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1.
Ling Wu  Shengkui Zhong  Jiajia Lu  Jiequn Liu  Fan Lv 《Ionics》2013,19(7):1061-1065
LiMn1-x Cr x PO4/C (x?=?0, 0.01, 0.03, and 0.05) compounds are synthesized by a sol–gel combined ball milling method. The effects of Cr doping on the structure, morphology, and electrochemical performance of LiMnPO4 are investigated. XRD analysis results indicate that all the samples exhibit the single LiMnPO4 phase and Cr ions substitute on Mn site (x?≤?0.03), with charge compensating vacancies on Li site. The vacancies are of benefit to improving the electronic conductivity of LiMnPO4. SEM studies reveal that Cr doping can effectively inhibit the aggregation of LiMnPO4 particles. Electrochemical tests show that the Cr-doped samples exhibit higher initial capacities and better cycling performance than the undoped one. LiMn0.97Cr0.03PO4/C exhibit the best electrochemical performance that the first specific discharge capacity is 132.4 mAh g?1 at 0.1 C rate, and the capacity retention is 94.8 % after 30 cycles.  相似文献   

2.
A series of Cr-substituted LiMn2O4 samples (LiCr x Mn2-x O4, 0?≤?x?≤?0.3) were synthesized by a urea-assisted combustion method to enhance pseudocapacitive properties of LiMn2O4 material in aqueous electrolyte. Their structure and morphology were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The LiCr x Mn2-x O4 and activated carbon (AC) electrode were used as the cathode and anode in hybrid supercapacitors, respectively, which capacitive properties were determined by cyclic voltammetry (CV), galvanostatic charge/discharge test, and electrochemical impedance spectroscopy (EIS) in Li2SO4 solution. The results revealed that the partial substitution of Mn3+ by Cr3+ decreased initial capacity, but it prevented capacity fading. In the working voltage of 0–1.4 V, the AC/LiCr0.1Mn1.9O4 capacitor delivered an initial specific capacitance of 41.6 F g?1 (based on the total active mass of two electrodes) at a current density of 100 mA g?1 in 1 M Li2SO4 solution. After 1,000 cycles, its capacity loss was only 1.7 %.  相似文献   

3.
A series of carbon-coated LiFe1???x Mn x PO4 compounds are prepared by a hydrothermal method at 170 °C for 12 h. The structure and morphology of the prepared composites are characterized to examine the effects of Mn2+ substitution. All LiFe1???x Mn x PO4 compositions are found to have an ordered olivine-type structure with homogeneous Fe2+ and Mn2+ distributions. The substitution leads to grain refinement from ~500 to ~150 nm, as well as to increased initial capacity and improved electronic conductivity. The amount of carbon coating varies with increased doping amount. The discharge curves of the LiFe1???x Mn x PO4/C materials reveal a high discharge plateau corresponding to Fe2+/3+ and no obvious plateau assigned to Mn2+/3+, although a slight contribution of manganese is detected. However, the electrochemical performance, including the discharge capacity and cyclic performance, deteriorates with increased Mn content in the composite.  相似文献   

4.
Carbon-coated Fe–Mg-homogeneously dispersed Li(Mn0.9Fe0.10)1???x Mg x PO4/C (x?=?0.00, 0.01, 0.03, 0.05, and 0.07) powders are synthesized via a mechano-chemical liquid-phase activation technique. Fine-sized and Fe2+ and Mg2+ evenly distributed precursors are formed using this efficient approach successfully. The synthesis temperature and the Mg2+ doping ratio are investigated and optimized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electrochemical measurements. Mg doping decreases the lattice parameters of LiMn0.9Fe0.1PO4/C, which will ease the expansion/shrinking effect during the insertion/de-insertion processes. Li(Mn0.9Fe0.1)0.95Mg0.05PO4/C synthesised at 700 °C with ~3 wt% of carbon additive presents the best comprehensive electrochemical properties, and it displays good rate capability with specific discharge capacity of 153 mAh g?1 at 0.1C, 140 mAh g?1 at 1C, and 132 mAh g?1 at 2C rate. The results suggest that the electrochemical performance of the LiMnPO4-based cathode is improved as (Mn0.9Fe0.1) is partially substituted by Mg.  相似文献   

5.
Nanocrystalline ?-Fe3?x Ni x N (0.0?≤?×?≤?0.8) particles are synthesized by precursor technique and nitridation of decomposed products in NH3 (g) in the temperature range 673 K-823 K. For x?=?0.1–0.4 compositions, single phase ?-Fe3?x Ni x N hexagonal structure with space group P63/mmc is formed, while for x?=?0.5–0.8, fcc γ′-Fe4?y Ni y N phase is also precipitated. The room temperature Mössbauer spectrum for all the compositions shows the presence of superparamagnetic doublet, which is attributed to ?-Fe3?x Ni x N phase. For x?=?0.5–0.8 compositions, two additional sextets are observed corresponding to two different iron sites, the corner position (Fec) and the fcc position (Fef), in γ′-Fe4?y Ni y N. The added Ni atoms preferentially substitute the corner Fec positions. The isomer shift, quadrupole splitting and hyperfine field values are found to change with the Ni content.  相似文献   

6.
A new polyanionic cathode material, Li3V2(PO4)3·LiMn0.33Fe0.67PO4/C for lithium-ion batteries, was synthesized using a sol-gel method and with N,N-dimethyl formamide as a dispersion agent. The analysis of electron transmission spectroscopy and X-ray diffraction revealed that the composite contained two phases. The material has high crystallinity with a grain size of 20–50 nm. The valence states of Mn, V, and Fe in the composite were analyzed by X-ray photoelectron spectroscopy. The electrochemical kinetics in Li3V2(PO4)3 is effectively enhanced by the incorporation of LiMnPO4 and LiFePO4, via structure modification and reduced Li diffusion length. The Li3V2(PO4)3·LiMn0.33Fe0.67PO4/C materials displayed high rate capacity and steady cycle performance with discharge capacity remained 148 mAh g?1 after 50 cycles at the rate of 0.2C. In particular, the composite exhibited excellent reversible capacities, with the values of 157, 134, 120, 102, and 94 mAh g?1 at charge/discharge 0.2, 0.5, 1, 2, and 5C rates, respectively.  相似文献   

7.
The transformations of phase composition of iron nanowires deposited into porous alumina template when annealing in the air were studied. The samples of iron nanowires of different diameter (8, 13, 15, 30 nm) were annealed for 1.5 h at temperature up to 600°C. In addition, for nanowires of 15 nm diameter the dependence of phase composition on annealing time was investigated. The phases were determined by applying Mössbauer spectroscopy. New Fe(II) and Fe(III) contributions to Mössbauer spectra were found and those were indentified as caused by the formation of hercynite FeAl2O4 and (Fe x Al1???x )2O3 with small x values (x?≤?0.15). It has been found that though initially the Fe(II) compound forms rapidly, afterwards its formation rate becomes lower than that of Fe(III) and after longer annealing time the Fe(III) content exceeds Fe(II) one.  相似文献   

8.
LiCo1???x Ca x PO4–graphitic carbon foam composites are prepared using a sol–gel method. The structural analysis reveals LiCoPO4 as major crystalline phase and Co2P2O7 (for x?=?0.0) and Co2P, Li3PO4, and (Ca,Co)3(PO4)2 (for x?≥?0.05) as secondary phases. The morphology consists of microcrystalline “islands” with acicular crystallites (5–50 μm size). Transmission electron microscopy (TEM) of the powders showed that the Ca is incorporated into the crystal structure evoking exaggerated grain growth. The voltammetric profiles show a decrease of the voltammetric surface between anodic and cathodic sweeps and a shift of the reduction potentials toward higher values (~4.6 V, x?=?0.1). The electrochemical measurements, at a discharge rate of C/10 (room temperature), show an increase of the discharge-specific capacity from 100 mAhg?1 for x?=?0.0 to 104 mAhg?1 for x?=?0.1. The ac impedance spectroscopy data revealed an improvement of the Li-ion conductivity at high content of Ca ions (x?=?0.1).  相似文献   

9.
M-type hexaferrites Ca0.2Sr0.8-xPrxFe12-yZnyO19 (0.00?≤?x?≤?0.40, 0.00?≤?y?≤?0.30) were synthesized by the ceramic process. The X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and a vibrating sample magnetometer (VSM) were used to investigate microstructure and magnetic properties of the M-type hexaferrites. The single-phase with hexagonal structure was obtained in all Pr–Zn substituted M-type hexaferrites, and with increasing Pr–Zn content, the 2θ values of (107) and (114) peaks shifted towards higher angles. With increasing Pr–Zn content, the lattice constant a basically kept unchanged, while the lattice constant c decreased. FESEM images of the hexaferrites showed that the hexagonal platelets had formed in the hexaferrites and the average grain size increased with increasing Pr–Zn content. The saturation magnetization (Ms), remanent magnetization (Mr) and Mr/Ms ratio first increased with increasing Pr–Zn content (0.00?≤?x?≤?0.24, 0.00?≤?y?≤?0.18), and then decreased with further increasing Pr–Zn content. The coercivity (Hc), magnetic anisotropy field (Ha) and effective magnetic anisotropy constant (Keff) increased with increasing Pr–Zn content (0.00?≤?x?≤?0.16, 0.00?≤?y?≤?0.12), and then decreased with further increasing Pr–Zn content.  相似文献   

10.
Single crystals of iron manganese sulfides Fe x Mn1 ? x S (0.25 ≤ x ≤ 0.29) are experimentally investigated using Mössbauer spectroscopy and x-ray diffraction. The Mössbauer spectra measured at 300 K exhibit a single broadened line characteristic of paramagnets. The isomer shift of this line is equal to 0.92–0.94 mm/s, which is typical of Fe2+ ions in the octahedral position. The quadrupole splitting (0.18–0.21 mm/s) suggests a distortion of the coordination polyhedron of iron ions in the Fe x Mn1 ? x S compounds.  相似文献   

11.
Magnetization and Mössbauer studies have been made for understanding magnetic behavior of three double perovskite systems La1.5Ca1.5Mn2???x Fe x O7 corresponding to x = 0.05, 0.10 and 0.50. These have been prepared following sol–gel route. Substitution of Fe does not lead to any major change in the tetragonal cell but increased iron leads to greater distortion in octahedral site. The three samples undergo paramagnetic–ferromagnetic transition. Curie temperature (T c) for the system with 0.05 Fe is ~150 K which is lower than (190 K) for the system without iron; with 0.50 Fe T c goes below 50 K. Iron goes as Fe3?+? and replaces Mn in ab plane. With increasing Fe the valence states of Mn get re-distributed in a way that number of the Jahn–Teller ions Mn3?+? increases and that of the pairs of Mn3?+?–O–Mn4?+? experiencing double exchange decreases.  相似文献   

12.
A relationship between waste-water cleaning ability and local structure of iron-containing soda-lime silicate glass, 15Na2O·15CaO·xFe2O3·(70-x)SiO2 (x?= 10–50 in mass%), abbreviated as NCFSx glass, was investigated by means of 57Fe-Mössbauer spectroscopy, redox titration with KMnO4 for the determination of chemical oxygen demand (COD) and inductively coupled plasma optical emission spectroscopy (ICP-OES). Mössbauer spectra of NCFSx glass with “x” of 10 and 30 were composed of two doublets: one due to FeIIIO4 tetrahedra (T d) with isomer shift (δ) of 0.23–0.26 mm s???1 and quadrupole splitting (Δ) 1.01–1.04 mm s???1, and the other due to FeIIO6 octahedra (O h) with δ of 1.00–1.03 mm s???1 and Δ of 2.03–2.05 mm s???1. Absorption area for FeII(T d) was decreased from 9.7 to 6.5 and 0.0 % when “x” was increased from 10 to 30 and 50. A leaching test performed with 500 mL of artificial waste water and 2.0 g of NCFS50 revealed waste-water cleaning ability of soda-lime glass, e.g., COD was reduced from 280 to 55.2 mg L???1 after 10 day-leaching. After 10 day-leaching, it proved that iron was dissolved into waste water to a level of 5.3 $_{7} \times 10^{-1}$  mg L???1. These results prove that organic matter could be effectively decomposed with iron-containing soda-lime silicate glass.  相似文献   

13.
解忧  张建民 《中国物理 B》2011,20(12):127302-127302
Under the generalized gradient approximation, the electronic structures and magnetic properties of Fe(1-x)Cox alloy nanowires encapsulated inside zigzag (10,0) carbon nanotubes (CNTs) are investigated systematically using firstprinciple density functional theory calculations. For the fully relaxed Fe(1-x)Cox/CNT structures, all the C atoms relax outwards, and thus the diameters of the CNTs are slightly increased. Formation energy analysis shows that the combining processes of all Fe(1-x)Cox/CNT systems are exothermic, and therefore the Fe(1-x)Coxalloy nanowires can be encapsulated into semiconducting zigzag (10,0) CNTs and form stable hybrid structures. The charges are transferred from the Fe(1-x)Coxnanowires to the more electronegative CNTs, and the Fe-C/Co-C bonds formed have polar covalent bond characteristics. Both the spin polarization and total magnetic moment of the Fe(1-x)Cox/CNT system are smaller than those of the corresponding freestanding Fe(1-x)Coxnanowire, and the magnetic moment of the Fe(1-x)Cox/CNT system decreases monotonously with increasing Co concentration, but the Fe(1-x)Cox/CNT systems still have a large magnetic moment, implying that they can be utilized in high-density magnetic recording devices.  相似文献   

14.
Cr-based chalcogenide spinels, which do not have heterovalency and distortion-induced ions such as manganese oxides with perovskite structure, have demonstrated the existence of colossal magnetoresistance. In order to investigate the magnetotransport phenomena and magnetic properties of sulfospinels Zn x Fe1?x Cr2S4, polycrystalline Zn x Fe1?x Cr2S4 samples were synthesized in the 0?≤?x?≤?0.2 range by a solid reaction method. The crystal structure for x?=?0.05, 0.1, and 0.2 turned out to be cubic at room temperature by X-ray diffraction measurement. In magnetoresistance measurement, Zn x Fe1?x Cr2S4 samples indicate that this system is semiconducting below about 150 K. The temperature of maximum magnetoresistance is almost consistent with Curie temperature. The isomer shift and the electric quadrupole shift of Zn x Fe1?x Cr2S4 samples by Mössbauer experiment show that Fe2+ ions occupy the tetrahedral site in the spinel structure. As the Zn ions are substituted for Fe ions, the Jahn–Teller relaxation slows down and the electric quadrupole shift increases. The magnetotransport phenomena of Zn x Fe1?x Cr2S4 is related to Jahn–Teller effect and half-metallic electronic structure, which are different from the double exchange interactions of the manganite La–Ca–Mn–O system or the triple exchange interactions of sulfospinel Cu x Fe1?x Cr2S4.  相似文献   

15.
A relationship between methylene blue (MB) decomposition ability under visible light and local structure of xFe2O3·(100-x)SiO2 glass abbreviated as xFS prepared by sol-gel method was investigated by 57Fe-Mössbauer spectroscopy, X-ray diffractometry (XRD) and ultraviolet-visible light absorption spectroscopy (UV-Vis). Mössbauer spectra of xFS glass with x of 10, 30 and 50 annealed at 1000 °C for 3 h were mainly composed of a paramagnetic doublet due to fayalite (Fe2SiO4), and magnetic sextets due to magnetite (Fe3O4) or hematite (α-Fe2O3). The absorption area (A) of α-Fe2O3 gradually increased from 0.0 to 10.3 and 100 % with the increasing Fe2O3 content (x) of annealed xFS glass. A leaching test performed by 20 mL of MB aqueous solution and 40 mg of annealed 50FS glass showed that MB concentration decreased from 16.2 to 4.7 μmol L?1 after 2 h with the first order rate constant of 1.8 × 10?4 s?1. These results prove that annealed iron silicate glass containing α-Fe2O3 can decompose MB effectively under visible light irradiation.  相似文献   

16.
By introducing nickel chemical into the precursor sol of LiFePO4, a series of Ni-doped LiFePO4 composite cathode materials, denoted as LiFe1???x Ni x PO4/C (x?=?0, 0.01, 0.03, 0.05 and 0.10) were prepared by a spray drying–carbothermal approach. The materials were characterized with X-ray diffraction (XRD), scanning electron microscope (SEM), and electrochemical impedance spectrum etc. It is found that the doping of nickel with appropriate amount caused a slight shift of diffraction peaks towards higher angles and enhanced the dispersion of nanoprimary particles, which could be observed from their XRD patterns and SEM images. For the sample with 3 mol% Ni doing, the charge transfer resistance reduced from 52.4?Ω of LiFePO4 to 18.7?Ω of LiFe0.97Ni0.3PO4/C, and the potential interval of the redox peaks reduced from 0.51 to 0.40 V, indicating the better reversible of Ni-doped materials. For the sample LiFe0.97Ni0.03PO4/C, its initial discharge capacities at various rates are 169.2 (0.2 C), 156.2 (1.0 C), 147.9 (2.0 C), 135.5 (5.0 C), and 94.0 (10.0 C)?mAh g?1, respectively, enhanced by 55.2 % (at 5.0 C) and 82.1 % (at 10.0 C) compared with LiFePO4. Furthermore, after 200 cycles of charge/discharge at 0.5 C, the capacity of LiFe0.97Ni0.03PO4/C only decreased 8.8 %, but over 25 % decrease was observed for LiFePO4/C.  相似文献   

17.
A series of Sm-CoMn substituted hexagonal ferrites with chemical composition of Sr0.85-xCa0.15SmxFe12-y(Co0.5Mn0.5)yO19 (0.00?≤?x?≤?0.60, (0.00?≤?y?≤?0.50) were synthesized by the solid-state reaction method. Microstructure and magnetic properties of the hexaferrites have been investigated by the X-ray diffraction, field emission scanning electron microscopy and a permanent magnetic measuring system. A single magnetoplumbite phase is exhibited in the hexaferrites with the substitutiom of Sm (0.00?≤?x?≤?0.12) and CoMn (0.00?≤?y?≤?0.10) contents. For the hexaferrites containing Sm (x?≥?0.24) and CoMn (y?≥?0.20), impurity phases are observed in the structure. The FESEM micrographs exhibit that the hexaferrites with different Sm-CoMn contents have formed hexagonal structures and the grain size of the hexaferrites remains unchanged with increasing Sm-CoMn content. The remanence (Br), Hk/Hcj ratios, and maximum energy product [(BH)max] decrease with increasing Sm-CoMn content (0.00?≤?x?≤?0.60, (0.00?≤?y?≤?0.50). Instrinsic coercivity (Hcj) and magnetic induction coercivity (Hcb) increase with increasing Sm-CoMn content (0.00?≤?x?≤?0.12, 0.00?≤?y?≤?0.10), and then decrease with increasing Sm-CoMn content (0.12?≤?x?≤?0.36, 0.10?≤?y?≤?0.30), while for the hexaferrites with Sm (x?≥?0.36) and CoMn (y?≥?0.30), with increasing Sm-CoMn content, Hcj increases and Hcb decreases.  相似文献   

18.
Alloys of Y1???x Gd x Fe2B y (x = 0, 0.25, 0.5, 0.75 and 1; y = 0, 0.1, 0.15 and 0.2) have been prepared and investigated for structural and magnetic properties. The compounds with x = 0 and 1 are found to form in single phase with C15-type cubic Laves phase structure, while those with x = 0.25, 0.5 and 0.75 are observed to form with small quantities of secondary (Y,Gd)Fe3 phase. The lattice parameters, Curie temperature and the average Fe hyperfine field are found to increase with increasing x. The Gd–Gd and Gd–Fe interactions are attributed to be the main reason for the enhancement of magnetic properties. Boron was found to stabilize the (Y,Gd)Fe2 phase without affecting the magnetic properties.  相似文献   

19.
The composite materials Cs(HSO4)1?x (H2PO4) x were investigated by X-ray phase analysis, differential scanning calorimetry, nuclear magnetic resonance (NMR) relaxation, pulsed field gradient NMR (PFG-NMR) and impedance spectroscopy. Three composite materials types x = 0.1 ÷ 0.3 mixture CsHSO4, α-Cs3(HSO4)2(H2PO4), β-Cs3(HSO4)2.5(H2PO4)0.5—compositions of area I; x = 0.4 ÷ 0.5 mixture α-Cs3(HSO4)2(H2PO4) and Cs2(HSO4)(H2PO4)—compositions of area II; x = 0.6 ÷ 0.9 mixture Cs2(HSO4)(H2PO4) and CsH2PO4—compositions of area III, were synthesized. The phase transition temperature from the low-to-high conductive phase for obtained composite materials is notably below (about 100 °C) than that for the individual components. The proton self-diffusion coefficients measured by PFG-NMR are lower than the diffusion coefficients calculated from proton conductivities data. The correlation times τ d controlling the 31P–1H magnetic dipole–dipole interaction were calculated according to data of the spin–lattice relaxation on 31P nuclei. The self-diffusion coefficients estimated from the Einstein equation are in good agreement with the experimental self-diffusion coefficients measured by PFG-NMR. It confirms the fact that the proton mobility is caused by the rotation of PO4 anion tetrahedra.  相似文献   

20.
Lanthanum ion (La3+)-substituted garnet nanoparticles Y3?x La x Fe5O12 (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) were fabricated by a sol–gel method. Their crystalline structures and magnetic properties were investigated by using X-ray diffraction (XRD), vibrating sample magnetometer (VSM), and Mössbauer spectrum. The XRD results show that samples of Y3?x La x Fe5O12 (0.0 ≤ x ≤ 0.8) are all single phase and the sizes of particles range from 32 to 65 nm. Those of Y2LaFe5O12 consisted of peaks from garnet and LaFeO3 structures. Compared to pure YIG, the saturation magnetization is larger when the La concentration x = 0.2. However, with increasing La concentration (x), it decreases obviously. Meanwhile, may be due to the enhancement of the surface spin effects, the saturation magnetization rises as the particle size is increased. Different from the pure YIG, the Mössbauer spectra of Y2.8La0.2Fe5O12 and Y2.2La0.8Fe5O12 are composed of four sets of six-line hyperfine patterns. The results tell us that the substitution of La3+ ions with large ionic radius (1.061 Å) will give rise to a microscopic structure distortion of the a- and d-sites to different degrees, and the Zeeman sextets from a- and d-sites begin to split into two sub-sextets, which is helpful to explain the phenomenon observed in the study of the magnetic property.  相似文献   

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