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1.
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   

2.
Carbon-coated olivine-structured LiFe0.5Co0.5PO4 solid solution was synthesized by a facile rheological phase method and applied as cathode materials of lithium-ion batteries. The nanostructure’s properties, such as morphology, component, and crystal structure for the samples, characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer, Emmett, and Teller (BET) determination, X-ray photoelectron spectroscopy (XPS), and the electrochemical performances were evaluated using constant current charge/discharge tests and electrochemical impedance spectroscopy (EIS). The results indicate that nanoplatelet- and nanorod-structured LiFe0.5Co0.5PO4/C composites were separately obtained using stearic acid or polyethylene glycol 400 (PEG400) as carbon source, and the surfaces of particles for the two samples are ideally covered by full and uniform carbon layer, which is beneficial to improving the electrochemical behaviors. Electrochemical tests verify that the nanoplatelet LiFe0.5Co0.5PO4/C shows a better capacity capability, delivering a discharge specific capacity of 133.8, 112.1, 98.3, and 74.4 mAh g?1 at 0.1, 0.5, 1, and 5 C rate (1 C?=?150 mA g?1); the corresponding cycle number is 5th, 11th, 15th, 20th, and 30th, respectively, whereas the nanorod one possesses more excellent cycling ability, with a discharge capacity of 83.3 mAh g?1 and capacity retention of 86.9% still maintained after cycling for 100 cycles at 0.5 C. Results from the present study demonstrate that the LiFe0.5Co0.5PO4 solid solution nanomaterials with favorable carbon coating effect combine the characteristics and advantage of LiFePO4 and LiCoPO4, thus displaying a tremendous potential as cathode of lithium-ion battery.  相似文献   

3.
The layered LiNi0.5Mn0.47Al0.03O2 was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO2 structure. This substitution of Al for Mn promotes the formation of Li(Ni0.472+Ni0.033+Mn0.474+Al0.033+)O2 structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni2+ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni2+(3a)–Mn4+(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni2+ (S = 1), Ni3+ (S = 1/2) and Mn4+ (S = 3/2) spin-only values. Delithiation has been made by the use of K2S2O8. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni4+ in the high spin configuration, while Ni2+(3a)–Mn4+(3b) ferromagnetic pairs remain, as the Li+(3b) ions linked to the Ni2+(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn4+ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.  相似文献   

4.
Several olivine phosphates were investigated in the last years as cathode materials for secondary lithium ion batteries. Among these compounds, LiFe x Co1 − x PO4 solid solutions might be interesting candidates because they should combine the high potential value of Co3+/Co2+ (higher than 4.5 V vs Li+/Li) with the relatively high charge–discharge rate of LiFePO4. Solid solutions were prepared by solid-state route and characterised by X-ray powder diffraction, cyclic voltammetry, impedance spectroscopy and the Hebb–Wagner method. The results show that also low amount of iron induces high electronic conductivity in the solid solutions.  相似文献   

5.
(K0.5Na0.5)(Nb1-xTax)O3 lead-free piezoelectric ceramics have been prepared by an ordinary sintering technique. The results of X-ray diffraction reveal that Ta5+ diffuses into the K0.5Na0.5NbO3 lattices to form a solid solution with an orthorhombic perovskite structure. Because of the high melting temperature of KTaO3, the (K0.5Na0.5)(Nb1-xTax)O3 ceramics can be sintered at higher temperatures. The partial substitution of Ta5+ for the B-site ion Nb5+ decreases both paraelectric/cubic–ferroelectric/tetragonal and ferroelectric/tetragonal–ferroelectric/orthorhombic phase transition temperatures, TC and TO-T. It also induces a relaxor phase transition and weakens the ferroelectricity of the ceramics. The ceramics become ‘softened’, leading to improvements in d33, kp, kt and εr and a decease in Ec, Qm and Np. The ceramics with x=0.075–0.15 become optimum, having d33=127–151 pC/N, kp=0.43–0.44, kt=0.43–0.44, εr=541–712, tanδ=1.75–2.48% and TC=378–329 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s  相似文献   

6.
AlF3-coating is attempted to improve the performance of LiNi0.5Mn1.5O4 cathode materials for Li-ion batteries. The prepared powders are characterized by scanning electron microscope, powder X-ray diffraction, charge/discharge, and impedance. The coated LiNi0.5Mn1.5O4 samples show higher discharge capacity, better rate capability, and higher capacity retention than the uncoated samples. Among the coated samples, 1.0 mol% AlF3-coated sample shows highest capacity after charge–discharged at 30 mA/g for 3 cycles, but 4.0 mol% coated sample exhibits the highest capacity and cycling stability when cycled at high rate of 150 and 300 mA/g. The 40th cycle discharge capacity at 300 mA/g current still remains 114.8 mAh/g for 4.0 mol% AlF3-coated LiNi0.5Mn1.5O4, while only 84.3 mAh/g for the uncoated sample.  相似文献   

7.
The magnetic properties of the Nd0.5Gd0.5Fe3(BO3)4 single crystal have been studied in principal crystallographic directions in magnetic fields to 90 kG in the temperature range 2–300 K; in addition, the heat capacity has been measured in the range 2–300 K. It has been found that, below the Néel temperature T N = 32 K down to 2 K, the single crystal exhibits an easy-plane antiferromagnetic structure. A hysteresis has been detected during magnetization of the crystal in the easy plane in fields of 1.0–3.5 kG, and a singularity has been found in the temperature dependence of the magnetic susceptibility in the easy plane at a temperature of 11 K in fields B < 1 kG. It has been shown that the singularity is due to appearance of the hysteresis. The origin of the magnetic properties of the crystal near the hysteresis has been discussed.  相似文献   

8.
LiNi0.5Mn0.5O2 powder was synthesized by a coprecipitation method. LiOH.H2O and coprecipitated [(Ni0.5Mn0.5)C2O4] precursors were mixed carefully together and then calcined at 900°C. Surface modified cathode materials were obtained by coating LiNi0.5Mn0.5O2 with a thin layer of amorphous carbon using table sugar and starch as carbon source. Both parent and carbon-coated samples have the characteristic layered structure of LiNi0.5Mn0.5O2 as estimated from X-ray diffractometry measurements. Transmission electron microscope showed the presence of C layer around the prepared particles. TGA analysis emphasized and confirmed the presence of C coating around LiNi0.5Mn0.5O2. It is obvious that the carbon coating appears to be beneficial for the electrochemical performance of the LiNi0.5Mn0.5O2. A capacity of about 150 mAh/g is delivered in the voltage range 2.5–4.5 V at current density C/15 for carbon coated LiNi0.5Mn0.5O2 in comparison with about 165 mAh/g obtained for carbon free LiNi0.5Mn0.5O2 at the same current density and voltage window. About 92% and 82% capacity retention was obtained at 50th cycle for coated LiNi0.5Mn0.5O2 using sucrose and starch, respectively; whereas, 75% was retained after only 30th cycle for carbon free LiNi0.5Mn0.5O2. This improvement is mainly attributed to the presence of thin layer of carbon layer that encapsulate the nanoparticles and improve the conductivity and the electrochemical performance of LiNi0.5Mn0.5O2.  相似文献   

9.
本文用DFT计算方法研究了LiFexMn1-xPO4的热力学稳定性和嵌/脱锂电位. 结果表明,LiFexMn1-xPO4固溶体的自由能比相分离的LiFePO4/LiMnPO4混合物略高,这两种形式可能在实际LiFexMn1-xPO4材料中共存. 计算表明,LiFexMn1-xPO4固溶体的嵌/脱锂电位随锰/铁比以及过渡金属离子的空间排列而变化,并用计算结果解释了放电曲线的形状. 采用固相反应法合成了LiFexMn1-xPO4材料并研究了其电化学性质,实验中观察到附加的放电平台,其出现可能与LiFexMn1-xPO4固溶体的存在有关.  相似文献   

10.
Magnetic and kinetic properties as well as transmission and absorption spectra of Hg 1−x−y Mn x Fe ySe (0.09 ≤ x ≤ 0.099 and 0.001 ≤ y ≤ 0.01) crystals are investigated at H ≈ 0.5–6 kOe in the temperature range T = 77–300 K. The band parameters are determined on the basis of experimental data. It is found that in the crystals under study at T ≈ 300 K, electron scattering by polar optical phonons dominates, direct optical band-to-band transitions occur, and replacement of a part of Mn atoms by Fe for x + y = 0.1 results in an increase in Eg op with Fe content. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 35–39, March, 2007.  相似文献   

11.
Using an ordinary ceramic fabrication technique, we fabricated lead-free (1-x)(K0.5Na0.5)NbO3-xBa(Ti0.95Zr0.05)O3 ceramics with CuO sintering aid . Ba(Ti0.95Zr0.05)O3 diffuses into (K0.5Na0.5)NbO3 to form a new solid solution. The ceramics with perovskite structure possess orthorhombic phase at x≤0.04 and become tetragonal phase at x≥0.06. Both the paraelectric cubic–ferroelectric tetragonal and the ferroelectric tetragonal–ferroelectric orthorhombic phase transition temperatures decrease with increasing the concentration of Ba(Ti0.95Zr0.05)O3. The doping of CuO effectively promotes the densification of the ceramics. The coexistence of the orthorhombic and tetragonal phases at 0.04<x<0.06 and the improvement in sintering performances of the ceramics significantly enhance the piezoelectric and dielectric properties at room temperature. The ceramics with x=0.04–0.06 and y=0.75–1.50 possess excellent properties: d33=119–185 pC/N, kP=37–44%, kt=35–49%, ε=341–1129, cosδ=0.7–4.4% and Tc=312–346 °C. PACS 77.65.-j; 77.84.Dy; 77.84.-s  相似文献   

12.
The specific features of the crystal structure and the magnetic state of stoichiometric lithium manganite in the structurally ordered Li[Mn2]O4 and disordered Li1 − δMnδ[Mn2 − δLiδ]O4 (δ = 1/6) states have been investigated using neutron diffraction, X-ray diffraction, and magnetic methods. The structurally disordered state of the manganite was achieved under irradiation by fast neutrons (E eff ≥ 1 MeV) with a fluence of 2 × 1020 cm−2 at a temperature of 340 K. It has been demonstrated that, in the initial sample, the charge ordering of manganese ions of different valences arises at room temperature, which is accompanied by orthorhombic distortions of the cubic spinel structure, and the long-range antiferromagnetic order with the wave vector k = 2π/c(0, 0, 0.44) is observed at low temperatures. It has been established that the structural disordering leads to radical changes in the structural and magnetic states of the LiMn2O4 manganite. The charge ordering is destroyed, and the structure retains the cubic symmetry even at a temperature of 5 K. The antiferromagnetic type of ordering transforms into ferrimagnetic ordering with local spin deviations in the octahedral sublattice due to the appearance of intersublattice exchange interactions.  相似文献   

13.
Emission spectra of three Cd0.6Mn0.4Te/Cd0.5Mg0.5Te superlattices with Cd0.6Mn0.4Te quantum-well (QW) widths of 7, 13, and 26 monolayers, respectively, and the same thickness (46 monolayers) of the Cd0.5Mg0.5Te barriers have been studied. The QW width affects the shape and spectral position of the Mn2+ intracenter luminescence (IL) band as a result of the crystal field being dependent on the position of the manganese ion with respect to the interface. Measured in identical experimental conditions, the exciton luminescence as compared to the IL is substantially higher in intensity in a QW than in a bulk CdMnTe crystal. Some samples of superlattices and bulk crystals exhibit, in addition to the conventional IL band near 2.0 eV, a weaker band at about 1.45 eV. This band apparently derives from intracenter transitions in the Mn2+ ions in the regions where the crystal lattice has the rock-salt rather than the conventional zinc blende structure.  相似文献   

14.
The atomic and magnetic structures of La0.5Ca0.5CoO3 cobaltite have been studied by the neutron diffraction technique at high pressures of up to 4 GPa in the 10- to 300-K temperature range. The pressure dependences of the structural parameters have been obtained. The Curie temperature increases with the pressure with the coefficient dT C/dP = 1 K/GPa, demonstrating the stability of the ground ferromagnetic (FM) state. The pressure dependence of the ground FM state in La0.5Ca0.5CoO3 is in drastic contrast with that for La1 − x Ca x CoO3 at a lower calcium content (x < 0.3). For the latter compound, the pressure suppressed the ground FM state and a large negative pressure coefficient of the Curie temperature (dT C/dP ∼ −10 K/GPa) was observed. The nature of such a phenomenon is analyzed in the framework of the double exchange model also taking into account the changes in the electron configuration of Co3+ ions.  相似文献   

15.
The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li6(Y,Gd,Eu)(BO3)3 have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li6Gd(BO3)3, Li6Eu(BO3)3, Li6Y0.5Gd0.5(BO3)3: Eu, and Li6Gd(BO3)3: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the 6 P J 8 S 7/2 transitions in the Gd3+ ion and the group of lines at 580–700 nm due to the 5 D 07 F J transitions (J = 0–4) in the Eu3+ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.  相似文献   

16.
The [N(CH3)4][N(C2H5)4]ZnCl4 compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P21212 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M * for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.  相似文献   

17.
The results of neutron diffraction studies of the La0.70Sr0.30MnO2.85 compound and its behavior in an external magnetic field are stated. It is established that in the 4–300 K temperature range, two structural perovskite phases coexist in the sample, which differ in symmetry (groups R[`3]cR\bar 3c and I4/mcm). The reason for the phase separation is the clustering of oxygen vacancies. The temperature (4–300 K) and field (0–140 kOe) dependences of the specific magnetic moment are measured. It is found that in zero external field, the magnetic state of La0.70Sr0.30MnO2.85 is a cluster spin glass, which is the result of frustration of Mn3+-O-Mn3+ exchange interactions. An increase in external magnetic field up to 10 kOe leads to fragmentation of ferromagnetic clusters and then to an increase in the degree of polarization of local spins of manganese and the emergence of long-range ferromagnetic order. With increasing magnetic field up to 140 kOe, the magnetic ordering temperature reaches 160 K. The causes of the structural and magnetic phase separation of this composition and formation mechanism of its spin-glass magnetic state are analyzed.  相似文献   

18.
We have studied photoluminescence and thermoluminescence (PL and TL) in CaGa2Se4:Eu crystals in the temperature range 77–400 K. We have established that broadband photoluminescence with maximum at 571 nm is due to intracenter transitions 4f6 5d–4f7 (8S7/2) of the Eu2+ ions. From the temperature dependence of the intensity (log I–103/T), we determined the activation energy (E a = 0.04 eV) for thermal quenching of photoluminescence. From the thermoluminescence spectra, we determined the trap depths: 0.31, 0.44, 0.53, 0.59 eV. The lifetime of the excited state 4f6 5d of the Eu2+ ions in the CaGa2Se4 crystal found from the luminescence decay kinetics is 3.8 μsec. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 1, pp. 112–116, January–February, 2009.  相似文献   

19.
The effects of dopant on the electrochemical properties of spinel-type Li3.97M0.1Ti4.94O12 (M = Mn, Ni, Co) and Li(4-x/3)CrxTi(5-2x/3)O12(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm2 between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr3+ dopant improved the reversible capacity and cycling stability over the pristine Li4Ti5O12. The substitution of the Mn3+ and Ni3+ slightly decreased the capacity of the Li4Ti5O12. Dopants such as Co3+ to some extent worsened the electrochemical performance of the Li4Ti5O12.  相似文献   

20.
The Dy3+ and Eu3+ activated K3Al2 (PO4)3 phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K3Al2 (PO4)3 was confirmed. In the photoluminescence emission spectra, the K3Al2(PO4)3:Dy3+ phosphor emits two distinctive colors: blue and yellow whereas K3Al2(PO4)3:Eu3+ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).  相似文献   

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