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1.
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   

2.
Uniform and spherical Li(Ni1/3Co1/3Mn1/3)O(2−δ)Fδ powders were synthesized via NH3 and F coordination hydroxide co-precipitation. The effect of F coordination agent on the morphology, structure and electrochemical properties of the Li(Ni1/3Co1/3Mn1/3)O(2−δ)Fδ were studied. The morphology, size, and distribution of (Ni1/3Co1/3Mn1/3)(OH)(2−δ)Fδ particle diameter were improved in a shorter reaction time through the addition of F. The study suggested that the added F improves the layered characteristics of the lattice and the cyclic performance of Li(Ni1/3Co1/3Mn1/3)O2 in the voltage range of 2.8-4.6 V. The initial capacity of the Li(Ni1/3Co1/3Mn1/3)O1.96F0.04 was 178 mAh g−1, the maximum capacity was 186 mAh g−1 and the capacity after 50 cycles was 179 mAh g−1 in the voltage range of 2.8-4.6 V.  相似文献   

3.
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   

4.
Non-spherical Li(Ni1/3Co1/3Mn1/3)O2 powders have been synthesized using a two-step drying method with 5% excess LiOH at 800 °C for 20 h. The tap-density of the powder obtained is 2.95 g cm−3. This value is remarkably higher than that of the Li(Ni1/3Co1/3Mn1/3)O2 powders obtained by other methods, which range from 1.50 g cm−3 to 2.40 g cm−3. The precursor and Li(Ni1/3Co1/3Mn1/3)O2 are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the precursor are 2+, 3+ and 4+, respectively. XRD results show that the Li(Ni1/3Co1/3Mn1/3)O2 material obtained by the two-step drying method has a well-layered structure with a small amount of cation mixing. SEM confirms that the Li(Ni1/3Co1/3Mn1/3)O2 particles obtained by this method are uniform. The initial discharge capacity of 167 mAh g−1 is obtained between 3 V and 4.3 V at a current of 0.2 C rate. The capacity of 159 mAh g−1 is retained at the end of 30 charge-discharge cycle with a capacity retention of 95%.  相似文献   

5.
In order to get homogeneous layered oxide Li[Ni1/3Mn1/3Co1/3]O2 as a lithium insertion positive electrode material, we applied the metal acetates decomposition method. The oxide compounds were calcined at various temperatures, which results in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni1/3Mn1/3Co1/3]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry and SEM. XRD experiment revealed that the layered Li[Ni1/3Mn1/3Co1/3]O2 material can be best synthesized at temperature of 800 °C. In that synthesized temperature, the sample showed high discharge capacity of 190 mAh g−1 as well as stable cycling performance at a current density of 0.2 mA cm−2 in the voltage range 2.3-4.6 V. The reversible capacity after 100 cycles is more than 190 mAh g−1 at room temperature.  相似文献   

6.
A series of LiNi1/3Mn1/3Co1/3O2 samples with α-NaFeO2 structure belonging to the D3d5 space group were synthesized using tartaric acid as a chelating agent by wet-chemical method. Different acid to metal-ion ratios R have been used to investigate the effect of this parameter on the physical and electrochemical properties. We have characterized the reaction mechanism, the structure, and morphology of the powders by TGA, XRD, SEM and TEM imaging, completed by magnetic measurements, Raman scattering spectroscopy, and complex impedance experiments. We find that the LiNi1/3Mn1/3Co1/3O2 sintered at 900 °C for 15 h with an acid to metal-ion ratio R = 2 was the optimum condition for this synthesis. For this optimized sample, only 1.3% of nickel-ions occupied the 3b Wyckoff site of the lithium-ions sublattice. The electrochemical performance has been investigated using a coin-type cell containing Li metal as the anode. The electronic performance is correlated to the concentration of the Ni(3b) defects that increase the charge transfer resistance and reduce the lithium diffusion coefficient. The optimized cell delivered an initial discharge capacity of 172 mAh g−1 in the cut-off voltage of 2.8-4.4 V, with a coulombic efficiency of 93.4%.  相似文献   

7.
Li[Ni(1/3−z)Co(1/3−z)Mn(1/3−z)Mgz]O2 (z = 0, 0.04) positive electrode materials were synthesized via a co-precipitation method. These materials have α-NaFeO2 () structure, as confirmed by X-ray diffraction (XRD) studies. Cation mixing in Li layer seemed to be decreased by Mg substitution as examined by Rietveld refinements of XRD data. Spherical morphologies were observed for the as-synthesized final products by scanning electron microscopy. Their electrochemical properties during charge and discharge were discussed. When magnesium ions are substituted, the initial reversible capacity reduced. However, the substitution for Mn sites in Li[Ni1/3Co1/3Mn1/3]O2 did not decrease the capacity because Mn sites substitution did not result in loss of electroactive elements in the compound. Differential scanning calorimetric studies showed the exothermic peaks of the charged electrode Li[Ni(1/3−z)Co(1/3−z)Mn(1/3−z)Mgz]O2 (z = 0.04) were significantly smaller than that of Li[Ni1/3Co1/3Mn1/3]O2, which means that thermal stability was greatly improved by Mg substitution even at highly delithiated state.  相似文献   

8.
Layered metastable lithium manganese oxides, Li2/3[Ni1/3−xMn2/3−yMx+y]O2 (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na2/3[Ni1/3−xMn2/3−yMx+y]O2 precursors. The Al and Co doping produced the T#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni1/3−xMn2/3−yMx+yO2 slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T#2-Li2/3[Ni1/3Mn2/3]O2 were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g−1 in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g−1 along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T#2 into the O2 structure was observed during the initial lithium deintercalation.  相似文献   

9.
Ultrafine powders of Li(Ni1/3Co1/3Mn1/3)O2 cathode materials for lithium-ion secondary batteries were prepared under mild hydrothermal conditions. The influence of the molar ratio of Li/(Ni + Co + Mn) was studied. The products were investigated by XRD, TEM and EDS. The final products were found to be well crystallized Li(Ni1/3Co1/3Mn1/3)O2 with an average particle size of about 10 nm.  相似文献   

10.
LiNi1/3Co1/3Mn1/3O2 and LiCoO2 cathode materials were synthesized by using a supercritical water (SCW) method with a metal salt solution in a batch reactor. Stoichiometric LiNi1/3Co1/3Mn1/3O2 was successfully synthesized in a 10-min reaction without calcination, while overlithiated LiCoO2 (Li1.15CoO2) was synthesized using the batch SCW method. The physical properties and electrochemical performances of LiNi1/3Co1/3Mn1/3O2 were compared to those of Li1.15CoO2 by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge/discharge cycling tests. The XRD pattern of LiNi1/3Co1/3Mn1/3O2 was found to be similar to that of Li1.15CoO2, showing clear splitting of the (0 0 6)/(1 0 2) and (1 0 8)/(1 1 0) peak pairs as particular characteristics of the layered structure. In addition, both cathode powders showed good crystallinity and phase purity, even though a short reaction time without calcination was applied to the SCW method. The initial specific discharge capacities of the Li1.15CoO2 and LiNi1/3Co1/3Mn1/3O2 powders at a current density of 0.24 mA/cm2 in 2.5-4.5 V were 149 and 180 mAh/g, and their irreversible capacity loss was 20 and 17 mAh/g, respectively. The discharge capacities of the Li1.15CoO2 and LiNi1/3Co1/3Mn1/3O2 powders decreased with cycling and remained at 108 and 154 mAh/g after 30 cycles, which are 79% and 89% of the initial capacities. Compared to the overlithiated LiCoO2 cathode powders, the LiNi1/3Co1/3Mn1/3O2 cathode powders synthesized by SCW method had better electrochemical performances.  相似文献   

11.
The complex perovskite oxide Ba(Zn1/3Nb2/3)O3 (BZN) has been studied for its attractive dielectric properties which place this material interesting for applications as multilayer ceramics capacitors or hyperfrequency resonators. This material is sinterable at low temperature with combined glass phase–lithium salt additions, and exhibits, at 1 MHz very low dielectric losses combined with relatively high dielectric constant and a good stability of this later versus temperature. The 2 wt.% of ZnO–SiO2–B2O3 glass phase and 1 wt.% of LiF-added BZN sample sintered at 900 °C exhibits a relative density higher than 95% and attractive dielectric properties: a dielectric constant ?r of 39, low dielectrics losses (tan(δ) < 10−3) and a temperature coefficient of permittivity τ? of 45 ppm/°C−1. The 2 wt.% ZnO–SiO2–B2O3 glass phase and 1 wt.% of B2O3-added BZN sintered at 930 °C exhibits also attractive dielectric properties (?r = 38, tan(δ) < 10−3) and it is more interesting in terms of temperature coefficient of the permittivity (τ? = −5 ppm/°C). Their good dielectric properties and their compatibility with Ag electrodes, make these ceramics suitable for L.T.C.C applications.  相似文献   

12.
We present the mechanism for the synthesis of a layered Li(Ni1/3Co1/3Mn1/3)O2 compound by a modified radiated gel method. Pure-phase Li(Ni1/3Co1/3Mn1/3)O2 material was achieved when the polymer gel was calcined at 900 °C between 15 and 30 h. The unit cell parameter c decreased, and a varied slightly with increased sintering time. Electrochemical characterization revealed that the optimized sample (25 h) had a high initial discharge capacity of 188 mAh/g (2.8-4.5 V, 20 mA/g), an excellent capacity retention of 90.1% after 30 cycles and a good rate performance.  相似文献   

13.
In this research, we studied the first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V. Properties, such as valence state of the transition metals and crystallographic features, were analyzed by X-ray absorption spectroscopy and X-ray and neutron diffractions. Especially, two plateaus observed around 3.75 and 4.54 V were investigated by ex situ X-ray absorption spectroscopy. XANES studies showed that the oxidation states of transition metals in Li[Ni1/3Co1/3Mn1/3]O2 are mostly Ni2+, Co3+ and Mn4+. Based on neutron diffraction Rietveld analysis, there is about 6% of all nickel divalent (Ni2+) ions mixed with lithium ions (cation mixing). Meanwhile, it was found that the oxidation reaction of Ni2+/Ni4+ is related to the lower plateau around 3.75 V, but that of Co3+/Co4+ seems to occur entire range of x in Li1−x[Ni1/3Co1/3Mn1/3]O2. Small volume change during cycling was attributed to the opposite variation of lattice parameter “c” and “a” with charging-discharging.  相似文献   

14.
A carbon coated Li3V2(PO4)3 cathode material for lithium ion batteries was synthesized by a sol-gel method using V2O5, H2O2, NH4H2PO4, LiOH and citric acid as starting materials, and its physicochemical properties were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), energy dispersive analysis of X-ray (EDAX), transmission electron microscope (TEM), and electrochemical methods. The sample prepared displays a monoclinic structure with a space group of P21/n, and its surface is covered with a rough and porous carbon layer. In the voltage range of 3.0-4.3 V, the Li3V2(PO4)3 electrode displays a large reversible capacity, good rate capability and excellent cyclic stability at both 25 and 55 °C. The largest reversible capacity of 130 mAh g−1 was obtained at 0.1C and 55 °C, nearly equivalent to the reversible cycling of two lithium ions per Li3V2(PO4)3 formula unit (133 mAh g−1). It was found that the increase in total carbon content can improve the discharge performance of the Li3V2(PO4)3 electrode. In the voltage range of 3.0-4.8 V, the extraction and reinsertion of the third lithium ion in the carbon coated Li3V2(PO4)3 host are almost reversible, exhibiting a reversible capacity of 177 mAh g−1 and good cyclic performance. The reasons for the excellent electrochemical performance of the carbon coated Li3V2(PO4)3 cathode material were also discussed.  相似文献   

15.
Spherical (Ni0.5Mn0.5)(OH)2 with different secondary particle size (3 μm, 10 μm in diameter) was synthesized by co-precipitation method. Mixture of the prepared hydroxide and lithium hydroxide was calcined at 950 °C for 20 h in air. X-ray diffraction patterns revealed that the prepared material had a typical layered structure with space group. Spherical morphologies with mono-dispersed powders were observed by scanning electron microscopy. It was found that the layered Li[Ni0.5Mn0.5]O2 delivered an initial discharge capacity of 148 mAh g−1 (3.0-4.3 V) though the particle sizes were different. Li[Ni0.5Mn0.5]O2 having smaller particle size (3 μm) showed improved area specific impedance due to the reduced Li+ diffusion path, compared with that of Li[Ni0.5Mn0.5]O2 possessing larger particle size (10 μm). Although the Li[Ni0.5Mn0.5]O2 (3 μm) was electrochemically delithiated to Li0.39[Ni0.5Mn0.5]O2, the resulting exothermic onset temperature was around 295 °C, of which the value is significantly higher than that of highly delithiated Li1−δCoO2 (∼180 °C).  相似文献   

16.
A positive electrode material for lithium ion battery applications was successfully synthesized using microwave irradiation. This microwave synthesis has several merits such as homogeneity of final product and much shorter reaction time compared to conventional synthetic methods. We synthesized spherical [Ni0.4Co0.2Mn0.4](OH)2 as a precursor by a co-precipitation method. The pelletized mixture of the precursor and lithium hydroxide was calcined under different reaction times and temperatures by applying 1200 W of microwave irradiation at 2.45 GHz. We determined the optimum conditions of microwave synthesis for positive electrode materials. The powders were characterized by X-ray diffraction, scanning electron microscopy, and electrochemical testing. The capacity, its retention, and thermal stability of Li[Ni0.4Co0.2Mn0.4]O2 synthesized by the microwave synthesis were comparable to the Li[Ni0.4Co0.2Mn0.4]O2 prepared by the high temperature calcination method.  相似文献   

17.
A novel method to improve the cycling performance of LiCo1/3Ni1/3Mn1/3O2 in lithium-ion batteries by 1.0 wt.% CeO2-coating is presented in this work. The crystalline structure and morphology of the synthesized powder have been characterized by XRD, SEM, TEM and their electrochemical performances were evaluated by CV, EIS and galvonostatic charge/discharge tests. It is found that CeO2 forms a layer on the surface of LiCo1/3Ni1/3Mn1/3O2 without destroying the crystal structure of the core material. Electrochemical test indicates that CeO2-coating could improve the cycling performance of LiCo1/3Ni1/3Mn1/3O2. At room temperature, the capacity retention of 1.0 wt.% CeO2-coated material is 93.2% after 12 cycles at 3.0 C while that of the bare sample is only 86.6%. ICP-OES proves the coating layer could protect the dissolution of the transition metal ions from LiCo1/3Ni1/3Mn1/3O2. From the analysis of EIS, the improvement of cycle ability could be attributed to the suppression of the reaction between cathode and electrolyte.  相似文献   

18.
In this study, the LiCoO2/LiNi1/3Mn1/3Co1/3O2 mixed cathode electrodes were prepared and their electrochemical performances were measured in a high cut-off voltage. As the contents of LiNi1/3Mn1/3Co1/3O2 in the mixed cathode increases, the reversible specific capacity and cycleability of the electrode enhanced, but the rate capability deteriorated. On the contrary, the rate capability of the cathode enhanced but the reversible specific capacity and cycleability deteriorated, according to increasing the contents of LiCoO2 in the mixed cathode. The cell of LiCoO2/LiNi1/3Mn1/3Co1/3O2 (50:50, wt.%) mixed cathode delivers a discharge capacity of ca. 168 mAh/g at a 0.2 C rate. The capacity of the cell decreased with the current rate and a useful capacity of ca. 152 mAh/g was obtained at a 2.0 C rate. However, the cell shows very stable cycleability: the discharge capacity of the cell after 20th charge/discharge cycling maintains ca. 163 mAh/g.  相似文献   

19.
Carbon coated Li3V2(PO4)3 cathode material was prepared by a poly(vinyl alcohol) (PVA) assisted sol-gel method. PVA was used both as the gelating agent and the carbon source. XRD analysis showed that the material was well crystallized. The particle size of the material was ranged between 200 and 500 nm. HRTEM revealed that the material was covered by a uniform surface carbon layer with a thickness of 80 Å. The existence of surface carbon layer was further confirmed by Raman scattering. The electrochemical properties of the material were investigated by charge-discharge cycling, CV and EIS techniques. The material showed good cycling performance, which had a reversible discharge capacity of 100 mAh g−1 when cycled at 1 C rate. The apparent Li+ diffusion coefficients of the material ranged between 9.5 × 10−10 and 0.9 × 10−10 cm2 s−1, which were larger than those of olivine LiFePO4. The large lithium diffusion coefficient of Li3V2(PO4)3 has been attributed to its special NASICON-type structure.  相似文献   

20.
This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a CuO/La2O3 composite catalyst at temperatures between 150 and 400 °C. A CuO/La2O3 composite catalyst was prepared by co-precipitation of copper nitrate and lanthanum nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (C0 = 1000 ppm), the space velocity (GHSV = 92,000 l/h), the relative humidity (RH = 12%) and the concentration of oxygen (O2 = 4%) affect the operational stability and the capacity for removing NH3. The catalysts that were characterized using FTIR, XRD, UV-Vis, BET and PSA, have shown that the catalytic behavior is related to the copper (II) oxide, while lanthanum (III) oxide may serve only to provide active sites for the reaction during a catalyzed oxidation run. The experimental results show that the extent of conversion of ammonia by SCO in the presence of the CuO/La2O3 composite catalyst was a function of the molar ratio. The ammonia was removed by oxidation in the absence of CuO/La2O3 composite catalyst, and around 93.0% NH3 reduction was achieved during catalytic oxidation over the CuO/La2O3 (8:2, molar/molar) catalyst at 400 °C with an oxygen content of 4.0%. Moreover, the effect of the reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of under 92,000 h− 1.  相似文献   

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