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1.
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   

2.
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   

3.
J. Jiang 《Electrochimica acta》2005,50(24):4778-4783
Samples of the layered cathode materials, Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 (x = 1/12, 1/4, 5/12, and 1/2), were synthesized at 900 °C. Electrodes of these samples were charged in Li-ion coin cells to remove lithium. The charged electrode materials were rinsed to remove the electrolyte salt and then added, along with EC/DEC solvent or 1 M LiPF6 EC/DEC, to stainless steel accelerating rate calorimetry (ARC) sample holders that were then welded closed. The reactivity of the samples with electrolyte was probed at two states of charge. First, for samples charged to near 4.45 V and second, for samples charged to 4.8 V, corresponding to removal of all mobile lithium from the samples and also concomitant release of oxygen in a plateau near 4.5 V. Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 samples with x = 1/4, 5/12 and 1/2 charged to 4.45 V do not react appreciably till 190 °C in EC/DEC. Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 samples charged to 4.8 V versus Li, across the oxygen release plateau, start to significantly react with EC/DEC at about 130 °C. However, their high reactivity is similar to that of Li0.5CoO2 (4.2 V) with 1 μm particle size. Therefore, Li[NixLi(1/3−2x/3)Mn(2/3−x/3)]O2 samples showing specific capacity of up to 225 mAh/g may be acceptable for replacing LiCoO2 (145 mAh/g to 4.2 V) from a safety point of view, if their particle size is increased.  相似文献   

4.
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   

5.
LiNi0.5Mn1.5O4 spinel has been prepared by an emulsion drying method which can intermix cations very homogeneously at the atomic scale. When the emulsion-dried precursor was fired at 750 °C for 24 h, the observed particle of the LiNi0.5Mn1.5O4 was nano-crystallite, being about 50 nm in diameter. The Rietveld refinement result clearly exhibited that the cubic spinel phase was successfully formed without any secondary phases, indicating that Li and transition metal cations occupied the 8a and 16d sites of the Fd3m structure, respectively. Li deintercalation from the spinel framework brings about a shift in the XRD peak toward higher angles and a peak splitting in the composition range δ=0-0.2 in LiδNi0.5Mn1.5O4, implying that the host structure is progressively oxidized from Ni2+ to Ni4+ and accompanied by a two phase reaction. The sample calcined at 750 °C for 24 h showed the best cyclability upon cycling due probably to better crystallinity and a smaller particle size. We suggest that this material can be used as a 4.5 V cathode material for Li-ion battery.  相似文献   

6.
A novel Li[Ni0.67Co0.15Mn0.18]O2 cathode material encapsulated completely within a concentration-gradient shell was successfully synthesized via co-precipitation. The Li[Ni0.67Co0.15Mn0.18]O2 has a core of Li[Ni0.8Co0.15Mn0.05]O2 that is rich in Ni, a concentration-gradient shell having decreasing Ni concentration and increasing Mn concentration toward the particle surface, and a stable outer-layer of Li[Ni0.57Co0.15Mn0.28]O2. The electrochemical and thermal properties of the material were investigated and compared to those of the core Li[Ni0.8Co0.15Mn0.05]O2 material alone. The discharge capacity of the concentration-gradient Li[Ni0.67Co0.15Mn0.18]O2 electrode increased with increasing upper cutoff voltage to 4.5 V, and cells with this cathode material delivered a very high capacity, 213 mAh/g, with excellent cycling stability even at 55 °C. The enhanced thermal and lithium intercalation stability of the Li[Ni0.67Co0.15Mn0.18]O2 was attributed to the gradual increase in tetravalent Mn concentration and decrease in Ni concentration in the concentration-gradient shell layer.  相似文献   

7.
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   

8.
Layered Li[Li0.2Ni0.2Mn0.6]O2 powder was modified by coating its surface with amorphous Al(OH)3. Energy dispersive spectroscopy (EDS) showed that nano-sized Al(OH)3 powders were homogeneously dispersed in the parent Li[Li0.2Ni0.2Mn0.6]O2 powders. Al(OH)3 coated Li[Li0.2Ni0.2Mn0.6]O2 exhibited an greater retention capacity at higher rates compared to uncoated Li[Li0.2Ni0.2Mn0.6]O2. The low area specific impedance (ASI) value of the Al(OH)3 is the major factor for its higher rate performance. The 1.4 wt.% Al(OH)3 coated sample had an impedance of 41 Ω cm2 while uncoated Li[Li0.2Ni0.2Mn0.6]O2 had a 57 Ω cm2 at 30-80% state of charge. Electrochemical impedance spectroscopy (EIS) also showed that the Al(OH)3 coated sample had a lower charge transfer resistance (Rct) than the uncoated sample. Differential scanning calorimetry (DSC) analysis showed that Al(OH)3 coating improved the thermal stability. Al(OH)3 coating increased the onset temperature of thermal decomposition and reduced the amount of heat for the exothermic peak.  相似文献   

9.
To fabricate all-solid-state Li batteries using three-dimensionally ordered macroporous Li1.5Al0.5Ti1.5(PO4)3 (3DOM LATP) electrodes, the compatibilities of two anode materials (Li4Mn5O12 and Li4Ti5O12) with a LATP solid electrolyte were tested. Pure Li4Ti5O12 with high crystallinity was not obtained because of the formation of a TiO2 impurity phase. Li4Mn5O12 with high crystallinity was produced without an impurity phase, suggesting that Li4Mn5O12 is a better anode material for the LATP system. A Li4Mn5O12/3DOM LATP composite anode was fabricated by the colloidal crystal templating method and a sol-gel process. Reversible Li insertion into the fabricated Li4Mn5O12/3DOM LATP anode was observed, and its discharge capacity was measured to be 27 mA h g−1. An all-solid-state battery composed of LiMn2O4/3DOM LATP cathode, Li4Mn5O12/3DOM LATP anode, and a polymer electrolyte was fabricated and shown to operate successfully. It had a potential plateau that corresponds to the potential difference expected from the intrinsic redox potentials of LiMn2O4 and Li4Mn5O12. The discharge capacity of the all-solid-state battery was 480 μA h cm−2.  相似文献   

10.
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   

11.
Lei Wen  Qi Lu  Guoxiang Xu 《Electrochimica acta》2006,51(21):4388-4392
This paper describes a novel simple redox process for synthesizing monodispersed MnO2 powders and preparation of spherical LiNi0.5Mn1.5O4 cathode materials by molten salt synthesis (MSS) method. Monodispersed MnO2 powders have been synthesized by using potassium permanganate and manganese sulfate as the starting materials. By using this redox method, it was found that monodispersed MnO2 powders with average particle size ∼5 μm can be easily obtained. Resultant MnO2 and LiOH, Ni(OH)2 was then used to synthesis LiNi0.5Mn1.5O4 cathode materials with retention of spherical particle shape by MSS method. The discharge capacity was 129 mAh g−1 in the first cycle and 127 mAh g−1 after 50 cycles under an optimal synthesis condition for 12 h at 800 °C.  相似文献   

12.
Hui Xia  M.O. Lai 《Electrochimica acta》2009,54(25):5986-5991
Kinetic and transport parameters of Li ion during its extraction/insertion into thin film LiNi0.5Mn0.5O2 free of binder and conductive additive were provided in this work. LiNi0.5Mn0.5O2 thin film electrodes were grown on Au substrates by pulsed laser deposition (PLD) and post-annealed. The annealed films exhibit a pure layered phase with a high degree of crystallinity. Surface morphology and thin film thickness were investigated by field emission scanning electron microscopy (FESEM). The charge/discharge behavior and rate capability of the thin film electrodes were investigated on Li/LiNi0.5Mn0.5O2 cells at different current densities. The kinetics of Li diffusion in these thin film electrodes were investigated by cyclic voltammetry (CV) and galvanostatic intermittent titration technique (GITT). CV was measured between 2.5 and 4.5 V at different scan rates from 0.1 to 2 mV/s. The apparent chemical diffusion coefficients of Li in the thin film electrode were calculated to be 3.13 × 10−13 cm2/s for Li intercalation and 7.44 × 10−14 cm2/s for Li deintercalation. The chemical diffusion coefficients of Li in the thin film electrode were determined to be in the range of 10−12-10−16 cm2/s at different cell potentials by GITT. It is found that the Li diffusivity is highly dependent on the cell potential.  相似文献   

13.
Well-ordered high crystalline LiNi0.5Mn1.5O4 spinel has been readily synthesized by a molten salt method using a mixture of LiCl and LiOH salts. Synthetic variables on the synthesis of LiNi0.5Mn1.5O4, such as synthetic atmosphere, LiCl salt amount, synthetic temperature, and synthetic time, were intensively investigated. X-ray diffraction (XRD) patterns and scanning electron microscopic (SEM) images showed that LiNi0.5Mn1.5O4 synthesized at 900 and 950 °C have cubic spinel structure () with clear octahedral dimension. LiNi0.5Mn1.5O4 spinel phase began to decompose at around 1000 °C accompanied with structural and morphological degradation. LiNi0.5Mn1.5O4 powders synthesized at 900 °C for 3 h delivered an initial discharge capacity of 139 mAh/g with excellent capacity retention rate more than 99% after 50 cycles.  相似文献   

14.
Li[Co1−zAlz]O2 (0 ≤ z ≤ 0.5) samples were prepared by co-precipitation and solid-state methods. The lattice constants varied smoothly with z for the co-precipitated samples but deviated for the solid-state samples above z = 0.2. The solid-state method may not produce materials with a uniform cation distribution when the aluminum content is large or when the duration of heating is too brief. Non-stoichiometric Lix[Co0.9Al0.1]O2 samples were synthesized by the co-precipitation method at various nominal compositions x = Li/(Co + Al) = 0.95, 1.0, 1.1, 1.2, 1.3. XRD patterns of the Lix[Co0.9Al0.1]O2 samples suggest the solid solution limit is between Li/(Co + Al) = 1.1 and 1.2. Electrochemical studies of the Li[Co1−zAlz]O2 samples were used to measure the rate of capacity reduction with Al content, found to be about −250 ± 30 (mAh/g)/(z = 1). Literature work on Li[Ni1/3Mn1/3Co1/3−zAlz]O2, Li[Ni1−zAlz]O2 and Li[Mn2−yAly]O4 demonstrates the same rate of capacity reduction with Al/(Al + M) ratio. These studies serve as baseline characterization of samples to be used to determine the impact of Al content on the thermal stability of delithiated Li[Co1−zAlz]O2 in electrolyte.  相似文献   

15.
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   

16.
High-voltage LiNi0.5Mn1.5O4 spinels were synthesized by a low temperature solution combustion method at 400 °C, 600 °C and 800 °C for 3 h. The phase composition, structural disordering, micro-morphologies and electrochemical properties of the products were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and constant current charge–discharge test. XRD analysis indicated that single phase LiNi0.5Mn1.5O4 powders with disordered Fd-3m structures were obtained by the method at 400 °C, 600 °C and 800 °C. The crystallinity increased with increasing preparation temperatures. XRD and FTIR data indicated that the degree of structural disordering in the product prepared at 800 °C was the largest and in the product prepared at 600 °C was the least. SEM investigation demonstrated that the particle size and the crystal perfection of the products were increased with increasing temperatures. The particles of the product prepared at 600 °C with ~200 nm in size are well developed and homogeneously distributed. Charge/discharge curves and cycling performance tests at different current density indicated that the product prepared at 600 °C had the largest specific capacity and the best cycling performance, due to its high purity, high crystallinity, small particle size as well as moderate amount of Mn3+ ions.  相似文献   

17.
C. Deng  L. Liu  K. Sun  D. Sun 《Electrochimica acta》2008,53(5):2441-2447
The layered Li[Ni1/3Co1/3Mn1/3]O2 powder with good crystalline and spherical shape was prepared by hydroxide co-precipitation method. The effects of pH value, NH4OH amount, calcination temperature and extra Li amount on the morphology, structure and electrochemical properties of the cathode material were investigated in detail. SEM results indicate that pH value affected both the morphology and the property of the cathode material, and the highest discharge capacity in the first cycle of 163 mAh g−1 (2.8-4.3 V) was obtained at pH value was 12. On the contrary, the NH4OH amount, which was used as a chelating agent, only affected the particle size distribution of the material. The calcination temperatures caused great difference in the structure and property of layered Li[Ni1/3Co1/3Mn1/3]O2, and the best electrochemical properties were obtained at the calcination temperature of 800 °C. Extra Li amount not only caused difference in the material structure, but also affected their electrochemical properties. With increasing Li amount, the lattice parameters (a and c) increased monotonously, and the highest first cycle coulombic efficiency (the ratio of discharge capacity to charge capacity in the first cycle) was obtained with the Li/M of 1.10. Therefore, the optimum synthetic conditions for the hydroxide co-precipitation reaction were: pH value was 12, NH4OH amount was 0.36 mol L−1, calcination temperature was 800 °C and the Li/M molar ratio was 1.10.  相似文献   

18.
Spherical Li[Ni0.4Co0.2Mn(0.4−x)Mgx]O2−yFy (x = 0, 0.04, y = 0, 0.08) with phase-pure and well-ordered layered structure have been synthesized by heat-treatment of spherical [Ni0.4Co0.2Mn0.4−xMgx]3O4 precursors with LiOH·H2O and LiF salts. The average particle size of the powders was about 10-15 μm and the size distribution was quite narrow due to the homogeneity of the metal carbonate, [Ni0.4Co0.2Mn(0.4−x)Mgx]CO3 (x = 0, 0.04) precursors. Although the Li[Ni0.4Co0.2Mn0.36Mg0.04]O1.92F0.08 delivered somewhat slightly lower initial discharge capacity, however, the capacity retention, interfacial resistance, and thermal stability were greatly enhanced comparing to the Li[Ni0.4Co0.2Mn0.4]O2 and Li[Ni0.4Co0.2Mn0.36Mg0.04]O2.  相似文献   

19.
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   

20.
Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation   总被引:1,自引:0,他引:1  
Li[Ni1/3Co1/3Mn1/3]O2 powders were synthesized from co-precipitated spherical metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2. The preparation of metal hydroxide was significantly dependent on synthetic conditions, such as pH, amount of chelating agent, stirring speed, etc. The optimized condition resulted in (Ni1/3Co1/3Mn1/3)(OH)2, of which the particle size distribution was uniform and the particle shape was spherical, as observed by scanning electron microscopy. Calcination of the uniform metal hydroxide with LiOH at higher temperature led to a well-ordered layer-structured Li[Ni1/3Co1/3Mn1/3]O2, as confirmed by Rietveld refinement of X-ray diffraction pattern. Due to the homogeneity of the metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2, the final product, Li[Ni1/3Co1/3Mn1/3]O2, was also significantly uniform, i.e., the average particle size was of about 10 μm in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.39 g cm−3, of which the value is comparable to that of commercialized LiCoO2. In the voltage range of 2.8-4.3, 2.8-4.4, and 2.8-4.5 V, the discharge capacities of Li[Ni1/3Co1/3Mn1/3]O2 electrode were 159, 168, and 177 mAh g−1, respectively. For elevated temperature operation (55 °C), the resulted capacity was of about 168 mAh g−1 with an excellent cyclability.  相似文献   

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