrolyte materials. The room temperature conductivity of pure starch-chitosan film is found to be (2.85 ± 1.31) × 10?10 S cm?1. The incorporation of 45 wt.% LiCF3SO3 increases the conductivity to (7.65 ± 2.27) × 10?5 S cm?1. Further conductivity enhancement up to (1.32 ± 0.35) × 10?3 S cm?1 has been observed on addition of 30 wt.% glycerol. This trend in conductivity is verified by XRD and dielectric analysis. The temperature dependence of conductivity of all electrolytes are Arrhenian.  相似文献   

11.
In this work, the commercial carbon paper was firstly peeled in K2CO3 solution and then was further treated in a KNO3 solution to form functional exfoliation graphene (FEG) on the commercial carbon paper. The FEG/carbon paper was characterized by Raman spectra and scanning electron microscopy, confirming that some typical layered fold graphenes were successfully peeled off and stood on the carbon paper matrix. Then, Fe3O4 nanoparticles (NPs) were grown on the surface of FEG/carbon paper and the as-prepared Fe3O4 NPs/FEG/carbon paper was directly used as supercapacitor electrode. The specific capacitance of Fe3O4 NPs/FEG/carbon paper was about 316.07 F g?1 at a current density of 1 A g?1. Furthermore, the FEG/carbon papers were also functionalized by benzene carboxylic acid to form FFEG/carbon papers, and then the Fe3O4 NPs were grown on the surface of FFEG/carbon paper. The specific capacitance of Fe3O4 NPs/FFEG/carbon paper was 470 F g?1 at a current density of 1 A g?1, superior to some previous reported results. This work might provide a new strategy to prepare various nanostructures on FFEG/carbon papers for future applications.  相似文献   

12.
Lead-free Na0.5Bi0.5TiO3 (NBT) and (1 ? x)Na0.5Bi0.5TiO3 + xBaTiO3 with x = 0.1 and 0.2 (where x = 0.1 and 0.2 are named as NBT1 and NBT2, respectively), (1 ? y)Na0.5Bi0.5TiO3 + yBa0.925Nd0.05TiO3 with y = 0.1 and 0.2 (where y = 0.1 and 0.2 are named as NBT3 and NBT4, respectively)-based relaxor ferroelectric ceramics were prepared using the sol-gel method. The crystal structure was investigated by X-ray diffraction (XRD) at room temperature (RT). The XRD patterns confirmed the presence of the rhombohedral phase in all the samples. The electrical properties of the present NBT-based samples were investigated by complex impedance and the modulus spectroscopy technique in the temperature range of RT–600 °C. The AC conductivity was found to increase with the substitution of Ba2+ ions to the NBT sample whereas it significantly decreased with the addition of Nd3+ ions. The more anion vacancies in Ba-added samples and the lower anion vacancies in Nd-added samples were found to be responsible for higher and lower conductivities, respectively.  相似文献   

13.
N. Nouiri  K. Jaouadi  N. Zouari  T. Mhiri 《Ionics》2017,23(6):1461-1470
The Rb3(HSeO4)2.5(H2PO4)0.5 compound was prepared and its thermal behavior and electric properties were investigated. The thermogravimetry (TGA) analysis and the differential scanning calorimetric (DSC) show the presence of a structural phase transition of the title compounds at 374 K which is confirmed by the variation of fp and σdc as a function of temperature. The complex impedance of the Rb3(HSeO4)2.5(H2PO4)0.5 compound has been investigated in the temperature range of 295–453 K and in the frequency range 209 Hz–1 MHz. The impedance plots show semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance Rp and constant phase elements CPE1 in series with fractal capacity CPE2. The frequency dependence of the conductivity is interpreted in terms of Jonscher’s law. The conductivity dc follows the Arrhenius relation. The near value of activation energies obtained from the analysis of modulus, conductivity data, and circuit equivalent confirm that the transport is through the ion hopping mechanism, dominated by the motion of the H+ proton in the structure of the investigated materials.  相似文献   

14.
We investigated the synergistic influences of synthesis methods (solid-state reaction vs. sol-gel process) and Zr4+ doping on the structure and ionic conductivity of perovskite-structured Li0.5La0.5TiO3 (LLTO) solid electrolytes. The lithium-ion conductivity of Li0.5La0.5Ti1???x Zr x O3 ceramic specimens was evaluated as a function of x value and compared carefully between those two synthesis methods. Regarding the conductivity, sol-gel process is better for the synthesis of LLTO than solid-state reaction. As a result, the highest grain conductivity is obtained in the sol-gel-derived pure LLTO sample with x?=?0, reaching 1.10?×?10?3 S?·?cm?1. Partial substitution of Zr4+ enlarges the LLTO’s grain aggregate size and increases the total superficial area of aggregates. Consequently, Zr4+ substitution not only affects the grain (bulk) conductivity, but more importantly, also improves the grain boundary conductivity and the total conductivity. The highest total conductivity is 5.84?×?10?5 S?·?cm?1 with x?=?0.04 by sol-gel process.  相似文献   

15.
Visible light Bi2O3/TiO2 nanocomposites are successfully prepared with different dosages of Bi2O3 by hydrothermal process. All the as-prepared samples are characterized by X-ray diffraction (XRD), scanning and transmission electron microscopes (SEM and TEM), Brunauer-Emmett-Teller analysis (BET), N2 adsorption-desorption measurement, and UV-Vis diffuse reflectance spectra (DRS). XRD and Raman spectra reveal the anatase phase of both TiO2 and Bi2O3/TiO2 nanocomposites. X-ray diffraction patterns demonstrate that the bismuth ions did not enter into the lattice of TiO2, and Bi2O3 is extremely dispersive on the surface of TiO2 nanoparticles. The incorporation of Bi2O3 in TiO2 leads to the spectral response of TiO2 in the visible light region and efficient separation of charge carriers. The enhanced visible light activity is tested by the photocatalytic degradation of methyl orange under light illumination, and the performance of Bi2O3/TiO2 nanocomposites are superior than that of pure TiO2 which is ascribed to the efficient charge separation and transfer across the Bi2O3/TiO2 junction. Bi2O3/TiO2 nanocomposite (20 mg) loaded with 0.25 of Bi2O3 dispersed in 50 ml of 5 ppm methyl orange solution exhibited the highest photocatalytic activity of 98.86% within 240 min of irradiation, which is attributed to the low band gap, high surface area, and the strong interaction between Bi2O3 and TiO2.  相似文献   

16.
Hierarchical structured ZnFe2O4@reduced graphite oxide@TiO2 (ZnFe2O4@RGO@TiO2) nanocomposite was prepared by an electrostatic layer-by-layer route, which played a synthetic effect of Fenton oxidation of ZnFe2O4 and photocatalytic oxidation of TiO2 to degrade fulvic acid (FA) solution under visible-light irradiation. In this method, RGO, as the middle layer, can effectively promote the photo-induced electron flow between the ZnFe2O4 and TiO2 and further improve the efficiency of the photo-Fenton oxidation. The influencing factors on photo-Fenton oxidation, including solution pH, catalyst, and H2O2 dosage, have also been investigated. The results illustrated that the ternary composite presented the enhanced catalytic performance. Under visible light irradiation, the degradation efficiency of the sample on the FA solution can reach 95.4% within 3 h. In addition, the catalyst exhibited superior stability and reusability, and its degradation efficiency was still up to 90% after 5 cycles. Therefore, the composite will be a kind of efficient photocatalyst and had a promising application for visible-light driven destruction of organic pollutants.  相似文献   

17.
A simple and highly efficient method is developed for in situ one-step preparation of carbon co-encapsulated anatase and rutile TiO2 nanocrystals (TiO2@C) with core-shell structure for lithium-ion battery anode. The synthesis is depending on the solid-phase reaction of titanocene dichloride with ammonium persulfate in an autoclave at 200 °C for 30 min. The other three titanocene complexes including bis(cyclopentadienyl)dicarbonyl titanium, cyclopentadienyltitanium trichloride, and cyclopentadienyl(cycloheptatrienyl)titanium are used instead to comprehensively investigate the formation mechanism and to improve the microstructure of the product. The huge heat generated during the explosive reaction cleaves the cyclopentadiene ligands into small carbon fragments, which form carbon shell after oxidative dehydrogenation coating on the TiO2 nanocrystals, resulting in the formation of core-shell structure. The TiO2 nanocrystals prepared by titanocene dichloride have an equiaxed morphology with a small diameter of 10–55 nm and the median size is 30.3 nm. Hundreds of TiO2 nanocrystals are encapsulated together by the worm-like carbon shell, which is amorphous and about 20–30 nm in thickness. The content of TiO2 nanocrystals in the nanocomposite is about 31.1 wt.%. This TiO2@C anode shows stable cyclability and retains a good reversible capacity of 400 mAh g?1 after 100 cycles at a current density of about 100 mA g?1, owing to the enhanced conductivity and protection of carbon shell.  相似文献   

18.
Anatase TiO2 nanoparticles were prepared by a simple sol-gel method at moderate temperature. X-ray powder diffraction (XRD) and Raman spectroscopy revealed the exclusive presence of anatase TiO2 without impurities such as rutile or brookite TiO2. Thermogravimetric analysis confirmed the formation of TiO2 at about 400 °C. Particle size of about 20 nm observed by transmission electron microscopy matches well with the dimension of crystallites calculated from XRD. The electrochemical tests of the sol-gel-prepared anatase TiO2 show promising results as electrode for lithium-ion batteries with a stable specific capacity of 174 mAh g?1 after 30 cycles at C/10 rate. The results show that improvement of the electrochemical properties of TiO2 to reach the performance required for use as an electrode for lithium-ion batteries requires not only nanosized porous particles but also a morphology that prevents the self-aggregation of the particles during cycling.  相似文献   

19.
Ni sintering at high temperature (~ 800 °C) operation drastically degrades the performance of Ni-yttria-stabilized zirconia (YSZ) anode in solid oxide fuel cell (SOFC). Mixed ionic and electronic conductive oxides such as CeO2 and Nb2O5 enhance the dispersion of Ni, CeO2 enhances the redox behavior and promotes charge transfer reactions, and Nb2O5 increases the triple phase boundary. In the present work, anode-supported SOFC is fabricated and tested in H2 fuel at 800 °C. YSZ and lanthanum strontium manganite (LSM)-YSZ are used as the electrolyte and composite cathode with NiO-YSZ, CeO2-NiO-YSZ, and Nb2O5-NiO-YSZ as an anode. The peak power density obtained for the cell with 10% CeO2–30% NiO-YSZ anode at the 5 and 25 h of operation is 330 and 290 mW cm?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm?2 at 5 h). The peak power density obtained for the cell with 10% Nb2O5–30% NiO-YSZ anode at the 5 and 25 h of operation is 301 and 285 mW cm?2 which is higher than that for 40% NiO-YSZ anode (275 mW cm?2 at 5 h). Physical characterization has been carried to study morphology, elemental analysis, particle size, and phase formation of the fabricated anode before and after cell operation to correlate the cell performance.  相似文献   

20.
Solid polymer electrolytes based on methyl cellulose (MC)-potato starch (PS) blend doped with ammonium nitrate (NH4NO3) are prepared by solution cast technique. The interaction between the electrolyte’s materials is proven by Fourier transform infrared (FTIR) analysis. The thermal stability of the electrolytes is obtained from thermogravimetric analysis (TGA). The room temperature conductivity of undoped 60 wt.% MC-40 wt.% PS blend film is identified to be (1.04 ± 0.19) × 10?11 S cm?1. The addition of 30 wt.% NH4NO3 to the polymer blend has optimized the room temperature conductivity to (4.37 ± 0.16) × 10?5 S cm?1. Conductivity trend is verified by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and dielectric analysis. Temperature-dependence of conductivity obeys Arrhenius rule. Conductivity is found to be influenced by the number density (n) and mobility (μ) of ions. From transference number measurements (TNM), ions are found to be the dominant charge carriers.  相似文献   

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