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1.
Han Xu  Jun Zong  Xing-jiang Liu 《Ionics》2018,24(7):1939-1946
The P2-type Na0.67Mn0.6Fe0.4O2 (NaMnFe), Na0.67Mn0.6Fe0.3Zn0.1O2 (NaMnFeZn), and Na0.67Mn0.6Fe0.2Zn0.1Ni0.1O2 (NaMnFeZnNi) are prepared using an acetate decomposition reaction and developed as promising cathode materials for high-capacity sodium-ion batteries. The XRD patterns show that Zn2+ and Ni2+ ions are successfully incorporated into the lattice of the Na-Mn-Fe-O system, and the P2-type structure remains unchanged after substitution. The charging/discharging tests exhibit that the Na0.67Mn0.6Fe0.4O2, Na0.67Mn0.6Fe0.3Zn0.1O2, and Na0.67Mn0.6Fe0.2Zn0.1Ni0.1O2 electrodes have the capacities of 200.4, 182.0, and 202.2 mAhg?1, respectively. The Na0.67Mn0.6Fe0.4O2 electrode has a higher initial capacity but faster capacity decay. When partially substituting Zn and Ni for Fe, the Na0.67Mn0.6Fe0.3Zn0.1O2 and Na0.67Mn0.6Fe0.2Zn0.1Ni0.1O2 electrodes exhibit lower reversible capacity but improved cycling stability (88.3 and 93.4% capacity retention over 100 cycles). The greatly improved electrochemical performance of the Na0.67Mn0.6Fe0.2Zn0.1Ni0.1O2 electrode apparently belongs to the contribution of the Zn2+ and Ni2+ substitution, which facilitates to alleviate the Jahn-Teller distortion of Mn and suppresses the polarization.  相似文献   

2.
The effect of oxygen isotope substitution on the properties of Pr0.5Ca0.5Mn1 ? x Cr x O3 manganites (x = 0, 0.02, 0.05) have been studied. The introduction of chromium favors (i) the decomposition of a charge-ordered state and (ii) the appearance of a ferromagnetic metallic phase in Pr0.5Ca0.5Mn1 ? x Cr x 16–18O3. The isotope substitution 16O → 18O leads to a decrease in the content of the ferromagnetic phase, an increase in the charge-ordering transition temperature (T CO), and a decrease in the ferromagnetic transition temperature (T FM). The isotope mass exponent is evaluated.  相似文献   

3.
The results of investigations of the magnetization, susceptibility, and magnetic-field-induced changes in the entropy of polycrystalline manganite (La0.6Ca0.4)0.9Mn1.1O3 near the magnetic phase transition have been presented. Magnetic measurements have been carried out at temperatures in the range from 210 to 310 K in magnetic fields of up to 9 T. The magnetocaloric effect has been revealed by measuring the magnetic-field dependences of magnetization. The magnitude of the magnetocaloric effect is compared with similar results obtained for other manganites.  相似文献   

4.
Cr-doped layered oxides Li[Li0.2Ni0.2???x Mn0.6???x Cr2x ]O2 (x?=?0, 0.02, 0.04, 0.06) were synthesized by co-precipitation and high-temperature solid-state reaction. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (TRTEM), X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS). XRD patterns and HRTEM results indicate that the pristine and Cr-doped Li1.2Ni0.2Mn0.6O2 show the layered phase. The Li1.2Ni0.16Mn0.56Cr0.08O2 shows the best electrochemical properties. The first discharge specific capacity of Li1.2Ni0.16Mn0.56Cr0.08O2 is 249.6 mA h g?1 at 0.1 C, while that of Li1.2Ni0.2Mn0.6O2 is 230.4 mA h g?1. The capacity retaining ratio of Li1.2Ni0.16Mn0.56Cr0.08O2 is 97.9% compared with 93.9% for Li1.2Ni0.2Mn0.6O2 after 80 cycles at 0.2 C. The discharge capacity of Li1.2Ni0.16Mn0.56Cr0.08O2 is 126.2 mA h g?1 at 5.0 C, while that of the pristine Li1.2Ni0.2Mn0.6O2 is about 94.5 mA h g?1. XPS results show that the content of Mn3+ in the Li1.2Ni0.2Mn0.6O2 can be restrained after Cr doping during the cycling, which results in restraining formation of spinel-like structure and better midpoint voltages. The lithium-ion diffusion coefficient and electronic conductivity of Li1.2Ni0.2Mn0.6O2 are enhanced after Cr doping, which is responsible for the improved rate performance of Li1.2Ni0.16Mn0.56Cr0.08O2.  相似文献   

5.
Misfit-layered calcium cobaltites (Ca3Co4O9, Ca3Co3.9Fe0.1O9, and Ca3Co3.9Mn0.1O9), as anode materials for lithium-ion batteries, were synthesized by a simple hydro-decomposition method. All synthesized samples do not show any impurity phase. They exhibited plate-like particle with the particle size of 1–2 μm. The specific capacities of doped samples showed higher electrochemical performance compared to the undoped sample. After charge/discharge of 50 cycles, the specific capacities of Ca3Co4O9, Ca3Co3.9Fe0.1O9, and Ca3Co3.9Mn0.1O9 were 343, 562, and 581 mAh g?1, respectively. The doped samples showed an increase of over 60% compared to the undoped sample. The cyclic voltammetry profile of the doped samples showed the enhanced reactivity corresponding to their improved electrochemical performance. The capacity improvement of doped samples resulted from the metal oxide/Li conversion reactions, volume change, and high reactivity.  相似文献   

6.
The ferrimagnetic compounds Ca(CuxMn3?x)Mn4O12 of the double distorted perovskites AC3B4O12 family exhibit a rapid increase of the ferromagnetic component in magnetization at partial substitution of square coordinated (Mn3+)C for (Cu2+)C. In the transport properties, this is seen as a change of the semiconducting type of resistivity for the metallic one. The evolution of magnetic properties of Ca(CuxMn3?x)Mn4O12 is driven by strong antiferromagnetic exchange interaction of (Cu2+)C with (Mn3+/Mn4+)B coordinated octahedra. The competing interactions of (Mn3+)C with (Mn3+/Mn4+)B lead to the formation of noncollinear magnetic structures that can be aligned by magnetic fields.  相似文献   

7.
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   

8.
A change in electric polarization (up to 300 μC/m2) upon magnetic-field suppression of a charge-ordered antiferromagnetic state upon a transition to the ferromagnetic conducting phase (H cr ~ 65–80 kOe at 4.2 K) is discovered in Pr0.6Ca0.4MnO3 and Nd0.6Ca0.4MnO3 single crystals. The transition is also accompanied by a jump in magnetization and magnetostriction. The dependence of the induced polarization sign on the polarity of the electric field in which the sample was preliminarily cooled indicates the existence of spontaneous electric polarization. The effect is the strongest in Nd0.6Ca0.4MnO3 and is weaker by a factor of 5–10 in Pr0.6Ca0.4MnO3, for which the tolerance factor is higher. The observed effect may be associated with recently predicted noncentrosymmetric structures in doped manganites with x ~ 0.5 (see D.V. Efremov, J. van den Brink, and D.I. Khomskii, Nature Materials 3, 853 (2004)), in which e g electrons are not localized upon charge and orbital ordering at one manganese ion, but are distributed among neighboring ions, thus forming an ordered polar dimer structure.  相似文献   

9.
AMn3V4O12 (A = Ca, Ce, and Sm) compounds with a perovskite structure are synthesized at high pressures and temperatures. The crystalline structure of these compounds (space group \(Im\bar 3\)Z = 2) is determined via X-ray analysis. If ions in the A sublattice are changed in the order Ca2+–Sm3+–Ce3+, the valence is redistributed from Ca2+Mn32+V44+O12 to Sm3+Mn32+V43.75+O12, and to Ce3+Mn32+V43.75+O12. The temperature dependences of the electrical resistivity are studied.  相似文献   

10.
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   

11.
12.
Layered lithium-enriched nickel manganese oxides Li1.2Ni0.2Mn0.6O2 have been synthesized and coated by fast ionic conductor Li3VO4 with varying amounts (1, 3, and 5 wt%) in this paper. The effect of Li3VO4 on the physical and electrochemical properties of Li1.2Ni0.2Mn0.6O2 has been discussed through the characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), discharge, cyclic performance, rate capability, and electrochemical impedance spectroscopy (EIS). The discharge capacity and coulomb efficiency of Li1.2Ni0.2Mn0.6O2 in the first cycle have been improved after Li3VO4 coating. And, the 3 wt% Li3VO4-coated Li1.2Ni0.2Mn0.6O2 shows the best discharge capacity (246.8 mAh g?1), capacity retention (97.3 % for 50 cycles), and rate capability (90.4 mAh g?1 at 10 C). Electrochemical impedance spectroscopy (EIS) results show that the R ct of Li1.2Ni0.2Mn0.6O2 electrode decreases after Li3VO4 coating, which is due to high lithium ion diffusion coefficient of Li3VO4, is responsible for superior rate capability.  相似文献   

13.
The indirect-coupling model is used to analyze the exchange magnetic structure of Pb3Mn7O15 in the hexagonal setting. The ratios of manganese ions Mn4+/Mn3+ in each nonequivalent position are determined. Pb3(Mn0.95Ge0.05)7O15 and Pb3(Mn0.95Ga0.05)7O15 single crystals are grown by the solution–melt method in order to test the validity of the proposed model. The structural and magnetic properties of the single crystals are studied. The magnetic properties of the grown single crystals are compared with those of nominally pure Pb3Mn7O15.  相似文献   

14.
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   

15.
The temperature dependences of the velocity of longitudinal sound, internal friction, and magnetization of the single crystal with the nominal composition La0.6Pr0.1Ca0.3MnO3 have been measured. It has been found that the substitution of praseodymium for lanthanum in La0.7Ca0.3MnO3 leads to a decrease in the velocity of sound and to an increase in the spontaneous magnetization. The method of determining the Curie temperature distribution function during a first-order transition has been proposed. It has been shown that, in the crystal under study, this function is asymmetric.  相似文献   

16.
Fluoroethylene carbonate (FEC) is investigated as the electrolyte additive to improve the electrochemical performance of high voltage LiNi0.6Co0.2Mn0.2O2 cathode material. Compared to LiNi0.6Co0.2Mn0.2O2/Li cells in blank electrolyte, the capacity retention of the cells with 5 wt% FEC in electrolytes after 80 times charge-discharge cycle between 3.0 and 4.5 V significantly improve from 82.0 to 89.7%. Besides, the capacity of LiNi0.6Co0.2Mn0.2O2/Li only obtains 12.6 mAh g?1 at 5 C in base electrolyte, while the 5 wt% FEC in electrolyte can reach a high capacity of 71.3 mAh g?1 at the same rate. The oxidative stability of the electrolyte with 5 wt% FEC is evaluated by linear sweep voltammetry and potentiostatic data. The LSV results show that the oxidation potential of the electrolytes with FEC is higher than 4.5 V vs. Li/Li+, while the oxidation peaks begin to appear near 4.3 V in the electrolyte without FEC. In addition, the effect of FEC on surface of LiNi0.6Co0.2Mn0.2O2 is elucidated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The analysis result indicates that FEC facilitates the formation of a more stable surface film on the LiNi0.6Co0.2Mn0.2O2 cathode. The electrochemical impedance spectroscopy (EIS) result evidences that the stable surface film could improve cathode electrolyte interfacial resistance. These results demonstrate that the FEC can apply as an additive for 4.5 V high voltage electrolyte system in LiNi0.6Co0.2Mn0.2O2/Li cells.  相似文献   

17.
Pr-doped Li4Ti5O12 in the form of Li4?x/3Ti5?2x/3PrxO12 (x = 0, 0.01, 0.03, 0.05, and 0.07) was synthesized successfully by an electrospinning technique. ICP shows that the doped samples are closed to the targeted samples. XRD analysis demonstrates that traces of Pr3+ can enlarge the lattice parameter of Li4Ti5O12 from 8.3403 to 8.3765 Å without changing the spinel structure. The increase of lattice parameter is beneficial to the intercalation and de-intercalation of lithium-ion. XPS results identify the existence form of Ti is mainly Ti4+ and Ti3+ in minor quantity in Li4?x/3Ti5?2x/3PrxO12 (x = 0.05) samples due to the small amount of Pr3+. The transition from Ti4+ to Ti3+ is conducive to the electronic conductivity of Li4Ti5O12. FESEM images show that all the nanofibers are well crystallized with a diameter of about 200 nm and distributed uniformly. The results of electrochemical measurement reveal that the 1D Li4?x/3Ti5?2x/3PrxO12 (x = 0.05) nanofibers display enhanced high-rate capability and cycling stability compared with that of undoped nanofibers. The high-rate discharge capacity of the Li4?x/3Ti5?2x/3PrxO12 (x = 0.05) samples is excellent (101.6 mAh g?1 at 50 °C), which is about 58.48 % of the discharge capacity at 0.2 °C and 4.3 times than that of the bare Li4Ti5O12 (23.5 mA g?1). Even at 10 °C (1750 mA g?1), the specific discharge capacity is still 112.8 mAh g?1 after 1000 cycles (87.9 % of the initial discharge capacity). The results of cyclic voltammograms (CV) and electrochemical impedance spectroscopy (EIS) illustrate that the Pr-doped Li4Ti5O12 electrodes possess better dynamic performance than the pure Li4Ti5O12, further confirming the excellent electrochemical properties above.  相似文献   

18.
(Ni0.8Mn0.1Co0.1)(OH)2 and Co(OH)2 secondly treated by LiNi0.8Mn0.1Co0.1O2 have been prepared via co-precipitation and high-temperature solid-state reaction. The residual lithium contents, XRD Rietveld refinement, XPS, TG-DSC, and electrochemical measurements are carried out. After secondly treating process, residual lithium contents decrease drastically, and occupancy of Ni in 3a site is much lower and Li/Ni disorder decreases. The discharge capacity is 193.1, 189.7, and 182 mAh g?1 at 0.1 C rate, respectively, for LiNi0.8Mn0.1Co0.1O2-AP, -NT, and -CT electrodes between 3.0 and 4.2 V in pouch cell. The capacity retention has been greatly improved during gradual capacity fading of cycling at 1 C rate. The noticeably improved thermal stability of the samples after being treated can also be observed.  相似文献   

19.
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   

20.
ESR spectra of Ce3+ ions in polycrystalline Sr2B5O9Br were studied, and the two crystallographic positions of the Ce3+ ion in this compound were identified on the basis of the data obtained. The ESR spectrum of Ce3+ ions with local charge compensation contains a broad line indicating the existence of several types of charge compensation. ESR spectra of Ce3+ ions in samples activated additionally by K+ ions are similar to those of the regular Ce3+ centers, which indicates that the effect of the univalent cation on Ce3+ is negligible.  相似文献   

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