Kinetic study of LiMn2O4 in process of lithium intercalation

Exchange current density of spinel LiMn2 O4 was studied by linear polarization. The relationship of the kinetic property with the structure of spinel LiMn2 O4 was investigated by studying the effect of the doping and surface coating on the kinetic properties of electrode material. The results show that the exchange current density of spinel LiMn2 O4 electrode increases with the increase of the amount for lithium intercalation at first, and then decreases. The maximal exchange current density appeares at the 80%-90% lithium intercalation. The similar phenomenon was observed on the doped spinel LiMn2 O4 electrode. Doping can enhance the exchange current density of spinel LiMn2 O4 material. However, the degree of the doping effect varies with the doped element varying. Surface coating can also enhance the exchange current density of spinel material, and the increment of value is higher than that of doped ones.     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

Influence on performance and structure of spinel LiMn2O4 for lithium-ion batteries by doping rare-earth Sm

The spinel LiMn₂O₄ used as cathode materials for lithium-ion batteries was synthesized by mechano-chemistry fluid activation process, and modified by doping rare-earth Sm. Thesting of X-ray diffraction, cyclic voltammograms, charge-discharge and SEM was carried out for LiMn₂O₄ cathode materials and the modified materials. The results show that the cathode materials doped rare earth Li _x Mn_2−y Sm _z O₄ (0.95⩽x⩽1.2, 0⩽y⩽0.3, 0⩽z⩽0.2) exhibit standard spinel structure, high reversibility of electrochemistry and excellent properties of charge-discharge. In EC: DMC(1 : 1)+1 mol/L LiPF₆ electrolyte with discharge capacity more than 130 mA · h/g, and its capacity is deteriorated less than 15% after 300 cycles at room temperature and less than 20% after 200 cycles at 55°C. At the same time, Crystal Field Theory was applied to explain the function and mechanism of doped rare earth element. Foundation item: Project (02JJY2081) supported by the Natural Science Foundation of Hunan Province     

球形LiMn1.5Ni0.5O4材料的嵌脱动力学

为明晰Li Mn1.5Ni0.5O4正极材料的动力学性能,采用水热辅助共沉淀法合成了尖晶石Li Mn1.5Ni0.5O4正极材料,并采用扫描电镜(SEM)、X射线粉末衍射(XRD)和电化学阻抗(EIS)研究了材料的结构和锂离子嵌脱动力学.实验结果表明:共沉淀法制备的Li Ni0.5Mn1.5O4材料颗粒呈均匀球形,且平均粒径较小,粒度分布较窄.在循环过程中,Li Ni0.5Mn1.5O4的电荷转移电阻增大,锂离子扩散系数减小,进而电子电导率和离子电导率下降.温度升高后,Li Ni0.5Mn1.5O4材料的溶液电阻变化不大,但是电荷转移电阻逐渐增大,锂离子扩散系数逐渐减小;此外,随着温度的升高,Li Ni0.5Mn1.5O4材料的溶解速度加快,从而导致SEI膜的厚度增大.Li Ni0.5Mn1.5O4材料的嵌脱锂动力学与温度和循环次数有密切关系.     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.     

基于双金属MOFs 制备Co3O4/In2O3 复合物及其气敏性能的研究

以硝酸铟(In(NO₃)₃·xH₂O)、对苯二甲酸(H₂BDC)、六水合硝酸钴(Co(NO₃)· 6H₂O) 为原料, 首先采用一锅油浴法合成了含有Co²⁺ 的铟基金属有机框架材料(MOFs) Co²⁺/CPP-3(In) 材料, 然后在450 ℃ 下焙烧制备Co₃O₄/In₂O₃ 复合物气敏材料, 将Co₃O₄/In₂O₃ 复合物的粉体制作成传感器, 并对其气敏性能进行研究。利用扫描电子显微镜和X 射线衍射仪(XRD) 对双金属MOFs Co²⁺/CPP-3(In) 材料和Co₃O₄/In₂O₃ 复合物进行表征, 采用静态配气法测试其气敏性能。结果表明, Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 样品的形貌保留了其MOFs 前驱体的棒状结构, 棱柱形框架更为突出, 表面呈凹陷状, 棒体中间粗两边细, 六角截面和棒体均布满了孔洞。结合EDX 和XRD 表征结果, Co²⁺/CPP-3(In) MOFs 前驱体完全转化成Co₃O₄/In₂O₃ 复合物; Co₃O₄/In₂O₃(n_Co : n_In = 0.4 : 1) 复合物在 70 ℃ 下对5×10^-6 H₂S 的气敏性能最优, 响应值达到153, 是同条件下纯备In₂O₃对H₂S 响应值的5 倍, 并且有较好的重复性、选择性和稳定性。     

Molar heat capacities of La2Mo2O9 and La1.9Sr0.1MO209-δ

The molar heat capacities of La2Mo209 and La1.9Sr0.1MO209-δ were obtained using the differential scanning calorimetry （DSC） technique in a temperature range from 298 to 1473 K. The DSC curve of La2Mo209 showed an endothermal peak around 834 K corresponding to a first-order monoclinic-cubic phase transition, and the enthalpy change accompanying this phase transition is 5.99 kJ/mol. No evident endothermal peak existed in the DSC curve of La1.9Sr0.1MO209-δ, but a broad thermal anomaly existed in its heat capacity curve at around 832 K. In addition, the heat capacity values of La2Mo209 and La1.9Sr0.1MO209-δ began to decrease at 1196 and 1330 K, respectively. The non-transitional heat capacity values of La2Mo209 and La1.9Sr0.1MO209-δ were formulated using multiple regression analysis in two temperature ranges.     

Luminescent properties of BaO-La2O3-B2O3 glasses with dopant

The luminescent properties of glasses synthesized in air atmosphere by conventional high temperature process were stud{ed. The emissions spectra of Eu^2 and Eu^3 were observed in BaO-La2O3-B2O3-Eu2O3 glasses.The results show that the broad emission peaks at 430 nm correspond to 5d→4f emission transition of Eu^2 , the sharp emission peaks at 592, 616, 650 and 250 nm correspond to 5^D0→1Fj(j=1--4) emission transition of Eu^3 ,respectively, which indicates that the BaO-La2O3a-B2O3-Eu2O3 glass can convert ultraviolet and green omponents of sunlight into blue and red light so as to increase the intensity of blue and red light, respectively. The luminescent in--tensity of Eu^2 increases with increasing the molar ratio of Tb^3 in BaO-La2O3-B2O3-Eu2O3a-Tb4O3 glasses, whereas the luminescent intensity of Eua^3 decreases. So the luminescent intensity of Eu(Ⅲ,Ⅱ) is influenced by Tb^3 .These phenomena can be explained by electron transfer mechanism; Eu^3 (4f6) Tb^3 (4f^8)→Eu^2 (4f′) Tb^4 (4f′). Taking advantage of the luminescent properties of BaO-La2O3-B2O3-Eu2O3 glasses, light-conversion glass for agriculture can be produced.     

Preparation and properties of 4.25Cu-0.75Ni／NiFe2O4 cermet

4.25Cu-0.75Ni/NiFe₂O₄ cermets were prepared by doping NiFe₂O₄ ceramic matrix with the mixed powders of Cu and Ni or Cu-Ni alloy powder as the electrical conducting metallic elements. The effects of technological parameters, such as the adding modes of metallic elements, the ball milling time, the sintering time and the sintering temperature, on the relative density and resistivity of the cermets were studied. The results show that the resistivity of 4.25Cu-0.75Ni/NiFe₂O₄ cermets decreases with increasing temperature, and has a turning point at 590 °C, which is similar to that of NiFe₂O₄ ceramic. The sintering temperature and adding modes of metallic elements have a great influence on the properties of 4.25Cu-0.75Ni/NiFe₂O₄ cermets. When the sintering temperature increases from 1200 °C to 1300 °C, the relative density increases from 89.86% to 95.33%, and the resistivity at 960 °C decreases from 0.11 Ω · cm to 0.03 Ω · cm, respectively. When the metallic elements are added with the mixed powders of Cu and Ni, the cermets of finely and uniformly dispersed metallic phase, high density and electric conductivity are obtained. The relative density and resistivity at 960 °C are 90.23% and 0.04 Ω · cm respectively for the cermet samples sintered at 1200 °C for 2 h, which are both better than those of the cermets prepared under the same technique conditions but with the metallic elements added as 85Cu-15Ni alloy powders. Foundation item: Project (G1999064903) supported by the National Key Fundamental Research and Development Program of China; project(2001AA335013) supported by the National High Technology Research and Development Program of China; project (50204014) supported by the National Natural Science Foundation of China     

纳米CuFe2O4活化过一硫酸盐降解诺氟沙星性能

为研究使用过一硫酸盐(PMS)的高级氧化技术去除水体中微量有机污染物的高效可行方法,通过柠檬酸辅助溶胶-凝胶法制备纳米CuFe_2O_4材料,以其为非均相催化剂,探究CuFe_2O_4/PMS体系对诺氟沙星(NFX)的降解性能.采用X射线衍射仪、电子透射显微镜、BET手段对材料进行表征,考察煅烧温度对纳米CuFe_2O_4结构及催化性能的影响,并试验纳米CuFe_2O_4的重复使用性和稳定性.探讨纳米CuFe_2O_4投加量、PMS浓度、溶液初始pH对CuFe_2O_4/PMS体系降解NFX性能的影响,并探究该体系的氧化活性物种及降解机理.结果表明:制备纳米CuFe_2O_4的最佳煅烧温度为400℃,该温度下纳米CuFe_2O_4晶型较好,比表面积较大,且表现出较高的催化活性;在纳米CuFe_2O_4/PMS体系中,控制NFX初始质量浓度为5 mg/L,最适宜的反应条件为:纳米CuFe_2O_4投加量为0.1 g/L、PMS浓度为0.5 mmol/L、初始溶液pH为9.5,该条件下反应30 min后NFX的去除率高达99%;纳米CuFe_2O_4能有效活化PMS生成·OH和SO_4~-·,SO_4~-·是实现NFX快速降解的主要活性物种.     

Structure and electrochemical properties of La, F dual-doped iLa0.01Mn1.99O3.99F0.01 cathode materials

The cathode materials LiMn₂O₄ and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG) measurements, X-ray diffraction (XRD), scanning electronic microscope (SEM), cyclic voltammetry (CV), and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa_0.01Mn_1.99O_3.99F_0.01 and LiLa_0.01Mn_1.99O₄ samples have smaller lattice parameters and unit cell volume than LiMn₂O₄. SEM indicates that LiLa_0.01Mn_1.99O_3.99F_0.01 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, LiLa_0.01Mn_1.99O₄, and LiLa_0.01Mn_1.99O_3.99F_0.01 are 129.9, 122.8, and 126.4 mAh·g⁻¹, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively. The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn₂O₄.     

Kinetics of Fe3O4 formation by air oxidation

The kinetics of Fe₃O₄ formation by air oxidation of slightly acidic suspension of Fe(OH)₂ was studied. The effects of initial concentration of Fe(II), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe₃O₄ formation is composed of two-step reaction, the first step is the formation of Fe(OH) ₂ ⁺ by oxidation of Fe(OH)⁺ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)⁺ and Fe(OH) ₂ ⁺ . The oxidation reaction is zero-order with respect to the concentration of Fe(II) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ · mol⁻¹.     

Al_2O_3包覆对富锂锰基正极材料Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2的电化学性能影响

采用水热法合成富锂三元正极材料,探究了最佳包覆比例下Al_2O_3包覆对材料的电化学性能影响.采用扫描电镜(SEM)和X射线衍射仪(XRD)表征了富锂三元正极材料的表面形貌和结构,通过循环伏安(CV)、交流阻抗(EIS)技术分析了材料电化学性的影响因素.结果表明,通过异丙醇铝水解制得了氧化铝包覆层,提高了材料的比容量,稳定了材料的结构.     

GO/CoFe2O4催化过硫酸盐降解邻苯二甲酸二丁酯效能

为高效地去除水中环境激素类污染物,采用共沉淀法合成了氧化石墨烯负载钴尖晶石铁氧体(GO/CoFe_2O_4)催化剂,催化过硫酸盐(PMS)去除水中邻苯二甲酸二丁酯(DBP).采用SEM、TEM、XPS、XRD对催化剂进行表征,研究不同条件下催化PMS去除水中DBP的效果,提出催化PMS反应机理.结果表明,GO/CoFe_2O_4为颗粒状尖晶石结构,室温下,DBP初始浓度为2μmol/L、催化剂投量为0.1 g/L、PMS浓度为20μmol/L、pH为7时,GO/CoFe_2O_4催化PMS体系对DBP的去除率可达89%,使用5次后催化效果仅降低5%.该新型复合催化剂高效、具有磁性、方便回收,具有良好的工程应用前景.     

第一性原理研究:Mg2+掺杂尖晶石型LiMn2O4的电子结构

尖晶石 LiMn₂O₄ 正极材料是在原有锂电池正极材料 LiCoO₂ 、LiNiO₂ 、LiMnO₂ 的基础上研发出来的优选 正极材料, 它相较于 LiCoO₂ 材料价格更加低廉热稳定性加强且安全性能有所提高。采用 Mg²⁺ 掺杂 LiMn₂O₄正极 材料, 利用基于密度泛函理论的第一性原理对 LiMg_0.5Mn_1.5O₄ 晶格常数与能带结构、态密度进行计算与分析。结 果表明: 新材料 LiMg_0.5Mn_1.5O₄ 的空间群为 F4332, 掺杂后晶胞参数 a 明显减小, 晶胞体积收缩; 掺杂量为 0.5 时明 显比掺杂量 0.125 时 Fermi 能量和能量密度高。Mg ²⁺ 掺杂能影响 LiMn₂O₄ 的晶体结构, 形成更加稳定的共价键。 掺杂量会改变 LiMn₂O₄ 的空间群影响到结构稳定性, 所以掺杂量不宜过大。     

水热法制备SrBi2Ta2O9陶瓷及其介电性能研究

采用水热法合成SrBi2Ta2O9(SBT)纳米粉体,成型后采用常规烧结法制备SBT陶瓷.利用XRD和SEM研究陶瓷的物相和微观形貌;利用介电温谱研究陶瓷的介电性能.结果表明:采用水热法能够制备出颗粒细小均匀、结构致密且物相纯净的SBT陶瓷;其居里温度为375℃,对应的介电常数为114.54.     

Corrosion resistance of plasma sprayed NiCrAl+(ZrO2+Y2O3) thermal barrier coating on 18-8 steel surface

The corrosion resistance of NiCrAl+(ZrO₂+Y₂O₃) thermal barrier coating, formed with the plasma spraying technique, on the 18 - 8 steel surface was investigated. The phase structure and morphology of the coating were analyzed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical corrosion behavior of the coating in 1.0 mol/L H₂SO₄ solution was studied by using electrochemical measurement methods. The results show that the gradient plasma spraying coating is composed of the NiCrAlY coating and the (ZrO₂+Y₂O₃) top coating, and the coating thickness is 360 μm. The microhardness of coating reaches 1 100 HV. The corrosion resistance of the plasma sprayed coating of the 18 - 8 steel surface is about 5 times as great as that of the original pattern. The corrosion resistance of the coating is enhanced notably. Foundation item: Project (5040202140) supported by Scientific Research Common Program of Beijing Municipal Commission of Education     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

Effect of sintering time on the electrochemical properties of spinel LiMn2O4 synthesized by solid-state reaction

LiMn2O4 powder as a cathode materials for rechargeable lithium-ion batteries was prepared by solid-state reaction from LitCO3 and electrolytic MnOz at different sintering periods （2, 6, 18, and 32 h）. X-ray diffraction （XRD） patterns of the prepared samples are identified as the spinel structure with a space group of Fd3 m. The lattice parameters almost remain the same as the sintering periods increase. The sample with a sintering period of 32 h shows good cycling performance at both low and nigh current densities, and also elevated temperature. It is believed that the excellent electrochemical behavior of this sample results from its good crystallinity and large grain size compared with other samples. Different electrochemical measurements were conducted to investigate the electrochemical properties of spinel LiMn204. 2008 University of Science and Technology Beijing. All rights reserved.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.