Na+掺杂对LiNi1/3Co1/3Mn1/3O2结构和电化学性质的影响

采用高温固相法成功制备了不同Na+掺杂浓度的Li_1-xNa_xNi_1/3Co_1/3Mn_1/3O₂锂离子电池正极材料,探究了Na元素掺杂对层状氧化物正极材料结构以及电化学性能的影响。通过X射线粉末衍射仪和扫描电子显微镜表征了材料的结构和形貌,结果表明,当x≤0.3时,样品不会出现其它杂相;当x＞0.3时,样品中会出现NaNi_1/3Co_1/3Mn_1/3O₂的杂相。同时随着掺杂浓度的增加,样品的阳离子混排度逐渐增加。电化学性能结果表明,少量Na+的掺入可以提高LiNi_1/3Co_1/3Mn_1/3O₂在0.2C,0.5C下的放电比容量并增强其循环稳定性,但会损坏材料的倍率性能。     

Comparative experiment on layered Li（Ni1/3Co1/3Mn1/3）O2 as the alternative material for LiCoO2

This work was financially supported by the National Natural Science Foundation of China （No.50472093）.     

Preparation of spherical and dense LiNi0.8Co0.2O2 lithium-ion battery particles by spray pyrolysis

With citric acid as a polymeric agent layered LiNi0.8Co0.2O2 materials were synthesized by a spray pyrolysis method. The LiNi0.sCo0.2O2 particles were characterized by means of XRD, SEM and TEM. The electrochemical performances of LiNi0.8Co0.2O2 particles were studied in a voltage window of 3.00-4.35 V and at a current density of 30 mA/g. The results show that in the pilot-scale spray pyrolysis process, the morphology of particles is dependent upon the precursor concentration and flux of carrier gas. The initial discharge capacity of the LiNi0.8Co0.2O2particles at 720 ℃ for 12 h is 187.3 mA.h/g, and the capacity remains 96.8% with excellent cycleability after 30 cycles. The LiNi0.8Co0.2O2 samples synthesized under the optimized conditions by the spray pyrolysis method shows a good electrochemical performance.     

LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2+LiMn_2O_4/软碳体系电池的研究

选用锰酸锂(Li Mn2O4)、复合镍钴锰酸锂(Li Ni1/3Co1/3Mn1/3O2)按不同比例混合作为正极,软碳作为负极材料,制备复合镍钴锰酸锂与锰酸锂混合型锂离子全电池(简称混合型锂离子全电池),选择质量分数为15%,35%的Li Mn2O4与Li Ni1/3Co1/3Mn1/3O2混合作为正极活性物质进行实验,研究Li Mn2O4对锂离子全电池充放电性能、安全性能、倍率放电性能、脉冲功率特性等的影响。结果表明:Li Mn2O4质量分数为35%时,既提升了锂离子全电池的电性能,又保证了其较高的安全性能;常温下电流为1I1(I1代表1 h率放电电流)充放电循环预计寿命可达到1 500周,55℃高温下电流为0.5I1充放电循环335周容量保持在92%以上;在放电深度(DOD)10%~80%内10 s脉冲充放电状态下,混合型锂离子全电池阻抗均在9 mΩ以下,50%DOD时的10 s放电比功率在700 W/kg以上。     

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.     

Electrochemical properties of spinel LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1 synthesized by solid-state reaction

Two types of spinel cathode powders, LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1, were synthesized by solid-state reaction. X-ray diffraction (XRD) patterns of the prepared samples were identified as the spinel structure with a space group of Fd 3 m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. The LiAl0.1Mn1.9O3.9F0.1 sample showed a little lower initial capacity, but better cycling performance than the LiMn2O4 sample at both room temperature and an elevated temperature. The Vanderbilt method was used to test the electrochemical conductivity of the LiMn2O4 samples. The electrochemical impedance spec-troscopy (EIS) method was employed to investigate the electrochemical properties of these spinel LiMn2O4 samples.     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

锌对Li（Ni_（1/3）Co_（1/3）Mn_（1/3））O_2电极首次脱锂过程电化学性能的影响

共沉积法制备不同含锌量的锂离子电池正极材料Li（Ni1/3Co1/3Mn1/3）O2.采用交流阻抗谱分析该正极材料在首次脱锂过程中的电化学特性以及锌对电极阻抗和锂离子扩散系数的影响.电极阻抗图谱分析结果表明：3.7～4.4V为电极发生电化学反应的电位区间;锌减小了电极材料的SEI膜阻抗和电荷转移阻抗;少量固溶锌提高了锂离子在材料固相中的扩散能力.     

Synthesis and characterization of high-voltage cathode material LiNi0.5Mn1.5O4 by one-step solid-state reaction

LiNi_0.5Mn_1.5O₄ was prepared under various conditions by one-step solid-state reaction in air and its properties were investigated by X-ray diffractormetry (XRD), scanning electron microscopy (SEM) and electrochemical measurement. XRD patterns show that LiNi_0.5Mn_1.5O₄ synthesized under various conditions has cubic spinel structure. SEM images exhibit that the particle size increases with increasing calcination temperature and time. Electrochemical test shows that the LiNi_0.5Mn_1.5O₄ calcined at 700 °C for 24 h delivers up to 143 mA · h/g, and the capacity retains 132 mA · h/g after 30 cycles. Foundation item: Project (76600) supported by Postdoctoral Science Foundation of Central South University     

Theoretic Diffraction Research on the Order-Disorder Effect of Transition Metal in Li(Ni1/3Co1/3Mn1/3)O2

Li(Ni_1/3Co_1/3Mn_1/3)O₂的(3b)位有序-无序效应研究

曹春晖^1,2, 张建¹, 杨传铮¹, 夏保佳¹

（1.上海微系统与信息技术研究所,上海 200050;

2.中国科学院大学, 北京100049）

创新点说明：

提出了有序度的概念,通过理论模拟了过渡金属在3b位不同有序度下的衍射情况。

研究目的：

借助理论衍射研究镍钴锰在三元材料中的占位情况,为实际得到的衍射数据分析起指导作用。

研究方法和结果：

借助Powercell程序模拟不同结构下的衍射情况。结果表明：对于Li(Ni1/3Co1/3Mn1/3)O2,基体衍射线的强度不随有序度而变化,有序度增加时,超点阵衍射线强度增加,但是即使对于有序度最大时,超点阵线的相对强度只有0.225%和0.043%。

结论：

3b位的有序无序很难通过常规的衍射实验观测到,必须提高X射线源的强度才可能观测到。

关键词：Li(Ni1/3Co1/3Mn1/3)O2, 有序-无序,超结构,衍射

     

SnO2及SnO2／Fe2O3复合微米材料的合成及表征

本文首先以SnCl2·2H2O为主要原料,无水乙醇为溶剂,利用溶剂热法于180℃反应24h得到了SnO2微球;再以所制备的SnO2微球为前驱体,FeCl3·6H2O为主要原料,通过水热法得到SnO2／Fe2O3复合材料．利用X射线粉末衍射仪（XRD）和扫描电子显微镜（SEM）对所得产物进行了表征．结果表明：所得的SnO2为四方锡石型,形貌为微球,平均直径约为2．0μm;复合后得到的SnO2／Fe2O3微球平均直径约为2．5μm．其中,Fe2O3为六方赤铁矿型,在复合物的表面以小颗粒的形式存在,尺寸约为200nm．另外,也对SnO3与SnO2／Fe2O3微球的形成过程进行了讨论．     

Ca1-3x/2Al2Si2O8:xEu3+荧光粉的发光和光温传感特性

为了探究稀土离子掺杂铝硅酸盐的光温特性,本文采用燃烧合成法制备了系列荧光粉材料Ca_1-3x/2Al₂Si₂O₈:xEu³⁺。X射线衍射结果表明掺杂Eu³⁺离子不会改变基质CaAl₂Si₂O₈的晶体结构。荧光光谱结果表明该荧光粉在近紫外光区域具有较强吸收,当被波长为393 nm的近紫外光激发后,其最大特征发射峰为611 nm,且Eu³⁺离子的最佳掺杂浓度为0.05。利用上升时间测温法研究了CaAl₂Si₂O₈:Eu³⁺荧光粉的光温传感特性,结果表明:随着Eu³⁺掺杂浓度的增加,上升时间单调递减,但当掺杂掺杂超过0.100时就会发生淬灭。Ca_0.985Al₂Si₂O₈:0.01Eu³⁺的相对灵敏度随温度的升高先增大后减小,并在520 K时达到最大值（0.024 K^-1）。上述研究表明该荧光粉具备优异的温度传感性能,在测温领域具有广泛的应用前景。     

Microstructure and microwave dielectric properties of CaO-B2O3-SiO2 glass ceramics with various B2O3 contents

The effects of B2O3 addition on both the sintering behavior and microwave dielectric properties of CaO-B2O3-SiO2 (CBS) glass ceramics were investigated by Fourier transform infrared spectroscopy (FTIR),X-ray diffractometry (XRD) and scanning electron microscopy (SEM).The results show that the increasing amount of B2O3 causes the increase of the contents of [BO3],[BO4] and [SiO4],which deduces the increase of CaB2O4 and α-SiO2 and the decrease of CaSiO3 correspondingly.No new phase is observed throughout the...     

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.     

Al2O3 coating for improving thermal stability performance of manganese spinel battery

The synthesis of Al₂O₃-coated and uncoated LiMn₂O₄ by solid-state method and fabrication of LiMn₂O₄/graphite battery were described. The structure and morphology of the powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The electrochemical and overcharge performances of Al₂O₃-coated and uncoated LiMn₂O₄ batteries were investigated and compared. The uncoated LiMn₂O₄ battery shows capacity loss of 16.5% after 200 cycles, and the coated LiMn₂O₄ battery only shows 12.5% after 200 cycles. The uncoated LiMn₂O₄ battery explodes and creates carbon, MnO, and Li₂CO₃ after 3C/10 V overcharged test, while the coated LiMn₂O₄ battery passes the test. The steadier structure, polarization of electrode and modified layer are responsible for the safety performance.     

Temperature dependence on reaction of CaCO3 and SO2 in O2/CO2 coal combustion

The temperature dependence on the reaction of desulfurization reagent CaCO₃ and SO₂ in O₂/CO₂ coal combustion was investigated by thermogravimetric analysis, X-ray diffraction measurement and pore structure analysis. The results show that the conversion of the reaction of CaCO₃ and SO₂ in air is higher at 500–1 100 °C and lower at 1 200 °C compared with that in O₂/CO₂ atmosphere. The conversion can be increased by increasing the concentration of SO₂, which causes the inhibition of CaSO₄ decomposition and shifting of the reaction equilibrium toward the products. XRD analysis of the product shows that the reaction mechanism of CaCO₃ and SO₂ differs with temperature in O₂/CO₂ atmosphere, i.e. CaCO₃ directly reacts with SO₂ at 500 °C and CaO from CaCO₃ decomposition reacts with SO₂ at 1 000 °C. The pore analysis of the products indicates that the maximum specific surface area of the products accounts for the highest conversion at 1 100 °C in O₂/CO₂ atmosphere. The results reveal that the effect of the atmosphere on the conversion is temperature dependence.     

Effect of nucleating agents on microstructure and mechanical properties of SiO2-Al2O3-ZrO2 glass-ceramics

SiO2-Al2O3-ZrO2 glasses with different nucleating agents were crystallized under special processing schedule. The microstructure and mechanical properties of the glass-ceramics in SiO2-Al2O3-ZrO2 system were investigated by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction and three-point bending method. The results show that ZrO2 is not an effective nucleating agent in SiO2-Al2O3-ZrO2 system, while TiO2 is effective for the separation of spinel, and P2O5 facilitates solubility of ZrO2 in glass and crystallization. The main crystalline phases of the glass-ceramics are spinel, anorthite and tetragonal zirconia. With the increase of ZrO2 content in the glass, glass-ceramics show higher bending strength （120 MPa） than others.     

NiCoCrAlY/Al_2O_3-13%TiO_2复合涂层的耐锌铝腐蚀性

为了解决热镀锌铝工艺中沉没辊受到熔融锌铝液腐蚀的问题,采用超音速火焰喷涂技术在316L基体上制备了NiCoCrAlY粘结层,并利用等离子喷涂技术制备了NiCoCrAlY/Al_2O_3-13%TiO_2复合涂层.结果表明,复合涂层界面处的热膨胀系数突变减缓,使得界面处的应力集中减少,从而对裂纹扩展起到延缓和抑制作用,因而复合涂层的抗裂性能增强.复合涂层在锌铝液中的使用寿命可以达到9 d,高于传统Al_2O_3-13%TiO_2涂层.复合涂层的结合强度也高于传统Al_2O_3-13%TiO_2涂层,但复合涂层的最终失效形式依然是由两种材料的热胀系数不匹配所导致的涂层开裂.     

反应温度对微波法合成Fe2V4O13光催化粉体及其光催化性能的影响

以Fe（NO3）3·9H2O和NH4VO3为原料,采用微波水热-煅烧两步法合成了片层状结构单斜相Fe2V4O13光催化剂．以罗丹明B溶液为目标降解物,对不同煅烧温度下合成的Fe2V4O13粉体的光催化性能进行了研究．结果表明：随着煅烧温度的升高,片层状颗粒不断长大,Fe2V4O13光催化剂的结晶性能逐渐增强,粉体的比表面积逐渐减小．350℃和550℃下制备出的片层状粉体分别是由300nm大小及1Arm大小的小颗粒和块状颗粒聚集生长而成,二者都不利于光催化性能的提高;450℃煅烧合成的Fe2V4O13粉体晶化强度良好且粉体间团聚现象较小,具有较大的比表面积,光催化反应活性位点多,有利于光催化反应的进行．该温度下合成的Fe2V4O13粉体在紫外光照射240rain后对罗丹明B溶液的降解率可达到79．0％．     

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.