Electrochemical performance of SrF2-coated LiMn2O4 cathode material for Li-ion batteries

SrF2-coated LiMn2O4 powders with excellent electrochemical performance were synthesized. The electrochemical performance of SrF2-coated LiMn2O4 electrodes was studied as function of the level of SrF2 coating. With increasing the amount of the coated-SrF2 to 2.0% （molar fraction）, the discharge capacity of LiMn2O4 decreases slightly, but the cycleability of LiMn2O4 at elevated temperature is improved obviously. In view of discharge capacity and cycleability, the 2.0% （molar fraction） coated sample shows optimum cathodic behaviors. When being cycled at 55 ℃, as-repared LiMn2O4 remains only 79% of its initial capacity after 20 cycles, whereas the 2.0% （molar fraction） coated sample shows initial discharge capacity of 108 mA-h/g, and 97% initial capacity retention.     

Preparation and electrochemical performance of nanosized Co3O4 via hydrothermal method

The hydrotalcite-type cobalt compounds were prepared through oxidation of Co（OH）2 gel using NH4OH as precipitating agent and H2O2 as oxidant. These hydrotalcite-type cobalt compounds were transformed into Co3O4 through hydrothermal decomposition with nanostructural deformation. The precursor and product were characterized by Fourier-transform infrared（FT-IR） spectrum, X-ray diffractometry（XRD） and transmission electron microscopy（TEM）. The electrochemical performances of as-prepared nanosized Co3O4 as anode materials in lithium-ion batteries were tested by charge-discharge test in the voltage range of 0-3.0 V. The influence of morphology of Co3O4 particle on the capacity and cycling performance was studied. The results show that the shape and size of the final product can be controlled by altering cobalt sources. The irregular cubic Co3O4 with the average particle size of about 10 nm shows the best electrochemical performance. After 10 charge-discharge cycles, the specific charge capacity retains 555 mA.h/g.     

Electrochemical property of LiFePO_4/C composite cathode with different carbon sources

To improve the performance of battery cathode materials that consist of carbonaceous organic material,carbon coatings on lithium iron phosphate (LiFePO_4/C)materials were synthesized by different carbon sources.LiFePO_4/C was synthesized by a combination method of sol-gel and gas-phase diffused permeation. LiFeO_4/C materials were prepared by coating different carbon contents. High-performance composite materials were prepared by combining carbon with element doped by two modified methods. The elements of Fe and C came from Fe3+and sucrose, glucose, citric acid. Thermogravimetrydifferential thermal analysis (TG-DTA), X-ray diffractometer (XRD), scanning electron microscope (SEM),cycle voltammetry (CV), and charge-discharge test were used to characterize and test the surface morphology,structure, and electrochemical performance. The results show that LiFePO_4/C synthesized with sucrose has higher specific discharge capacity than the other materials. The specific discharge capacity of this material is 84.27 mAh·g~(-1). The capacity retention could attain 94%of the initial discharge capacity after 30 cycles, showing good electrochemical performance.     

Synthesis and physicochemical properties of LiLa0.01Mn1.99O3.99F0.01 cathode materials for lithium ion batteries

Spinel lithium manganese oxide cathode materials were synthesized using the ultrasonic-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis （DTA） and thermogravimetry （TG）, powder X-ray diffraction （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, and the charge-discharge test. TG-DTA shows that significant mass loss occurs in two temperature regions during the synthesis of LiLa0.01Mn1.9903.99F0.01. XRD data indicate that all samples exhibit the same pure spinel phase, and LiLa0.01Mn1.9903.99F0.01 and LiLa0.01Mn1.9904 samples have a better crystallinity than LiMn2O4. SEM images indicate that LiLa0.01Mn1.9903.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn2O4, LiLa0.01Mn1.99O4, and LiLa0.01Mn1.99O3.99F0.01 are 130, 123, and 126 mAh·g^-1, respectively, and the capacity retention rates of the initial value, after 50 cycles, are 84.8%, 92.3%, and 92.1%, respectively. The electrode coulomb efficiency and CV reveal that the electrode synthesized by the ultrasonic-assisted sol-gel （UASG） method has a better re- versibility than the electrode synthesized by the sol-gel method.     

Preparation of NaV1−xAlxPO4F cathode materials for application of sodium-ion battery

The effects of Al doping on the electrochemical properties of NaVPO4F as a cathode material for sodium-ion batteries were investigated. Al-doped NaV1-xAlxPO4F （x=0, 0.02） samples were prepared by a simple high temperature solid-state reaction involving VPO4 and NaF for the application of cathode material of sodium-ion batteries. The crystal structure and morphology of the material were studied by Flourier-infrared spectrometry（FT-IR）, X-ray diffractometry（XRD） and scanning electron microscopy（SEM）. The results show that NaV1-xAlxPO4F （x=0, 0.02） has a typical monoclinic structure. The effects of Al doping on the performance of the cathode material were analyzed in terms of the crystal structure, charge-discharge curves and cycle performance. It is found that NaV0.98Al0.02PO4F shows an improved cathodic behavior and discharge capacity retention compared with the undoped samples in the voltage range of 3.0-4.5 V. The electrodes prepared from NaV0.98Al0.02PO4F deliver an initial discharge capacity of 80.4 mA.h/g and an initial coulombic efficiency of 89.2%, and the capacity retention is 85% after 30th cycle. Though the Al-doped samples have lower initial capacities, they show better cycle performance than Al-free samples.     

Charge-discharge process of MnO2 supercapacitor

Mechanochemical synthesis of α-MnO2 was carried out with KMnO4 and Mn（CH3COO）2 in 1：1 mole ratio. The electrochemical performance of MnO2 electrode was investigated by cyclic voltammograms and alternating current impedance. The charge-discharge process of MnO2 supercapacitor in 6 mol/L KOH was studied within 1.2 V at 200 mA/g, suggesting that it displays double-layer capacibility in low potential scope and pseudo-capacitance properties in high potential scope. It is found that Mn3O4, an electrochemical inert, mainly forms in the initial 40 charge-discharge cycles. During cycling, the pseudo-capacitance properties disappear and the discharge curves are close to ideal ones, indicating double-layer capability. The maximum capacitance of MnO2 electrode is as high as 416 F/g, and retains 240 F/g after 200 cycles. The equivalent series resistance increases from 17 to 41Ω.     

Powder electrochemical properties with different particle sizes of spinel LiAl0.05Mn1.95O4 synthesized by sol-gel method

An Al-doped spinel lithium manganese oxide was prepared by the adipic acid-assisted sol-gel method at 800℃, and the cathode materials （Liml0.05Mnl.9504） with different particle sizes were obtained through ball milling. The effects of particle size on the electrochemical performance of LiAl0.05Mnl.9504 samples were investigated by differential thermal analysis and thermogravimetry, X-ray diffraction, galvanostatic charge-discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The results indicate that all samples with different particle sizes show the same pure spinel phase and good crystal structure; LiAlo.osMnl.9504 with Dso = 17.3 μm shows better capacity retention; LiAlo.osMnl.gsO4 cathode materials with small particle size have a bigger resistance of charge transfer than the large one, and the particle size has significant effects on the electrochemical performance of Al-doped spinel LiMn2O4 cathode materials.     

Preparation and electrochemical properties of LiMn1.95M0.05O4 （M=Cr, Ni）

The preparation process and electrochemical properties of LiMn2O4 and LiMnl.95M0.05O4 （M = Cr, Ni） were studied. The results show that the decomposition temperature range of xerogel prepared with lithium acetate and manganese acetate as raw rnaterials is large and the decomposition speed is slow. Oxygen consumed is apt to get a prompt supplement during the preparation of LiMn2O4, and carbonization of the organic matter can be reduced or avoided, which is favorable to the combination of lithium and manganese. Using lithium acetate, manganese acetate, chromium nitrate, and nickel nitrate as raw materials and adopting the citric acid complexing method, it has been found that the prepared powders have high purity, high quality stability, and even doping characters. With the increase of sintering temperature, the particle size and crystal lattice constant of LiMn1.95M0.05O4 （M = Cr, Ni） enhance. However, the purity of the product is relatively high and has no obvious change, which is advantageous to the control of the quality of LiMn1.95M0.0504 （M = Cr, Ni）. Doping with a small amount of Cr3. and Ni^2＋ can stabilize the spinel structure of LiMn2O4, suppress the Jahn-Teller effect, and improve the cycling properties but reduce the initial capacity.     

Preparation and characterization of spinel LiMn2O4 nanorods as lithium-ion battery cathodes

The hydrothermal synthesis of single-crystallineβ-MnO2 nanorods and their chemical conversion into single-crystalline LiMn2O4 nanorods by a simple solid-state reaction were reported.This method has the advantages of producing pure,single-phase and crystalline nanorods.The LiMn2O4 nanorods have an diameter of about 300 nm.The discharge capacity and cyclic performance of the batteries were investigated.The LiMn2O4 nanorods show better cyclic performance with a capacity retention ratio of 86.2% after 100 cycles.Battery cyclic studies reveal that the prepared LiMn2O4 nanorods have high capacity with a first discharge capacity of 128.7 mA·h/g.     

High-rate capability of spinel LiNi0.05Mn1.95O4 cathode for Li-ion batteries prepared via coprecipitated precursor

Spinel LiNi0.05Mn1.95O4 cathode material for lithium ion batteries was synthesized by solid-state reaction from coprecipitated Ni-Mn hydroxide precursors and characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM） and galvanostatic charge-discharge tests. It is found that LiNi0.05Mn1.95O4 powder has an ordered cubic spinel phase （space group Fd3m） and exhibits superior rate capability. After 450 cycles, the LiNi0.05Mn1.95O4/carbonaceous mesophase spheres（CMS） Li-ion batteries can retain 96.0% and 93.3% capacity at 5C and 10C charge/discharge rate, respectively, compared with 85.3% （5C） and 80.5% （10C） retention for LiMn204 batteries. However, the initial discharge capacity of LiNi0.05Mn1.95O4/CMS batteries at 1C charge/discharge rate （96.20 mA.h/g） is slightly lower than that of the LiMn2O4 batteries （100.98 mA.h/g） due to the increased average oxidation state of Mn inLiNi0.05Mn1.95O4.     

Mg、F复合掺杂尖晶石LiMg0.1Mn1.9O3.95F0.05的合成和电化学行为研究

以己二酸为配位体采用溶胶-凝胶法合成了LiMn2O4,Mg掺杂或Mg和F复合掺杂的尖晶石锂镁氧化物正极材料.对合成出的样品采用X-射线衍射仪、X-光电子能谱、扫描显微电子镜、循环伏安测试和充放电测试仪进行了详细的研究.X-射线衍射结果表明,所有的样品都具有相同的纯尖晶石相,LiMg0.1Mn1.9O4和LiMg0.1Mn1.9O3.95F0.05与LiMn2O4的样品相比,具有较小的晶格参数和晶胞体积.X-光电子能谱试验结果表明,在LiMn2O4中,Mn3 和Mn4 的相对量分别为50.2%和49.8%,而LiMg0.1Mn1.9O3.95F0.05中Mn3 和Mn4 的相对量分别为48.4%和51.6%.扫描电镜结果显示,LiMg0.1Mn1.9O3.95F0.05颗粒尺寸略小、尺寸分布窄,形态结构更为规整.循环伏安实验显示,Mg和F复合掺杂的尖晶石具有更好的可逆性.LiMn2O4,LiMg0.1Mn1.9O4,LiMg0.1Mn1.9O3.95F0.05样品的首次放电能量和能量保持率分别为123、111、114 mAh·g-1和86.5%、92.3%、90.9%,且LiMg0.1Mn1.9O4和LiMg0.1Mn1.9O3.95F0.05具有比LiMn2O4更高的库仑效率.     

合成温度对LiMn1.95Mg0．05O4结构与性能的影响

用柠檬酸辅助溶胶一凝胶法在不同温度下合成了LiMn1.95Mg0．05O4正极材料。用X射线衍射、充放电测试以及电化学阻抗谱分析技术研究了不同合成温度对LiMn1.95Mg0．05O4结构和电化学性能的影响。结果表明：合成温度对LiMn1.95Mg0．05O4正极材料的晶相结构、电化学性能有显著影响,LiMn1.95Mg0．05O4尖晶石相的生成和长大与其合成的温度有密切的关系,合成的最佳温度为750℃;在750℃条件下合成的LiMn1.95Mg0．05O4具有较高的电化学活性和较好的晶相结构;高温合成有利于提高LiMn1.95Mg0．05O4正极材料的放电容量,低温合成有利于提高其循环性能。     

Improving the electrochemical performance of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries using LiF additive during fabrication

LiMn2O4/graphite batteries using LiF additive were fabricated and their electrochemical performance including discharge,cycling and storage performances were tested and compared with LiF-free LiMn2O4/graphite batteries.The LiMn2O4/graphite battery with LiF added shows better capacity (107.5 mAh/g),cycling performance (capacity retention ratio of 93% after 100 cycles),and capacity recovery ratio (98.1%) than the LiF-free battery.The improvement in electrochemical performance of the LiF-added LiMn2O4/graphite...     

Synthesis and characterization of Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3-coated LiMn_2O_4 by wet chemical route

Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 was prepared by wet chemical route. The phase,surface morphology,and electrochemical properties of the prepared powders were characterized by X-ray diffraction,scanning electron micrograph,and galvanostatic charge-discharge experiments. Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 has similar X-ray diffraction patterns as LiMn2O4. The corner and border of Li1.3Al0.3Ti1.7(PO4)3-coated LiMn2O4 particles are not as clear as the uncoated one. The two powders show similar values of l...     

Synthesis and physicochemical properties of LiLa0.01Mnt.99O3.99F0.01 cathode materials for lithium ion batteries

Spinel lithium manganese oxide cathode materials were synthesized using the ultrasonic-assisted sol-gel method.The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG),powder X-ray diffraction (XRD),scanning electron microscopy (SEM),cyclic voltammetry (CV),and the charge-discharge test.TG-DTA shows that significant mass loss occurs in two temperature regions during the synthesis of LiLa0.01Mn1.99O3.99F0.01.XRD data indicate that all samples exhibit the same pure spinel phase,and LiLa0.01Mn1.99O3.99F0.01 and LiLa0.01Mn1.99O4 samples have a better crystallinity than LiMn2O4. SEM images indicate that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution.The charge-discharge test reveals that the initial capacities of LiMn2O4,LiLa0.01Mn1.99O4,and LiLa0.01Mn1.99O3.99F0.01 are 130,123,and 126 mAh·g-1,respectively,and the capacity retention rates of the initial value,after 50 cycles,are 84.8%,92.3%,and 92.1%,respectively.The electrode coulomb efficiency and CV reveal that the electrode synthesized by the ultrasonic-assistexi sol-gel (UASG) method has a better reversibility than the electrode synthesized by the sol-gel method.     

熔融浸渍法LiMn2O4的制备及性能

利用电解二氧化锰（EMD）和碳酸锂为原料，采用熔融浸渍法合成了尖晶石型锂锰氧化物LiMn2O4，并用热重分析（TGA）、粉末X射线衍射技术研究了合成条件对产物的晶体结构、电化学性能的影响。研究结果表明，在合成的后续阶段反应时间的长短对产物的晶体结构和电化学性能的影响很大，时间长，会使LiMn2O4分解为Li2MnO3和Mn2O3;LiMn2O4的初始放电比容量也随反应时间的延长而下降。在最佳条件下合成的LiMn2O4的首次放电比容量高达132.4mAh/g，50次循环后的放电比容量还保持在125.6mAh/g的水平。     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料,通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD),场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析,并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明,Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构,包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善,1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1,充放电循环500次后容量保持率分别为88.4%和78.2%,而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1,500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1,而未包覆材料的活化能为36.24 kJ?mol-1,包覆有效降低了材料Li+扩散所需克服的能垒,提高了材料的电化学性能。     

以Mn3O4为前驱体制备尖晶石型LiMn2O4及其性能

采用改进的固相反应法合成了高性能的锂离子电池正极材料LiMn2O4。首先,以廉价的MnSO4为原料,通过水解氧化法制备纳米级Mn3O4前驱体;然后,将Mn3O4和Li2CO3混合均匀,在750℃固相反应20 h,得到尖晶石型LiMn2O4。用X射线衍射(XRD)和扫描电镜(SEM)对Mn3O4前驱体和LiMn2O4样品进行表征,用充放电测试和循环伏安技术对LiMn2O4样品进行电化学性能研究。结果表明:所制备的LiMn2O4具有完整的尖晶石型结构,且晶体粒子分布均匀。所制备的LiMn2O4材料在3.0~4.4 V之间,室温(25℃)下,在0.2C倍率下首次放电比容量为130.6 mA.h/g;在0.5C倍率下首次放电比容量为127.1 mA.h/g,30次循环后,容量仍有109.5 mA.h/g,且样品具有较好的高温性能。