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1.
By employment of nano-sized pre-prepared Mn3O4 as precursor, LiMn2O4 particles have been successfully prepared by facile solid state method and sol-gel route, respectively. And the reaction mechanism of the used precursors of Mn3O4 is studied. The structure, morphology, and element distribution of the as-synthesized LiMn2O4 samples are characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Compared with LiMn2O4 synthesized by facile solid state method (SS-LMO), LiMn2O4 synthesized by modified sol-gel route (SG-LMO) possesses higher crystallinity, smaller average particle size (~175 nm), higher lithium chemical diffusion coefficient (1.17 × 10?11 cm2 s?1), as well as superior electrochemical performance. For example, the cell based on SG-LMO can deliver a capacity of 85.5 mAh g?1 at a high rate of 5 °C, and manifests 88.3% capacity retention after 100 cycles at 0.5 °C when cycling at 45 °C. The good electrochemical performance of the cell based on SG-LMO is ascribed mainly to its small particle size, high degree of dispersion, and uniform element distribution in bulk material. In addition, the lower polarization potential accelerates Li+ ion migration, and the lower atom location confused degree maintains integrity of crystal structure, both of which can effectively improve the rate capability and cyclability of SG-LMO.  相似文献   

2.
Undoped and different concentration Nd3+ doped SrNb2O6 powders with columbite structure were synthesized by molten salt process using a mixture of strontium nitrate and niobium (V) oxide and NaCl-KCl salt mixture as a flux under relatively low calcining temperature. X-ray diffraction analysis results indicated that SrNb2O6 phases found to be orthorhombic columbite single phase for undoped, 0.5 and 3 mol% Nd3+ doping concentrations. Phase composition of the powders was examined by SEM-EDS analyses. Radioluminescence properties of Nd3+ doped samples from UV to near-IR spectral region were studied. The emissions increased with the doping concentration of up to 3 mol%, and then decreased due to concentration quenching effect. There is a sharp emission peak around 880 nm associated with 4F5/2 → 4I9/2 transition in the Nd3+ ion between 300 and 1100 nm. The broad emission band intensity was observed from 400 to 650 nm where the peak intensities increased by increasing Nd3+ doping concentration. All the measurements were taken under the room temperature.  相似文献   

3.
Europium ions (Eu3+) and Lithium ions (Li+) codoped gadolinium orthovanadate with a tetragonal phase had been successfully synthesized by an efficient hydrothermal method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) were utilized to characterize the microstructure, morphology, and luminescent properties of as-prepared samples. The various concentrations (0~14 at.%) of Li ions were applied to investigate the effect of Li+ co-doping concentration on the crystalline structure, microstructure, and emission intensity of GdVO4:Eu3+, Li+ nanophosphors. The results demonstrated that Li+ ion co-doping changes the lattice parameters in two different ways. Moreover, the optical photoluminescent property was obtained when the Li+ co-doping concentration is 10 at.%. The influence of Li+ co-doping on the concentration quenching effect of Eu3+ was discussed as well. The concentration quenching threshold of Eu3+ was increased distinguishably. The potential mechanism was proposed in this paper.  相似文献   

4.
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   

5.
A Pr3+:KLu(WO4)2 crystal with dimension of 30 × 30 × 15 mm3 was grown in the K2W2O7 flux. A slice was cut from the crystal, and the polarized absorption and fluorescence spectra were measured at room temperature. Based on the J-O theory, the oscillator intensity parameters Ω t (t = 2, 4, 6), spontaneous emission probabilities and branch ratios were estimated and good results had been obtained. Furthermore, the crystal has a relatively large emission cross-section in the region of 615–630 nm with the highest value of 14.5 × 10?20 cm2, which indicates that the crystal is good for the application in red emission laser. The emission decay time for 1D2 and 3P0 multiplets was discussed. By adapting the I-H model to fit the emission decay curves, the lifetime for 1D2 at 607 nm and 3P0 at 615 nm are 19.72 μs and 8.95 μs, respectively. Then the corresponding fluorescence quantum efficiencies of the two multiplets reach 83.7 % and 87.9 %, respectively. All the studies illustrate that this crystal is potential in red emission laser application.  相似文献   

6.
The non-doped and doped Nd3+ of Ca9.03Na1.08La0.62(VO4)7 crystals were grown by the Czochralski technique. The effective segregation coefficients of Na+ and Nd3+ ions in the crystal were measured to be about 0.5 and 1.1, respectively. The XPS analysis of Ca9.03Na1.08La0.62(VO4)7 crystal indicates that the vanadium in the crystal is a mixture of V4+ (1.46 at. %) and V5+ (98.54 at. %). The hardness of Nd:Ca9.03Na1.08La0.62(VO4)7 crystal is about 383.1 VDH. Nd:Ca9.03Na1.08La0.62(VO4)7 crystal exhibits similar thermal expansion coefficients along the a (11.2×10-6 K-1) and c (13.7×10-6 K-1) axes, indicating a low thermal expansion anisotropy (αca≈1.2). The qualitative frequency-doubling experiment shows that the doping of Na+ ion can help reduce the scattering of frequency-doubling light, and the intensity of SHG for Ca9.03Na1.08La0.62(VO4)7 crystal is found to be about 3.5 times as large as that of KDP. The polarized absorption and fluorescence spectra are analyzed based on Judd–Ofelt theory, which exhibits that the π-polarized absorption and stimulated emission cross sections are 6.07×10-20 cm2 with an FWHM 12.0 nm at 810 nm and 1.42×10-19 cm2 at 1069 nm, respectively. The fluorescence lifetime is 115 μs at room temperature. All the results indicate that Nd:Ca9.03Na1.08La0.62(VO4)7 crystal is a candidate of self-frequency doubling laser material. PACS 42.62.Fi; 42.70.Mp; 81.10.Fq  相似文献   

7.
A series of Li3V2(PO4)3/C composite cathodes have been prepared by the organic solvent replacement drying method. Five kinds of organic solvent including ethyl alcohol, butyl alcohol, 2-methoxyethanol, 1,2-propylene glycol, and ethylene glycol were used in the drying process to replace the water respectively. Powder X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge tests were employed to analyze the crystal structure, morphology, and electrochemical properties of the as-prepared materials. The results show that the organic solvent has a great influence on the secondary particle size of the as-synthesized materials. Special emphasis is placed on the sample prepared with 1,2-propylene glycol, which has the smallest average particle size and uniform distribution, thus leading to the best high rate performance and long-term cycling stability. The electrode exhibits average specific discharge capacities of 127.6, 128.3, 127.7, 126.7, 125.5, 124.4, 121.9, and 117.0 mAh g?1 at 0.1, 0.2, 0.5, 1, 3, 5, 10, and 20C, respectively. More encouragingly, this sample delivers an outstanding cycle life with capacity retention of up to 94.68% even after 1000 cycles at 20C. Moreover, EIS results demonstrate that this sample has the minimum resistance and the largest apparent lithium ion diffusion coefficient (1.569 × 10?7 cm2 s?1) which can facilitate to the Li+ diffusion during the charge/discharge process. Our results indicate that this preparation strategy can be facile and versatile for the synthesis of other high-rate and high-capacity intercalation materials.  相似文献   

8.
A comparison of electrochemical performance between LiFe0.4Mn0.595Cr0.005PO4/C and LiMnPO4/C cathode materials was conducted in this paper. The cathode samples were synthesized by a nano-milling-assisted solid-state process using caramel as carbon sources. The prepared samples were investigated by XRD, SEM, TEM, energy-dispersive X-ray spectroscopy (EDAX), powder conductivity test (PCT), carbon-sulfur analysis, electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge cycling. The results showed that LiFe0.4Mn0.595Cr0.005PO4/C exhibited high specific capacity and high energy density. The initial discharge capacity of LiFe0.4Mn0.595Cr0.005PO4/C was 163.6 mAh g?1 at 0.1C (1C = 160 mA g?1), compared to 112.3 mAh g?1 for LiMnPO4/C. Moreover, the Fe/Cr-substituted sample showed good cycle stability and rate performance. The capacity retention of LiFe0.4Mn0.595Cr0.005PO4/C was 98.84 % over 100 charge-discharge cycles, while it was only 86.64 % for the pristine LiMnPO4/C. These results indicated that Fe/Cr substitution enhanced the electronic conductivity for the prepared sample and facilitated the Li+ diffusion in the structure. Furthermore, LiFe0.4Mn0.595Cr0.005PO4/C composite presented high energy density (606 Wh kg?1) and high power density (574 W kg?1), thus suggested great potential application in lithium ion batteries (LIBs).  相似文献   

9.
Undoped and PbNb2O6:Eu3+ (1.0 ≤ x ≤ 6.0 mol%) phosphors were synthesized at 1100 °C for 3.5 h by the conventional solid state reaction method. Synthesized PbNb2O6:Eu3+ phosphors were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and Photoluminescence (PL) analyses. The PL spectra showed series of excitation peaks between 350 and 430 nm due to the 4f–4f transitions of Eu3+. For 395.0 nm excitation, emission spectra of Eu3+ doped samples were observed at 591 nm (orange) and 614 nm (red) due to the 5D0 → 7F1 transitions and 5D0 → 7F2 transitions, respectively. PL analysis results also showed that the emission intensity increased by increasing Eu3+ ion content. No concentration quenching effect was observed. The CIE chromaticity color coordinates (x,y) of the PbNb2O6:Eu3+ phosphors were found to be in the red region of the chromaticity diagram.  相似文献   

10.
Yb3+-Tm3+ co-doped up-conversion powder phosphors using Zn(AlxGa1-x)2O4 (ZAGO) as the host materials were synthesized via solid-state reaction successfully. In addition, the morphology, structural characterization and up-conversion luminescent properties were all investigated by scanning electron microscope (SEM), x-ray diffraction (XRD) and fluorescence spectrophotometer (F-7000), respectively. Under the excitation of a 980 nm laser, all as-prepared powders can carry out blue emission at about 477 nm (corresponding to 1G4 → 3H6 transition of Tm3+ ions), and red emission at about 691 nm (attributed to 3F3 → 3H6 transition of Tm3+ ions). Also, the influence of doping Al3+ ions were investigated. In brief, the doping of Al3+ ions has no effect on the position of emission peak. Howbeit the up-conversion efficiency and intensity of ZAGO:Yb,Tm phosphors are stronger than ZGO:Yb,Tm and ZAO:Yb,Tm phosphors, while the crystallinity is the opposite. More particularly, all as-prepared powder phosphors emit strong luminescence, which is observable by the naked eye, demonstrating the potential applications in luminous paint, luminescent dye, etc.  相似文献   

11.
Mn1.5Co1.5O4 hierarchical microspheres have been successfully synthesized via a solvothermal method and an annealing procedure. Mn1.5Co1.5O4 exhibits advanced cycling performance, and it retains a reversible capacity of 633 mA h g?1 at a current density of 400 mA g?1 with a coulombic efficiency of 99.0% after 220 cycles. Its remarkable performance is attributed to the hierarchical structure assembled with nanorods, which increases the contact area between each nanorod and electrolyte. More significantly, the open space between neighboring nanorods and the pores on the surface of nanorods can improve Li+ ion diffusion rate. Furthermore, the nanorods have rapid one-dimensional Li+ diffusion channels, which not only possess a large specific surface area for high activity but accommodate the volume change during lithiation–delithiation processes. Therefore, Mn1.5Co1.5O4 hierarchical microspheres can act as a promising alternative anode material for lithium-ion battery.  相似文献   

12.
Spinel-type LiNi0.5Mn1.5O4 (LNMO) cathode materials for lithium ion batteries have been synthesized via a modified oxalate co-precipitation method. By virtue of the co-precipitation of Li+ with transition metal ions, the target materials can be obtained through one-pot reaction without subsequent mixing with lithium salts. What’s more, a uniform distribution between the lithium and transition metal ions at molecular level could be realized, which is beneficial for final electrochemical performances. The physical and electrochemical properties of the material are characterized by XRD, TGA, EDS, FT-IR, SEM, CV, EIS, and charge/discharge tests. The results prove that the as-prepared material owns a cubic spinel structure with a space group of Fd-3m, high crystallinity, uniform particle size, and excellent electrochemical performances. A higher initial capacity and superior rate performance are delivered compared with that of material by conventional co-precipitation method. High capacities of 131.7 and 104.0 mAh g?1 could be displayed at 0.5 and 10 C, respectively. Excellent cycle stability is also demonstrated with more than 98.5 % capacity retention after 100 cycles at 1 C.  相似文献   

13.
Advanced Li-air battery architecture demands a high Li+ conductive solid electrolyte membrane that is electrochemically stable against metallic lithium and aqueous electrolyte. In this work, an investigation has been carried out on the microstructure, Li+ conduction behaviour and structural stability of Li7La3-x Y x Zr2O12 (x = 0.125, 0.25 and 0.50) prepared by conventional solid-state reaction technique. The phase analysis of Li7La3-x Y x Zr2O12 (x = 0.125, 0.25 and 0.50) sintered at 1200 °C by powder X-ray diffraction (PXRD) and Raman confirms the formation of high Li+ conductive cubic phase (\( Ia\overline{3}d \)) lithium garnets. Among the investigated lithium garnets, Li7La2.75Y0.25Zr2O12 sintered at 1200 °C exhibits a maximized room temperature total (bulk + grain boundary) Li+ conductivity of 3.21 × 10?4 S cm?1 along with improved relative density of 96 %. The preliminary investigation on the structural stability of Li7La2.75Y0.25Zr2O12 in the solutions of 1 M LiCl, dist. H2O and 1 M LiOH at 30 °C/50 °C indicates that the Li7La2.75Y0.25Zr2O12 is relatively stable against 1 M LiCl and dist. H2O. Further electrochemical investigation is essential for practical application of Li7La2.75Y0.25Zr2O12 as protective solid electrolyte membrane in aqueous Li-air battery.  相似文献   

14.
A crystalline structure of LiCoO2 sample was synthesized at different stirring times via sol-gel method. This was followed by the electrochemical characterization of LiCoO2 in 5 M LiNO3 aqueous electrolyte. The hexagonal LiCoO2 was stirred for 30 h produced the highest peak intensity and smallest particle size. A morphological analysis showed the particle size distribution within the range of 0.32–0.47 μm. At lower scan rates of cyclic voltammetry, three pairs of redox peaks at ESCE = 0.81/0.65, 0.89/0.83 and 1.01/0.95 V were observed. The peak separation was proportionally consistent with Li+ diffusion coefficients of 7.42 × 10?8 cm2 s?1 (anodic) and 3.59 × 10?8 cm2 s?1 (cathodic). For specific capacity, the LiCoO2 demonstrated a higher initial specific capacity (115.49 mA h g?1). A small difference (1.92 Ω) in the charge transfer resistance before and after a charge discharge analysis indicated that the Li+ ions had been well-diffused during the intercalation/de-intercalation process.  相似文献   

15.
A. Oueslati 《Ionics》2017,23(4):857-867
A lithium yttrium diphosphate LiYP2O7 was prepared by a solid-state reaction method. Rietveld refinement of the X-ray diffraction pattern suggests the formation of the single phase desired compound with monoclinic structure at room temperature. The infrared and Raman spectrum of this compound was interpreted on the basis of P2O7 4? vibrations. The AC conductivity was measured in the frequency range from 100 to 106 Hz and temperatures between 473 and 673 K using impedance spectroscopy technique. The obtained results were analyzed by fitting the experimental data to the equivalent circuit model. The Cole–Cole diagram determined complex impedance for different temperatures. The angular frequency dependence of the AC conductivity is found to obey Jonscher’s relation. The temperature dependence of σ AC could be described in terms of Arrhenius relation with two activation energies, 0.87 eV in region I and 1.36 eV in region II. The study of temperature variation of the exponent(s) reveals two conduction models: the AC conduction dependence upon temperature is governed by the correlated barrier hopping (CBH) model in region I (T < 540 K) and non-overlapping small polaron tunneling (NSPT) model in region II (T > 540 K). The near value of activation energies obtained from the equivalent circuit and DC conductivity confirms that the transport is through ion hopping mechanism dominated by the motion of the Li+ ion in the structure of the investigated material.  相似文献   

16.
Antimony trioxide (Sb2O3) nanoparticles with particle size range from 2 to 12 nm were successfully synthesized by chemical reducing method. Antimony trichloride was reduced by hydrazine with the presence of sodium hydroxide (NaOH) as catalyst in ethylene glycol at 120 °C for 1 h. Effects of hydrazine concentration ([N2H5OH]/[Sb3+] = 0.75, 5, 10, 20, and 30, when concentration of NaOH was fixed [NaOH]/[Sb3+] = 3) and NaOH concentration ([NaOH]/[Sb3+] = 0, 1, 3, and 5, when concentration of hydrazine was fixed [N2H5OH]/[Sb3+] = 10) on the particle size and shape of the Sb2O3 nanoparticles were investigated. Transmission electron microscope, selected area electron diffraction pattern, and high resolution electron microscope were employed to study the morphology and crystallinity of the nanoparticles. It was observed that the particle size decreased and remained constant when [N2H5OH]/[Sb3+]) ≥ 10 and [NaOH]/[Sb3+] = 3. Further study on the crystallinity and phase of the nanoparticles was assisted by X-ray diffractometer (XRD). XRD revealed a cubic phase of Sb2O3 (ICDD file no. 00-043-1071) with preferred plane of (622) and lattice spacing of 1.68 Å. Correlation between UV–visible absorption wavelengths of the nanoparticles and their sizes was established.  相似文献   

17.
Li3V2(PO4)3 glass-ceramic nanocomposites, based on 37.5Li2O-25V2O5-37.5P2O5 mol% glass, were successfully prepared via heat treatment (HT) process. The structure and morphology were investigated by X-ray diffraction (XRD) and scanning electron microscope (SEM). XRD patterns exhibit the formation of Li3V2(PO4)3 NASICON type with monoclinic structure. The grain sizes were found to be in the range 32–56 nm. The effect of grain size on the dynamics of Li+ ions in these glass-ceramic nanocomposites has been studied in the frequency range of 20 Hz–1 MHz and in the temperature range of 333–373 K and analyzed by using both the conductivity and modulus formalisms. The frequency exponent obtained from the power law decreases with the increase of temperature, suggesting a weaker correlation among the Li+ ions. Scaling of the conductivity spectra has also been performed in order to obtain insight into the relaxation mechanisms. The imaginary modulus spectra are broader than the Debye peak-width, but are asymmetric and distorted toward the high frequency region of the maxima. The electric modulus data have been fitted to the non-exponential Kohlrausch–Williams–Watts (KWW) function and the value of the stretched exponent β is fairly low, suggesting a higher ionic conductivity in the glass and its glass-ceramic nanocomposites. The advantages of these glass-ceramic nanocomposites as cathode materials in Li-ion batteries are shortened diffusion paths for Li+ ions/electrons and higher surface area of contact between cathode and electrolyte.  相似文献   

18.
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   

19.
Lithium-rich cathode material Li[Li0.2Ni0.13Co0.13Mn0.54]O2 doped with trace Mo is successfully synthesized by a sol-gel method. The X-ray diffraction patterns show that trace Mo substitution increases the inter-layer space of the material, of which is benefiting to lithium ion insertion/extraction among the electrode materials. The (CV) tests demonstrate the decrease of polarization, and on the other hand, the lithium ion diffusion coefficient (D Li) of the modified material turns out to be larger, which indicates a faster electrochemical process. As a result, the Mo doped material possesses high rate performance and good cycling stability, and the initial discharge capacity reaches 149.3 mAh g?1 at a current density of 5.0 °C, and the residual capacity is 144.0 mAh g?1 after 50 cycles with capacity retention of 96.5 % in the potential range of 2.0–4.8 V at room temperature.  相似文献   

20.
S/Li4Ti5O12 cathode with high lithium ionic conductivity was prepared for Li-S battery. Herein, nano Li4Ti5O12 is used as sulfur host and fast Li+ conductor, which can adsorb effectively polysulfides and improve remarkably Li+ diffusion coefficient in sulfur cathode. At 0.5 C, S/Li4Ti5O12 cathode has a stable discharge capacity of 616 mAh g?1 at the 700th cycle and a capacity loss per cycle of 0.0196% from the second to the 700th cycle, but the corresponding values of S/C cathode are 437 mAh g?1 and 0.0598%. Even at 2 C, the capacity loss per cycle of S/Li4Ti5O12 cathode is only 0.0273% from the second to the 700th cycle. The results indicate that Li4Ti5O12 as the sulfur host plays a key role on the high performance of Li-S battery due to reducing the shuttle effect and enhancing lithium ionic conductivity.  相似文献   

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