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1.
A precursor of TiO2–LiCo1/3Ni1/3Mn1/3O2 was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO2-coated material can be indexed by α-NaFeO2 layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO2 compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO2-coated LiCo1/3Ni1/3Mn1/3O2 material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO2-coated LiCo1/3Ni1/3Mn1/3O2 sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO2-coated LiCo1/3Ni1/3Mn1/3O2 was improved.  相似文献   

2.
In this investigation, Mn3O4 spinel-type oxide was synthesized at low temperature using the Pechini process. We employed a sol-gel route, in which a solution of Mn(II) in a mixture of citric acid and ethylene glycol was heated to form a polymeric precursor, followed by annealing at lower temperature. The oxide obtained was identified by X-ray diffraction, scanning electron spectroscopy, and Raman spectroscopy. The results revealed that the formation of Mn3O4 hausmannite structure with a minor secondary phase of MnSO4 occurred at or above 280 °C. The sample powder consisted of fine grains with homogeneous morphology and an average size close to 1 μm was obtained. This new preparation procedure yielded an electrode oxide which appears to be a promising cathode material for fuel cells and metal-air batteries.  相似文献   

3.
Effects of two different precipitants of Na2CO3 and Na2C2O4 on LiNi0.5Mn1.5O4 (LNMO) cathode materials, which are prepared by a modified co-precipitation method, have been investigated. Various measurements have been applied to characterize the physical and electrochemical performances of LNMO. Compared with the LNMO prepared by the oxalate co-precipitation (LNMO2), the material synthesized by the carbonate co-precipitation (LNMO1) not only shows more uniform porosity and smaller particles but also has a better rate capability and cycling performance. In addition, the sample prepared by carbonate has a stable spherical structure, due to the fact that carbonate co-precipitation with less gas release during calcination can prevent the destruction of the as-prepared LNMO material structure and promote the formation of regular particle and aperture. Based on the electrochemical test results, LNMO1 shows greatly enhanced electrochemical performance of a high initial discharge capacity of 125.6 mAh g?1 at 0.25 °C, as well as a preferably capacity retention of 96.5% after 100 cycles at 0.5 °C. And even at a high rate of 10 °C, the discharge capacity of LNMO1-based cell still approaches 83.1 mAh g?1.  相似文献   

4.
In this study, well-crystallized Li4Mn5O12 powder was synthesized by a self-propagating combustion method using citric acid as a reducing agent. Various conditions were studied in order to find the optimal conditions for the synthesis of pure Li4Mn5O12. The precursor obtained was then annealed at different temperatures for 24 h in a furnace. X-ray diffraction results showed that Li4Mn5O12 crystallite is stable at relatively low temperature of 400 °C but decompose to spinel LiMn2O4 and monoclinic Li2MnO3 at temperatures higher than 500 °C. The prepared samples were also characterized by FESEM and charge-discharge tests. The result showed that the specific capacity of 70.7 mAh/g was obtained within potential range of 4.2 to 2.5 V at constant current of 1.0 mA. The electrochemical performances of Li4Mn5O12 material was further discussed in this paper.  相似文献   

5.
The Li-rich cathode material Li[Li0.2Mn0.54Ni0.13Co0.13]O2 had been successfully synthesized by a carbonate coprecipitation method. The effects of substituting traces of Al element for different transitional metal elements on the crystal structure and surface morphology had been investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy. The results revealed that all the materials showed similar XRD patterns and surface morphology. It was demonstrated that LNCMAl1 exhibited the superior electrochemical performance. The discharge capacity was 265.2 mAh g?1 at 0.1 C and still maintained a discharge capacity of 135.6 mAh g?1 at 5.0 C. The capacity retention could still be 58.2 and 66.8% after 50 cycles at 1.0 and 2.0 C, respectively. Electrochemical impedance spectra results proved that the remarkably improved rate capability and cycling performance could be ascribed to the low charge transfer resistance and enhanced reaction kinetics.  相似文献   

6.
AlF3-coating is attempted to improve the performance of LiNi0.5Mn1.5O4 cathode materials for Li-ion batteries. The prepared powders are characterized by scanning electron microscope, powder X-ray diffraction, charge/discharge, and impedance. The coated LiNi0.5Mn1.5O4 samples show higher discharge capacity, better rate capability, and higher capacity retention than the uncoated samples. Among the coated samples, 1.0 mol% AlF3-coated sample shows highest capacity after charge–discharged at 30 mA/g for 3 cycles, but 4.0 mol% coated sample exhibits the highest capacity and cycling stability when cycled at high rate of 150 and 300 mA/g. The 40th cycle discharge capacity at 300 mA/g current still remains 114.8 mAh/g for 4.0 mol% AlF3-coated LiNi0.5Mn1.5O4, while only 84.3 mAh/g for the uncoated sample.  相似文献   

7.
Li[Ni1/3Co1/3Mn1/3]O2 and Sn-doped Li[Ni1/3Co1/3Mn1/3]O2 cathode materials for lithium battery are synthesized by a solid-state method. The samples are characterized by X-ray diffraction, scanning electron microscope, electrochemical impedance spectroscopy (EIS), and charge–discharge test. The results show that the Sn-doped Li[Ni1/3Co1/3Mn1/3]O2 has a typical hexagonal α-NaFeO2 structure and strawberry-like shape with uniform particle size. It has also been found that the Sn-doped Li[Ni1/3Co1/3Mn1/3]O2 reveals better electrochemical performances than that without Sn doping. The EIS results suggest that Sn presence decreases the total resistance of Li[Ni1/3Co1/3Mn1/3]O2, which should be related to the improvement on the electrochemical properties.  相似文献   

8.
The high-voltage spinel LiNi0.5Mn1.5O4 (LNMO) with submicron particle size (LNMO-8505P70010) has been synthesized based on nickel-manganese compound, which is obtained from pre-sintering the nickel-manganese hydroxide precipitation at 850 °C. The LNMO materials based on nickel-manganese hydroxide (LNMO-70010, LNMO-850570010, and LNMO-8501070010) have also been synthesized for comparison to study the pre-sintering impact on the properties of LiNi0.5Mn1.5O4 material. The morphologies and structures of the obtained samples have been analyzed by X-ray powder diffraction and scanning electron microscopy. The nickel-manganese compound has a spinel structure with high crystallinity, making it a good precursor to form high-performance LNMO with lower content of Mn3+ and impurity. The obtained LNMO-8505P70010 delivers discharge capacities of 125.4 mA h g?1 at 0.2 C, and the capacity retention of 15 C reaches 73.8 % of the capacity retention of 0.2? C. Furthermore, it shows a superior cyclability with the capacity retention of 96.4 % after 150 cycles at 5 ?C. Compared with the synthesis method without pre-sintering, the synthesis method with pre-sintering can save energy while reaching the same discharge specific capacity.  相似文献   

9.
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   

10.
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   

11.
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   

12.
In this work, Li2ZrF6, a lithium salt additive, is reported to improve the interface stability of LiNi0.5Mn1.5O4 (LNMO)/electrolyte interface under high voltage (4.9 V vs Li/Li+). Li2ZrF6 is an effective additive to serve as an in situ surface coating material for high-voltage LNMO half cells. A protective SEI layer is formed on the electrode surface due to the involvement of Li2ZrF6 during the formation of SEI layer. Charge/discharge tests show that 0.15 mol L?1 Li2ZrF6 is the optimal concentration for the LiNi0.5Mn1.5O4 electrode and it can improve the cycling performance and rate property of LNMO/Li half cells. The results obtained by electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) demonstrate that Li2ZrF6 can facilitate the formation of a thin, uniform, and stable solid electrolyte interface (SEI) layer. This layer inhibits the oxidation decomposition of the electrolyte and suppresses the dissolution of the cathode materials, resulting in improved electrochemical performances.  相似文献   

13.
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   

14.
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   

15.
LiSmxMn2–xO4 samples were synthesized via co-precipitation technique. The structural properties of the synthesized materials were studied using X-ray diffraction analysis and it confirmed the cubic spinel structure for all the compounds. The lattice parameter of LiMn2O4 was observed to be 8.2347 Ǻ and it decreased with Sm3+ concentration, due to the shrinkage in cell volume aided by higher binding energy between Sm-O bond. The SEM micrographs were analyzed using Image processing software (Image-J) to ascertain the pore and grain properties. The microwave synthesis had been observed to control the bulk grain formation and had yielded lesser porous and nanoparticles. The particle size distributions obtained through photocross correlation laser diffraction analysis had shown that LiMn2O4 with 60 nm and Sm-doped compounds with ∼30 nm, respectively. The cyclic voltammetry studies had revealed the decrease in electrocatalytic behavior in the initial cycle for compounds doped with Sm3+ ion. The initial capacities of LiMn2O4, LiSm0.05Mn1.95O4 and LiSm0.10Mn1.90O4 substituted compounds were observed to be 134.87 mAhg−1, 132.22 mAhg−1 and 126.41 mAhg−1, respectively. The cells were simulated using 1D model namely Dualfoil5.1 program. The simulated results coincide well with the measured results. The cycle life studies reveal 93% capacity retention of samarium-0.05-doped samples when compared with 78.4% of the LiMn2O4.  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.
LiNi0.5Mn0.5O2 powder was synthesized by a coprecipitation method. LiOH.H2O and coprecipitated [(Ni0.5Mn0.5)C2O4] precursors were mixed carefully together and then calcined at 900°C. Surface modified cathode materials were obtained by coating LiNi0.5Mn0.5O2 with a thin layer of amorphous carbon using table sugar and starch as carbon source. Both parent and carbon-coated samples have the characteristic layered structure of LiNi0.5Mn0.5O2 as estimated from X-ray diffractometry measurements. Transmission electron microscope showed the presence of C layer around the prepared particles. TGA analysis emphasized and confirmed the presence of C coating around LiNi0.5Mn0.5O2. It is obvious that the carbon coating appears to be beneficial for the electrochemical performance of the LiNi0.5Mn0.5O2. A capacity of about 150 mAh/g is delivered in the voltage range 2.5–4.5 V at current density C/15 for carbon coated LiNi0.5Mn0.5O2 in comparison with about 165 mAh/g obtained for carbon free LiNi0.5Mn0.5O2 at the same current density and voltage window. About 92% and 82% capacity retention was obtained at 50th cycle for coated LiNi0.5Mn0.5O2 using sucrose and starch, respectively; whereas, 75% was retained after only 30th cycle for carbon free LiNi0.5Mn0.5O2. This improvement is mainly attributed to the presence of thin layer of carbon layer that encapsulate the nanoparticles and improve the conductivity and the electrochemical performance of LiNi0.5Mn0.5O2.  相似文献   

18.
Ag1.8Mn8O16 nanorods have been synthesized on a large scale by a facile hydrothermal route. The effects of experimental conditions including reaction time and reactant concentration on the phase and morphology of the final products were investigated systematically. The products were characterized by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray (EDX) spectroscopy. Electrochemical lithium-storage capabilities of the as-formed nanostructured Ag1.8Mn8O16 were also evaluated. Interestingly, the as-formed Ag1.8Mn8O16 nanorods possess the unique one-dimensional structure and in situ silver loading, which are beneficial features for electrochemical lithium-storage applications. The results suggest their potential use as cathode materials for lithium-ion batteries.  相似文献   

19.
Among the various cathode materials explored for sodium-ion batteries (SIBs), NaMn0.33Ni0.33Co0.33O2, with a layered oxide structure, is a promising material due to its high theoretical capacity (240 mAhg?1). We have synthesized NaMn0.33Ni0.33Co0.33O2 using two different types of precursors, namely metal acetates and metal nitrates by the sol-gel method. XRD patterns confirm the formation of a stable phase of the material at 900 °C. Coupled TGA-FTIR analysis was used to optimize the calcination conditions and to understand the hydrolysis and condensation mechanism of the sol-gel precursors. FTIR spectra extracted at different temperatures reveal the polymer network-forming tendency of the acetate ligands whereas the polymerization is inhibited in the nitrate precursors. SEM analysis shows spherical and platelet morphologies of samples synthesized from nitrate and acetate precursors, respectively. Using in situ impedance and galvanostatic charge/discharge studies, we observed that the precursors used to synthesize the cathode material influence the electrochemical properties of the material, as in this case, where we observe a 20 % improvement in terms of capacity by using acetate precursors instead of nitrate precursors.  相似文献   

20.
In this work, we research two series of Mn-substituted bismuth molybdates: Bi26-2xMn2xMo10O69-d and Bi26Mo10-2yMn2yO69-d. The synthesis of powder samples is performed by the conventional solid state technology. Samples are characterized by X-ray diffraction, scanning electron microscopy, and chemical analysis methods, and it is shown that single phase Bi26-2xMn2xMo10O69-d and Bi26Mo10-2yMn2yO69-d complex oxides form up to x = 0.8 and y = 0. We use densitometry, grain size measurements and scanning electron microscopy to study the morphology of ceramic pellets and powders. This issue reveals formation of dense ceramic samples with low porosity (≤3%). High-temperature X-ray diffraction is used to define small deviation of unit cell parameters from their linear dependence on temperature. Measurement of electrical conductivity is made using a.c. impedance spectroscopy method. We observe the decrease of electrical conductivity in Bi26-2xMn2xMo10O69-d series depending on dopant concentration.  相似文献   

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