Structure and electrochemical properties of LiMn2O4

LiMn2O4, a cathode material of lithium ion battery, was prepared by the citric acid complexing method using lithium acetate and manganese acetate as raw materials. The type of atom location confused degree, the confused degree and judgement method in LiMn2O4 were analyzed. The effect of sintering temperature on structure and electrochemical properties of LiMn2O4 was also investigated. The results show that the atom location confused degree increases with the decrease of the X-ray diffraction peak intensity ratio of LiMn2O4, Ⅰ111/Ⅰ311. The type of atom location confused degree depends on the variation tendency of Ⅰ111/Ⅰ311 and Ⅰ311/Ⅰ400 value. If the variation tendency is the same, it belongs to the 16c type location confusion, however, if the variation tendency is contrary, it belongs to the anti-spinel type location confusion. When the sintering temperature is low, it is apt to produce the anti-spinel location confusion in LiMn2O4. With the increase of sintering temperature, the confused degree with the anti-spinel type gradually reduces, however, the confused degree with 16c type increases to some extent. When the atom location confusion with the anti-spinel type appears in LiMn2O4, both the initial discharging capacity and cycling properties of LiMn2O4 reduce. However, the atom location confusion with 16c type does not affect the charge and discharge properties of LiMn2O4.     

Effect of Cr doping on secondary phases and electrical properties of zinc oxide ceramic thick film varistors

In order to get high-performance low voltage varistors, Cr2O3 doped ZnO ceramic thick films were fabricated by modified sol-gel process. The precursors were fabricated by dispersing doped-ZnO ceramic nano-powders in the sols, which were prepared by dissolving zinc acetate dihydrate into 2-methoxyethanol and stabilized by diethanolamine and glacial acetic acid and doped with a concentrated solution of bismuth nitrate, phenylstibonic acid, cobalt nitrate, manganese acetate and chromium nitrate. The results show that ZnCr2O4 phase can form in ZnO based ceramic films doped 1.0% （mole fraction） Cr2O3. Three secondary phases, such as Bi2o3, Zn7Sb2O12, and ZnCr2O4 phases, are detected in the thick films. The Raman spectra show that the intensity and the position of Raman bands of Zn7Sb2O12 and ZnCr2O4 phases change obviously with increasing Cr203 doping. The nonlinearity coefficient α of ZnO thick films is 7.0, the nonlinear voltage is 6 V, and the leakage current density is 0.7 μA/mm^2.     

Preparation and characterization of LiMn1. 5 Me0.5O4（Me=Ti, Fe, Ni, Zn） for lithium-ion battery cathode materials

Based on synthesizing pure spinel type lithium manganese oxides, the derivations such as LiMn1.5Ti0.5O4, LiMn1.5Fe0.5O4, LiMn1.5Ni0.5O4 and LiMn1.5Zn0.5O4 were prepared using solid-step-sintering method. The structures were characterized by using XRD, SEM and laser granulometer. The electrochemical measurement results show that the element of iron or nickel can raise the discharging plateau voltage of LiMn2O4 , and element titanium improves the electrochemistry property of LiMn2O4 little, while element zinc destroys the electrochemistry property of LiMn2O4. The influence of elements of titanium, iron, nickel, or zinc on the structure of LiMn2O4 pure phase was discussed from the viewpoint of structural chemistry.     

Electrochemical performances and structure characteristic of LiMn2O4-xYx（Y=F, Cl, Br） compounds

Spinel LiMn2 O4-x Yx (Y=F, Cl, Br) compounds were prepared by solid-state reaction and the electrochemically galvanostatic charge-discharge cycles were performed using as-prepared compounds as cathode material. The influence of halogens on their lattice constants and the relation of electrochemical properties and their lattice constants were investigated. It is concluded that when the lattice constants are smaller than that of LiMn2O4, the reversible capacity fade is suppressed and the initial capacity sacrifice is observed. When the content of fluorine is 0.05, the lattice constant of LiMn2O3.95 F0.05 is larger than that of LiMn2O4, the initial capacity is improved. An efficient method was found to control the lattice constants of LiMn2O4 through the addition of halogen, and to improve the electrochemical performance of LiMn2O4. The LiMn2O3.95 F0.05 shows excellent electrochemical charge-discharge performance, with high initial capacity of 143 mAh/g and nearly no capacity loss after 116 cycles.     

Insertion/removal kinetics of lithium ion in spinel LiCuxMn2-xO4

The insertion/removal processes of lithium ion in spinel lithium manganese oxide（LiMn204） and copper doped spinel lithium manganese oxide （LiCuxMn2-xO4） on a powder microelectrode were studied by electrochemical impedance spectroscopy（EIS）, cyclic voltammetry（CV） and X-ray diffractometry（XRD）. The insertion/removal process of lithium ion in the spinel oxides consists of three steps： charge transfer of lithium ion on the surface of the spinel oxides, diffusion and occupation of lithium ion in the lattice of the spinel oxide. Similar to chromium, the doping of copper in spinel lithium manganese oxide results in the increase of the charge transfer resistance and the double layer capacitance for lithium insertion or removal, and the decrease of the diffusion coefficient of lithium ion in the lattice of spinel oxide. However, the insertion capacitance, a parameter reflecting the occupation of lithium ion in the lattice of the spinel oxide, is hardly influenced by the doping of copper. The influence of the doped copper on the kinetic process of lithium insertion/removal in spinel lithium manganese oxide is related to the contraction of spinel lattice.     

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.     

An investigation on stability of biomass reduced manganese dioxide ore

In this study,how to improve the stability of reduced manganese oxide ore was discussed by investigating reoxidation conditions and kinetics mechanism in the cooling process of manganese dioxide ore reduced by biomass.The effects of the temperature and time,chip size of biomass,raw materials thickness and different additives on stability of the products were determined.The valence variation of manganese in ore and the reoxidation kinetics of reduced products were studied.The results show that decrease of reduction temperature and time,and increase of raw materials thickness and little H2SO4 additive are favorable for the stability of the reduced products.The kinetics mechanism of the reoxidation is controlled by diffusion with dynamic apparent activation energy of E1=25.10 kJ·mol-1,and conformation of manganese in the process is changed from MnO to Mn3O4.     

Preparation of 5N high purified indium by the method of chemical purification-electrolysis

The application of indium requires high purity indium as material. 5N high purity indium had been prepared by the method of a combination of chemically smelting and electrolysis. Smelting time was l 0 min, the abstraction rate of cadmium was 80%-90% when used solution of I2-KI and glycerine to smelt indium. 4N metal indium was used as anode, high purity indium as cathode, In:(SO4)3-H2SO4 system as electrolyte, and In content is 100 g/L, pH 2-3 and current density 80- 100 A/m:. The thallium was removed by smelting indium using 15% Nt-LCl-glycerine solution for 20 min and tin by smelting indium using NaOH and NaNO3 for 20 min. The removed rate of tin was 60%.The product quality of indium reached national standard of 5N high purity indium.     

PREPARATION OF MULTI-WALLED CARBON NANOTUBES USING NiO CATALYST SYNTHESIZED BY HYDROTHERMAL METHOD

The Ni(OH)2/SiO2 binary colloid was prepared using Ni(NO3)2.6H2O and (C2H5O)4SiO4 as starting materials and was used to form NiO/SiO2. composite powder by hydrothermal method and desiccant method in open air respectively. Multi-walled carbon nanotubes (MWCNTs) were synthesized respectively by chemical vapor deposition using the NiO/SiO2 catalyst prepared by different methods. The phase and morphology of the catalysts and the morphology, output yield and purity of MWCNTs were compared by XRD, TEM and SEM. The results show that the catalyst powder prepared by hydrothermal method, compared with that by desiccant method, is smaller, better dispersion and has stronger catalytic activity. Pure MWCNTs with smaller tube diameter and narrow range could be obtained at a high yield using that NiO/SiO2 powder prepared by hydrothermal method as catalyst.     

Electrochemical performance of LiNi_(0.5)Mn_(0.5)O_2 with different synthesis methods

Li Ni0.5Mn0.5O2 as a cathode material for Li-ion battery was prepared by the metal acetate decomposition method, sol–gel method, and carbonate co-precipitation method, respectively. The influences of synthesis methods on the physical and electrochemical behaviors of Li Ni0.5Mn0.5O2 were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical tests. XRD patterns show that both the sol–gel and carbonate co-precipitation methods can form single phase of layered structure, while a trace of Ni O impurity is observed via the metal acetate decomposition method. SEM results show the as-prepared carbonate particle has a spherical morphology with an average diameter of 10 lm, consisted of primary nano-sized particles with particle diameter of200 nm. The sample prepared by the carbonate co-precipitation method exhibits the highest discharge specific capacity and the best cycling stability, which results from the steady homogeneity of precursor constant by the fixation of CO2-3group. It can deliver an initial discharge specific capacity of 186.3 m Ahág-1, and retain 170 m Ahág-1after100 cycles at a current rate of 20 m Aág-1in the voltage range of 2.5–4.7 V at 25 °C. Moreover, even at the high temperature of 55 °C, it still delivers a reversible specific capacity of 222.6 m Ahág-1with little capacity loss after 30 cycles.     

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 of modified LiMn2O4 by solid-state reaction

Modified lithium manganese oxides were prepared by solid-state reaction of LiMn2O4 and LiCoO2 as raw materials. A study was carried out by TG-DSC,XRD, DSC and electrochemical to analyse the reaction process and structural characterization of products. The results show that the LiMn2O4 reacts chemically with LiCoO2 at high temperature. All of Li and partial Co atoms can insert into the LiMn2O4 crystal lattice and a newly formed spinel phase-modified LiMn2O4 was obtained. The distribution of Co content is even in modified LiMN2O4 compound. The modified LiMn2O4 compound exhibits improved cycling stability at room and elevated temperature in comparison with the pure LiMn2O4.     

锂离子电池正极材料锰酸锂派生物LiMn1.75Me0.25O4(Me=Ti, Fe, Ni)的制备与表征

在合成纯相尖晶石型锰酸锂的基础上 ,采用固相分段法制备了锰酸锂派生物LiMn1.75Ti0 .2 5O4 ,LiMn1.75Fe0 .2 5O4 和LiMn1.75Ni0 .2 5O4 。用XRD ,SEM和粒度测试仪分别对试样进行了表征。电化学检测表明 ,Fe和Ni元素能够提高锰酸锂的放电平台电压 ,Ti元素不能改善锰酸锂的电化学性能。从结构化学角度初步探讨了Fe ,Ni和Ti元素对纯相尖晶石型锰酸锂结构的影响。     

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。     

Synthesis and electrochemical properties of sol-gel derived LiMn2O4cathode for lithium-ion batteries

Spinel LiMn2O4 has been considered to be the most promising alternative cathode material for the new generation of lithium-ion batteries in terms of its low cost, non-toxicity and easy manufacture. The spinel lithium manganese mixed oxides were prepared from lithium nitrate, manganese nitrate and citric acid by asol-gel method and were characterized by thermogravimetric analysis, X-ray diffraction, cyclic voltammetry and constant current charging-discharging technique. The different sintering temperatures for different time have strong influence on the structure, initial discharge capacity and cycling performance of the lithium manganese oxide. It shows that the lithium manganese oxides sintered at 700 ℃ for 10 h have a single spinel structure and better electrochemical properties. The initial discharging capacity can be up to 125.9 mAh·g-1 , even after six cycles, it still retains 109.1 mAh·g-1 .     

掺Cr对LiMnO2的影响

采用固相反应合成了LiMnO2和LiMn0.9Cr0.1O2，Cr的加入改变了LiMnO2的结构，与LiMnO2正交结构(空间群Pmnm)相比，LiMn0.9Cr0.1O2具有单斜结构(空间群C2／m)。充放电过程中，LiMnO2和LiMn0.9Cr0.1O2结构产生向尖晶石结构的不可逆转变。在首次放电过程中，LiMnO2只存在2．9V的电压平台，随着循环次数的增加，在2．9V和4V电压平台容量都有所增加。与LiMnO2不同，LiMn0.9Cr0.1O2在首次放电过程中存在有2．9V和4V电压平台，随着循环次数的增加，4V电压平台容量逐渐减小，在一定循环次数下，只有2．9V的电压平台存在。因此，Cr的掺杂不仅改变了LiMnO2的结构，而且改变其电化学行为。     

电解二氧化锰预处理对制备锰酸锂性能的影响(英文)

分别采用酸洗、预烧、浸渍掺铬的方式对电解二氧化锰(EMD)进行预处理,研究EMD预处理对制备锰酸锂性能的影响。采用XRD、ICP等手段对预处理的EMD及制备的锰酸锂进行表征,并通过Li/LiMn2O4电池的充放电测试对其电化学性能进行评估。结果表明,酸洗后EMD中的钠、硫等无机杂质含量显著降低;预烧能够有效去除EMD吸附的水分和有机杂质,扩大孔径,增多反应活性位点;对EMD进行浸渍掺铬的预处理,能够得到更加均质的掺铬锰酸锂材料LiCr0.05Mn1.95O4,并表现出较好的结构稳定性及容量保持率。