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1.
Spherical LiNi1/2Mn1/2O 2 powders were synthesized from LiOH . H2O and coprecipitated metal hydroxide, (Ni1/2Mn1/2)(OH)2. The average particle size of the powders was about 10 m and the size distribution was quite narrow due to the homogeneity of the metal hydroxide, (Ni1/2Mn1/2)(OH)2. The tap-density of the LiNi1/2Mn1/2O2 powders was approximately 2.2 g cm–3, which is comparable to the tap-density of commercial LiCoO2. The LiNi1/2Mn1/2 O2electrode delivered a discharge capacity of 152, 163, 183, and 189 mA h g–1 in the voltage ranges of 2.8–4.3, 2.8–4.4, 2.8–4.5, and 2.8–4.6 V, respectively, with good cyclability. Furthermore, Al(OH)3-coated LiNi1/2Mn1/2O2exhibited excellent cycling behavior and rate capability compared to the pristine electrode.  相似文献   

2.
A lithium insertion material having the composition LiNi0.3Co0.3Mn0.3Fe0.1O2 was synthesized by simple sol-gel method. The structural and electrochemical properties of the sample were investigated using X-ray diffraction spectroscopy (XRD) and the galvanostatic charge-discharge method. Rietvelt analysis of the XRD patterns shows that this compound can be classified as α-NaFeO2 structure type (R3m; a=2.8689(5) Å and 14.296(5) Å in hexagonal setting). Rietvelt fitting shows that a relatively large amount of Fe and Ni ion occupy the Li layer (3a site) and a relatively large amount of Li occupies the transition metal layer (3b site). LiNi0.3Co0.3Mn0.3Fe0.1O2 when cycled in the voltage range 4.3–2.8 V gives an initial discharge capacity of 120 mAh/g, and stable cycling performance. LiNi0.3Co0.3Mn0.3Fe0.1O2 in the voltage range 2.8–4.5 V has a discharge capacity of 140 mAh/g, and exhibits a significant loss in capacity during cycling. Ex-situ XRD measurements were performed to study the structure changes of the samples after cycling between 2.8–4.3 V and 2.8–4.5 V for 20 cycles. The XRD and electrochemical results suggested that cation mixing in this layered structure oxide could be causing degradation of the cell capacity.  相似文献   

3.
The Li-rich layered cathode material, Li[Ni0.2Li0.2Mn0.6]O2, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O3–LiCoO2-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg−1 to a stable capacity of over 260 mA hg−1 after the 10th cycle. It delivers a larger capacity of 258 mA hg−1 at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn4+/Mn3+.  相似文献   

4.
Nickel-rich layered materials are prospective cathode materials for use in lithium-ion batteries due to their higher capacity and lower cost relative to LiCoO2. In this work, spherical Ni0.8Co0.1Mn0.1(OH)2 precursors are successfully synthesized through a co-precipitation method. The synthetic conditions of the precursors - including the pH, stirring speed, molar ratio of NH4OH to transition metals and reaction temperature - are investigated in detail, and their variations have significant effects on the morphology, microstructure and tap-density of the prepared Ni0.8Co0.1Mn0.1 (OH)2 precursors. LiNi0.8Co0.1Mn0.1O2 is then prepared from these precursors through a reaction with 5% excess LiOH· H2O at various temperatures. The crystal structure, morphology and electrochemical properties of the Ni0.8Co0.1Mn0.1 (OH)2 precursors and LiNi0.8Co0.1Mn0.1O2 were investigated. In the voltage range from 3.0 to 4.3 V, LiNi0.8Co0.1Mn0.1O2 exhibits an initial discharge capacity of 193.0mAh g-1 at a 0.1 C-rate. The cathode delivers an initial capacity of 170.4 mAh g-1 at a 1 C-rate, and it retains 90.4% of its capacity after 100 cycles.  相似文献   

5.
LiNi1-y MyO2 (M = Ga, In and Tl, y = 0.010, 0.025 and 0.050) with small y were synthesized by the combustion method by calcining in an O2 stream at 750 °C for 36 h. XRD analyses, SEM observation and measurement of the variation of discharge capacity with the number of cycles were carried out. All the samples had the Rm structure and LiNi1-y In y O2 contained LiInO2 phase as an impurity. Among LiNi1-y Ga y O2 the sample with y = 0.025 had a relatively large first discharge capacity (172.2 mAh g−1) and relatively good cycling performance (discharge capacity 140.3 mAh g−1 at n = 20). For LiNi0.975M0.025O2 (M = Ga, In and Tl), the first discharge capacity decreased in the order of the substituted element Ga, In and Tl. The variations of cation mixing and hexagonal ordering with the substituted element (decrease in I003/I104 and increase in R-factor from M = Ga through M = Tl) are considered to lead to the behavior of the first discharge capacity with the substituted element. LiNi0.975Tl0.025O2 had the smallest degradation rate of the discharge capacity.  相似文献   

6.
A layered LiNi0.8Co0.2O2 solid solution, which is a promising cathode material for secondary lithium batteries, was successfully synthesized by an emulsion drying method. Because electrochemical properties significantly depend on the conditions of the synthesis, the calcination temperature was carefully determined on the basis of X-ray diffraction and TG studies. The prepared cathodes were characterized by means of SEM, BET, X-ray diffraction, Rietveld refinement, cyclic voltammetry and a charge-discharge experiment. From the Rietveld analysis, it was found that powder calcined at 800 °C for 12 h exhibits a well ordered and lower cation mixed layered structure than the others. The cyclic voltammetry experiment shows that phase transformation can be suppressed considerably by increasing the calcination temperature to 800 °C. The highest discharge capacity of 188.4 mA h g−1 was obtained from the sample prepared at 800 °C. Furthermore, a high capacity retention ratio of 88.1% was found for the initial value after 50 cycles at a constant current density of 40 mA g−1 between 2.7 VLi/Li+ and 4.3 VLi/Li+. In the rate capability test, the cathode delivered a higher discharge capacity of 153.1 mA h g−1 at a 4 C (800 mA g−1) rate.  相似文献   

7.
The effect of surface area on the electrochemical properties and thermal stability of Li[Ni0.2Li0.2Mn0.6]O2 powders was characterized using a charge/discharge cycler and DSC (Differential Scanning Calorimeter). The surface area of the samples was successfully controlled from ~4.0 to ~11.7 m2 g−1 by changing the molar ratio of the nitrate/acetate sources and adding an organic solvent such as acetic acid or glucose. The discharge capacity and rate capability was almost linearly increased with increase in surface area of the sample powder. A sample with a large surface area of 9.6–11.7 m2 g−1 delivered a high discharge capacity of ~250 mAh g−1 at a 0.2 C rate and maintained 62–63% of its capacity at a 6 C rate versus a 0.2 C rate. According to the DSC analysis, heat generation by thermal reaction between the charged electrode and electrolyte was not critically dependent on the surface area. Instead, it was closely related to the type of organic solvent employed in the fabrication process of the powder.  相似文献   

8.
The optimum conditions for synthesizing LiNi1-y Co y O2 (y=0.1, 0.3 and 0.5) by a simplified combustion method, in which the preheating step is omitted, and the electrochemical properties of these materials were investigated. The optimum condition for synthesizing LiNi0.9Co0.1O2 by the simplified combustion method is calcination at 800 °C for 12 h in air in 3.6 mole ratio of urea to nitrate. The LiNi0.9Co0.1O2 synthesized under these conditions shows the smallest R-factor{(I 006+I 102)/I 101} and the largest I 003/I 104, indicating better hexagonal ordering and less cation mixing, respectively. The LiNi0.7Co0.3O2 synthesized at 800 °C for 12 h in air in 3.6 mole ratio of urea to nitrate has the largest first discharge capacity 156.2 mA h g−1 at 0.5C and shows relatively good cycling performance. This sample shows better hexagonal ordering and less cation mixing than the other samples. The particle size of the LiNi0.7Co0.3O2 is relatively small and its particles are spherical with uniform particle size.  相似文献   

9.
LiNi0.4Co0.3Mn0.3O2 thin film electrodes are fabricated from LiNi0.4Co0.3Mn0.3O2 raw powder at room temperature without pretreatments using aerosol deposition that is much faster and easier than conventional methods such as vaporization, pulsed laser deposition, and sputtering. The LiNi0.4Co0.3Mn0.3O2 thin film is composed of fine grains maintaining the crystal structure of the LiNi0.4Co0.3Mn0.3O2 raw powder. In the cyclic voltammogram, the LiNi0.4Co0.3Mn0.3O2 thin film electrode shows a 3.9-V anodic peak and a 3.6-V cathodic peak. The initial discharge capacity is 44.6 μAh/cm2, and reversible behavior is observed in charge-discharge profiles. Based on the results, the aerosol deposition method is believed to be a potential candidate for the fabrication of thin film electrodes.  相似文献   

10.
Recently, there have been many reports on efforts to improve the rate capability and discharge capacity of lithium secondary batteries in order to facilitate their use for hybrid electric vehicles and electric power tools. In the present work, we present a ZrO2-coated Li[Li1/6Mn1/2Co1/6Ni1/6]O2. The bare Li[Li1/6Mn1/2Co1/6Ni1/6]O2 shows a high initial discharge capacity of 224 mAh g−1 at a 0.2 C rate. Owing to the stability of ZrO2, it was possible to enhance the rate capability and cyclability. After 1 wt% ZrO2 coating, the ZrO2-coated Li[Li1/6Mn1/2Co1/6Ni1/6]O2 showed a high discharge capacity of 115 mAh g−1 after 50 cycles under a 6 C rate, whereas the bare Li[Li1/6Mn1/2Co1/6Ni1/6]O2 showed a discharge capacity of only 40 mAh g−1 and very poor cyclability under the same conditions. Based on results of XRD and EIS measurements, it was found that the ZrO2 suppressed impedance growth at the interface between the electrodes and electrolyte and prevented collapse of the layered hexagonal structure.  相似文献   

11.
Spinel Li4Mn5O12 was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO2-AC) were prepared by a method in which KMnO4 was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li4Mn5O12 and MnO2-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li4Mn5O12/MnO2-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li4Mn5O12/MnO2-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g−1 was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g−1 in 1 mol L−1 Li2SO4 solution. The charge/discharge mechanism of Li4Mn5O12 and MnO2-AC was discussed.  相似文献   

12.
A cathode material for lithium-ion batteries–LiNi1/3Co1/3Mn1/3O2–was prepared by solution combustion synthesis and characterized by XRD, SEM, and galvanostatic charge/discharge cycling. The sample calcined at 950°C for 10 h showed best charge/discharge performance. An initial discharge capacity (C) of 150.5 mA h g–1 retained 95.7% of its value after 75 charge/discharge cycles at Ic = 14 mA g–1 (0.2C rate), Id = 70 mA g–1 (0.5C rate).  相似文献   

13.
LiNi1/2Mn1/2O2 electrodes with layered structure were synthesized by solid-state reaction between lithium hydroxide and mixed Ni,Mn oxides obtained from co-precipitated Ni,Mn carbonates and hydroxides and freeze-dried Ni,Mn citrates. The temperature of the solid-state reaction was varied between 800 and 950 °C. This method of synthesis allows obtaining oxides characterized with well-crystallized nanometric primary particles bounded in micrometric aggregates. The extent of particle agglomeration is lower for oxides obtained from freeze-dried Ni,Mn citrates. The local Mn4+ surrounding in the transition metal layers was determined by X-band electron paramagnetic resonance (EPR) spectroscopy. It has been found that local cationic distribution is consistent with α,β-type cationic order with some extent of disordering that depends mainly on the precursors used. The electrochemical extraction and insertion of lithium was tested in lithium cells using Step Potential Electrochemical Spectroscopy. The electrochemical performance of LiNi1/2Mn1/2O2 oxides depends on the precursors used, the synthesis temperature and the potential range. The best electrochemical response was established for LiNi1/2Mn1/2O2 prepared from the carbonate precursor at 900 °C. The changes in local environment of Mn4+ ions during electrochemical reaction in both limited and extended potential ranges were discussed on the basis of ex situ EPR experiments.  相似文献   

14.
K.M. Shaju 《Electrochimica acta》2003,48(11):1505-1514
Layered Li(Ni1/2Mn1/2)O2 was prepared by the solution and mixed hydroxide methods, characterised by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) and studied by cyclic voltammetry (CV) and charge discharge cycling in CC and CCCV modes at room temperature (r.t.) and at 50 °C. The XPS studies show about 8% of Ni3+ and Mn3+ ions are present in Li(Ni2+1/2Mn1/24+)O2 due to valency-degeneracy. The compound prepared at 950 °C, 12 h, solution method gives a second cycle discharge capacity of 150 mA h g−1 (2.5-4.4 V) at a specific current of 30 mA g−1 and retains 137 mA h g−1 at the end of 40 cycles. CV shows that the redox process at 3.7-4.0 V corresponds to Ni2+↔Ni4+ and clear indication of Mn3+/4+ couple was noted at 4.2-4.5 V. The observed capacity-fading (2.5-4.4 V) is shown to be contributed by the polarisation at the end of charging. The cathodic capacity is stable up to 40 cycles in the voltage window, 2.5-4.2 V both at room temperature and 50 °C.  相似文献   

15.
Layered Li[Ni0.5−xMn0.5−xZr2x]O2 (x = 0, 0.025) have been prepared by the mixed hydroxide and molten-salt synthesis method. The individual particles of synthesized materials have a sub-microsize range of 200-500 nm, and LiNi0.475Mn0.475Zr0.05O2 has a rougher surface than that of LiNi0.5Mn0.5O2. The Li/Li[Ni0.5−xMn0.5−xZr2x]O2 (x = 0, 0.025) electrodes were cycled between 4.5 and 2.0 V at a current density of 15 mA/g, the discharge capacity of both cells increased during the first ten cycles. The discharge capacity of the Li/LiNi0.475Mn0.475Zr0.05O2 cell increased from 150 to 220 mAh/g, which is 50 mAh/g larger than that of the Li/LiNi0.5Mn0.5O2 cell. We found that the oxidation of oxygen and the Mn3+ ion concerned this phenomenon from the cyclic voltammetry (CV). Thermal stability of the charged Li[Ni0.5−xMn0.5−xZr2x]O2 (x = 0, 0.025) cathode was improved by Zr doping.  相似文献   

16.
S. Zhang  C. Deng  B.L. Fu  L. Ma 《Powder Technology》2010,198(3):373-400
A carbonate co-precipitation method was employed to prepare spherical Li[Ni1/3Co1/3Mn1/3]O2 cathode material. The precursor, [Ni1/3Co1/3Mn1/3]CO3, was prepared using ammonia as chelating agent under CO2 atmosphere. The spherical Li[Ni1/3Co1/3Mn1/3]O2 was prepared by mixing the precalcined [Ni1/3Co1/3Mn1/3]CO3 with LiOH followed by high temperature calcination. The preparation conditions such as ammonia concentration, co-precipitation temperature, calcination temperature and Li/[Ni1/3Co1/3Mn1/3] ratio were varied to optimize the physical and electrochemical properties of the prepared Li[Ni1/3Co1/3Mn1/3]O2. The structural, morphological, and electrochemical properties of the prepared LiNi1/3Co1/3Mn1/3O2 were characterized by XRD, SEM, and galvanostatic charge-discharge cycling. The optimized material has a spherical particle shape and a well ordered layered structure, and it also has an initial discharge capacity of 162.7 mAh g− 1 in a voltage range of 2.8-4.3 V and a capacity retention of 94.8% after a hundred cycles. The optimized ammonia concentration, co-precipitation temperature, calcination temperature, and Li/[Ni1/3Co1/3Mn1/3] ratio are 0.3 mol L− 1, 60 °C, 850 °C, and 1.10, respectively.  相似文献   

17.
The generation of active chlorine on Ti/Sn(1−x)Ir x O2 anodes, with different compositions of Ir (x = 0.01, 0.05, 0.10 and 0.30 ), was investigated by controlled current density electrolysis. Using a low concentration of chloride ions (0.05 mol L−1) and a low current density (5 mA cm−2) it was possible to produce up to 60 mg L−1 of active chlorine on a Ti/Sn0.99Ir0.01O2 anode. The feasibility of the discoloration of a textile acid azo dye, acid red 29 dye (C.I. 16570), was also investigated with in situ electrogenerated active chlorine on Ti/Sn(1−x)Ir x O2 anodes. The best conditions for 100% discoloration and maximum degradation (70% TOC reduction) were found to be: NaCl pH 4, 25 mA cm−2 and 6 h of electrolysis. It is suggested that active chlorine generation and/or powerful oxidants such as chlorine radicals and hydroxyl radicals are responsible for promoting faster dye degradation. Rate constants calculated from color decay versus time reveal a zero order reaction at dye concentrations up to 1.0 × 10−4 mol L−1. Effects of other electrolytes, dye concentration and applied density currents also have been investigated and are discussed.  相似文献   

18.
Elemental doping for substituting lithium or oxygen sites has become a simple and effective technique to improve the electrochemical performance of layered cathode materials. Compared with single-element doping, this work presents an unprecedented contribution to the study of the effect of Na+/F co-doping on the structure and electrochemical performance of LiNi1/3Mn1/3Co1/3O2. The co-doped Li1-zNazNi1/3Mn1/3Co1/3O2-zFz (z = 0.025) and pristine LiNi1/3Co1/3Mn1/3O2 materials were synthesized via the sol–gel method using EDTA as a chelating agent. Structural analyses, carried out by X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, revealed that the Na+ and F dopants were successfully incorporated into the Li and O sites, respectively. The co-doping resulted in larger Li-slab spacing, a lower degree of cation mixing, and the stabilization of the surface structure, which substantially enhanced the cycling stability and rate capability of the cathode material. The Na/F co-doped LiNi1/3Mn1/3Co1/3O2 electrode delivered an initial specific capacity of 142 mAh g−1 at a 1C rate (178 mAh g−1 at 0.1C), and it maintained 50% of its initial capacity after 1000 charge–discharge cycles at a 1C rate.  相似文献   

19.
Sen Zhang 《Electrochimica acta》2007,52(25):7337-7342
Li[Ni1/3Co1/3Mn1/3]O2 cathode material for lithium ion batteries was prepared by mixing metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2, with 6% excess LiOH followed by calcinations. The (Ni1/3Co1/3Mn1/3)(OH)2 with secondary particle of about 12 μm was prepared by hydroxide co-precipitation. The tap density of the obtained Li[Ni1/3Co1/3Mn1/3]O2 powder was 2.56 ± 0.21 g cm−3. The powder was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), particle size distribution (PSD) and galvanostatic charge-discharge cycling. The XRD pattern of Li[Ni1/3Co1/3Mn1/3]O2 revealed a well ordered hexagonal layered structure with low cation mixing. Secondary particles with size of 13-14 μm and primary particles with size of about 1 μm can be identified from the SEM observations. In the voltage range of 2.8-4.3 V, the initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 electrode was 166.6 mAh g−1, and 96.5% of the initial capacity was retained after 50 charge-discharge cycling.  相似文献   

20.
Layered Li[Ni1/2Mn1/2]O2 was synthesized by an ultrasonic spray pyrolysis method. The Li[Ni1/2Mn1/2]O2 powder was characterized by means of X-ray diffraction, charge/discharge test, and cyclic voltammetry. The discharge capacity increases linearly with increase of the upper cut-off voltage limit and attains a high discharge capacity of 187 mA h g–1 between 2.8 and 4.6 V with excellent cyclability. A cyclic voltammetric study of the Li[Ni1/2Mn1/2]O2 electrode showed only one redox peak implying no structural phase change during cycling.  相似文献   

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