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1.
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   

2.
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   

3.
Li[Ni1/3Co(1-x)/3Mn1/3Fe x/3] O2(x?=?0.0, 0.1, 0.3, 0.5, 0.7, and 0.9) cathode materials have been synthesized via hydroxide co-precipitation method followed by a solid state reaction. Thermogravimetry (TG) and differential thermal analysis (DTA) measurements were utilized to determine the calcination temperature of precursor sample. The crystal structure features were characterized by X-ray diffraction (XRD). The electrochemical properties of Li[Ni1/3Co(1-x)/3Mn1/3Fe x/3]O2 were compared by means of cyclic voltammetry (CV), electrochemical impedance spectroscopy(EIS), and galvanostatic charge/discharge test. Electrochemical test results indicate that Li[Ni1/3Co0.9/3Mn1/3Fe0.1/3] O2 decrease charge transfer resistance and enhance Li+ ion diffusion velocity and thus improve cycling and high-rate capability compared with Li[Ni1/3Co1/3Mn1/3]O2. The initial discharge specific capacity of Li[Ni1/3Co0.9/3Mn1/3Fe0.1/3] O2 was 178.5 mAh/g and capacity retention was 87.11 % after 30 cycles at 0.1C, with the battery showing good cycle performance.  相似文献   

4.
Relationships between the performance and the crystallite size of the microsized spherical Li(Ni0.5Co0.2Mn0.3)O2 cathode material composed of aggregated nanosized primary particles have been comprehensively studied. The cathode material was synthesized by a high-temperature solid-state method. The results obtained by XRD, Rietveld refinement, SEM, HR-TEM, DSC, and galvanostatic test show that the crystallite size (XS) of Li(Ni0.5Co0.2Mn0.3)O2 is greatly affected by the temperature in the range of 750 to 820 °C. Most of all, the crystallite size plays a unique role in the performance of the material. That is, the electrochemical characteristics of Li(Ni0.5Co0.2Mn0.3)O2, such as discharge capacity, rate performance, and thermal stability, are closely related to the crystallite size. Furthermore, the retention of discharge capacity is determined by that of crystallite size in Li(Ni0.5Co0.2Mn0.3)O2 after 100 cycles.  相似文献   

5.
(Ni0.6Co0.2Mn0.2)(OH)2 precursor has been successfully prepared using hydroxide co-precipitation method. The thermodynamic model of hydroxide co-precipitation with sodium DL-lactate as an eco-friendly chelating agent is proposed. The microstructures of (Ni0.6Co0.2Mn0.2)(OH)2 precursors and Li(Ni0.6Co0.2Mn0.2)O2 cathode materials are investigated using X-ray diffractometer and scanning electronic microscopy, while the electrochemical performances of Li(Ni0.6Co0.2Mn0.2)O2 cathode materials are measured using a charge–discharge test. The influences of pH value on the structure and morphological and electrochemical performances of Li(Ni0.6Co0.2Mn0.2)O2 cathode materials have been discussed in detail. The results show that the sample at pH?=?11.5 exhibits the best lamellar structure and lowest cation mixing, while the sample at pH?=?11.0 delivers the most uniform and full particles and possesses the highest initial charge–discharge performance of 183.4 mAh/g and the best coulombic efficiency of 77.9% at the voltage range of 3.0–4.3 V. Even after 100 cycles, its discharge capacity still remains 165.2 mAh/g with the best retention rate of 90.1%. Furthermore, the sample at pH?=?11.0 delivers the highest discharge capacity at each current density. Even if discharged at 5C (1000 mA/g), the capacity of 115.6 mAh/g has been achieved. The sample at pH?=?11.0 exhibits the highest Li-ion diffusion coefficients (2.072?×?10?12 cm2/s).  相似文献   

6.
Electron spin resonance (ESR) measurements have been performed on polycrystalline samples of Pr0.6Ca0.4Mn1-xRuxO3 (x = 0, 0.1). The substitution of Ru in the Mn-site strengthens ferromagnetic interactions due to the double exchange between the Mn3+ and Mn4+ species and super-exchange between the Ru5+ and Mn3+ species. The temperature dependence of the ESR spectra indicates development of magnetic phase separation in Pr0.6Ca0.4Mn0.9Ru0.1O3 in contrast with the un-doped sample.  相似文献   

7.
The layered Li1.2Mn0.54Ni0.13Co0.13O2 lithium-rich manganese-based solid solution cathode material has been synthesized by a simple solid-state method. The as-prepared material has a typical layered structure with R-3m and C2/m space group. The synthesized Li1.2Mn0.54Ni0.13Co0.13O2 has an irregular shape with the size range from 200 to 500 nm, and the primary particle of Li1.2Mn0.54Ni0.13Co0.13O2 has regular sphere morphology with a diameter of 320 nm. Electrochemical performances also have been investigated. The results show that the cathode material Li1.2Mn0.54Ni0.13Co0.13O2 prepared at 900 °C for 12 h has a good electrochemical performance, which can deliver a high initial discharge capacity of 233.5, 214.2, 199.3, and 168.1 mAh g?1 at 0.1, 0.2, 0.5, and 1 C, respectively. After 50 cycles, the capacity retains 178.0, 166.3, 162.1, and 155.9 mAh g?1 at 0.1, 0.2, 0.5, and 1 C, respectively. The results indicate that the simple method has a great potential in synthesizing manganese-based cathode materials for Li-ion batteries.  相似文献   

8.
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   

9.
The LaF3-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 nanoparticles were synthesized via co-precipitation method followed by simple chemical deposition process. The crystal structure, particle morphology, and electrochemical properties of the bare and coated materials were studied by XRD, SEM, TEM, charge–discharge tests. The results showed that the surface coating on Li[Li0.2Mn0.54Ni0.13Co0.13]O2 nanoparticles were amorphous LaF3 layer with a thickness of about 10–30 nm. After the surface modification with LaF3 films, the coating layer served as a protective layer to suppress the side reaction between the positive electrode and electrolyte, and the Li[Li0.2Mn0.54Ni0.13Co0.13]O2 oxide demonstrated the improved electrochemical properties. The LaF3-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 electrode delivered the capacities of 270.5, 247.9, 197.1, 170.0, 142.7, and 109.5 mAh g?1 at current rates of 0.1, 0.2, 0.5, 1, 2, and 5 C rate, respectively. Besides, the capacity retention was increased from 85.1 to 94.8 % after 100 cycles at 0.5 C rate. It implied surface modification with LaF3 played an important role to improve the cyclic stability and rate capacity of the Li-rich nickel manganese oxides.  相似文献   

10.
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   

11.
(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   

12.
LiNi0.5Co0.2Mn0.3O2 particles of uniform size were prepared through carbonate co-precipitation method with acacia gum. The precursor of carbonate mixture was calcined at 800 °C, and a well-crystallized Ni-rich layered oxide was got. The phase structure and morphology were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The micro-sized particles delivered high initial discharge capacity of 164.3 mA h g?1 at 0.5 C (1 C?=?200 mA g?1) between 2.5 and 4.3 V with capacity retention of 87.5 % after 100 cycles. High reversible discharge capacities of 172.4 and 131.4 mA h g?1 were obtained at current density of 0.1 and 5 C, respectively. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were performed to further study the LiNi0.5Co0.2Mn0.3O2 particles. Anyway, the excellent electrochemical performances of LiNi0.5Co0.2Mn0.3O2 sample should be attributed to the use of acacia gum.  相似文献   

13.
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   

14.
Guoqiang Liu  Lei Wen  Yue Li  Yulong Kou 《Ionics》2015,21(4):1011-1016
The pure phase P2-Na2/3Ni1/3Mn2/3O2 was synthesized by a solid reaction process. The optimum calcination temperature was 850 °C. The as-prepared product delivered a capacity of 158 mAh g?1 in the voltage range of 2–4.5 V, and there was a phase transition from P2 to O2 at about 4.2 V in the charge process. The P2 phase exhibited excellent intercalation behavior of Na ions. The reversible capacity is about 88.5 mAh g?1 at 0.1 C in the voltage range of 2–4 V at room temperature. At an elevated temperature of 55 °C, it could remain as an excellent capacity retention at low current rates. The P2-Na2/3Ni1/3Mn2/3O2 is a potential cathode material for sodium-ion batteries.  相似文献   

15.
To suppress the capacity fade of Li-rich Li1.2Ni0.13Co0.13Mn0.54O2 material as cathode materials for lithium-ion battery, we introduce a LiF coating layer on the surface to improve the cycling performance of Li1.2Ni0.13Co0.13Mn0.54O2 material. The modified sample shows a capacity of 163.2 mAh g?1 with a capacity retention of 95% after 100 cycles at a current density of 250 mA g?1, while the pristine sample only delivers a capacity of 129.9 mAh g?1 with a capacity retention of 82%. Compared with the pristine material, the LiF-modified sample exhibits an obvious enhancement in the electrochemical performance, which will be very beneficial for this material to be commercialized on the new energy vehicles and other related areas.  相似文献   

16.
The structure of an LiNi0.4Fe0.6O2 cubic solid solution is determined using magnetic measurements and electron diffraction. It is found that this solid solution has a microinhomogeneous structure due to the formation of superparamagnetic clusters. The electron diffraction analysis of LiNi0.4Fe0.6O2 samples has revealed diffuse scattering characteristic of the substitutional short-range order in ordered solid solutions with a B1-type structure. It is shown that the short-range order is associated with the LiNiO2-type rhombohedral superstructure (space group \(R\bar 3m\)), i.e., with the redistribution of lithium and nickel atoms in the (111)B1 alternating planes. The short-range order is observed in regions with a nickel content higher than the mean nickel content corresponding to the macroscopic composition.  相似文献   

17.
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   

18.
The Li(Ni0.6Co0.15Mn0.25)1?x (CuTi) x O2 (x = 0.00, 0.01, 0.02, 0.03) cathode materials were synthesized via a hydroxide co-precipitation method followed by a solid-state reaction. The elementary composition, crystal structure features, morphology, and electrochemical performances of the powders were investigated in detail by inductively coupled plasma-atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD), Rietveld refinement, scanning electron microscopy (SEM), galvanostatic charge/discharge test, electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), respectively. The results of XRD and Rietveld refinements demonstrate that Cu and Ti co-substitution does not destroy the crystal structure, but can decrease cation ordering level and improve structural integrity. Electrochemical results show that Cu and Ti addition also results in an improved rate and cycling performances compared to pristine LiNi0.6Co0.15Mn0.25O2. An increase in rate performance and cycle stability upon copper and titanium co-substitution is related to the better hexagonal structure and enhanced kinetics of the intercalation process. Especially, Li(Ni0.6Co0.15Mn0.25)0.99(CuTi)0.01O2 exhibits the best rate performance and cycle stability among all samples with discharge specific capacity of 178.8 mAh/g and capacity retention of 90.6% after 30 cycles at 0.2C, which are higher than those of other materials.  相似文献   

19.
To improve the electrochemical performance of Nickel-rich cathode material LiNi0.8Co0.1Mn0.1O2, an in situ coating technique with Li2ZrO3 is successfully applied through wet chemical method, and the thermoelectrochemical properties of the coated material at different ambient temperatures and charge-discharge rates are investigated by electrochemical-calorimetric method. Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) tests demonstrate that the Li2ZrO3 coating decreases the electrode polarizatoin and reduces the charge transfer resistance of the material during cycling. Moreover, it is found that with the ambient temperatures and charge-discharge rates increase, the specific capacity decreases, the amount of heat increases, and the enthalpy change (ΔH) increases. The specific capacity of the cells at 30 °C are 203.8, 197.4, 184.0, and 174.5 mAh g?1 at 0.2, 0.5, 1.0, and 2.0 C, respectively. Under the same rate (2.0 C), the amounts of heat of the cells are 381.64, 645.32, and 710.34 mJ at 30, 40, and 50 °C. These results indicate that Li2ZrO3 coating plays an important role to enhance the electrochemical performance of LiNi0.8Co0.1Mn0.1O2 and reveal that choosing suitable temperature and current is critical for solving battery safety problem.  相似文献   

20.
A series of samples in the system Ni0.65Zn0.35CuxFe2-xO4 (x = 0, 0.1, 0.2, 0.3, 0.4 and 0.5) were prepared by the usual ceramic technique. The thermoelectric power and the magnetic susceptibility were measured. The transition from the ferrimagnetic to the paramagnetic state is accompanied by an increase in the thermo EMF. NiZn ferrite shows n-type conductivity due to the presence of Fe2+ ions. The addition of Cu2+ ions creates lattice vacancies which give rise to p-type conductivity.

The Tawfik coefficient was determined for NiZn ferrite in the paramagnetic state. This coefficient was reduced by addition of Cu up to x < 0.5.  相似文献   

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