无机超细粉体改性锂离子电池隔膜的研究进展

综述了近年来无机超细粉体改性锂离子电池隔膜的研究进展,首先介绍了已在锂电隔膜改性上商业应用的Al₂O₃和AlOOH对传统聚烯烃膜和新型静电纺丝膜的改性方法和改性效果,随后又对常规无机材料TiO₂和SiO₂粉体对锂电隔膜的改性进行了叙述,最后对BN等非常规隔膜改性无机材料进行了简介;总结和讨论了无机材料改性后隔膜的组分、结构和性能对锂离子电池综合性能的影响,并对其无机材料改性锂电池隔膜的未来发展趋势进行了展望。     

化学交联聚酰亚胺隔膜增强锂离子电池性能研究

隔膜作为锂离子电池的重要组成部分,用于阻隔阴极和阳极直接接触,同时为锂离子在电极间的传输提供有效通道。聚酰亚胺隔膜因其具有充放电循环寿命长、机械强度适中、良好的电绝缘性能以及自熄能力等优点,而受到广泛关注。以对苯二甲胺作为交联剂,将聚酰亚胺隔膜进行化学交联,研究了交联时间与隔膜形貌、结构及性能之间的构效关系。随着交联时间的增加,隔膜的孔隙率和吸液率逐渐降低,电解液接触角和机械强度逐渐增大。电化学测试表明,随着交联时间的增加,隔膜的本体阻抗逐渐增大,进而离子电导率逐渐降低,而交联隔膜的界面阻抗均远小于未交联隔膜,且交联隔膜的电化学窗口也均大于未交联隔膜。通过组装半电池测试发现,交联隔膜所组装电池的倍率性能和循环性能均优于未交联隔膜,当交联时间为48 h时,电池性能表现最优,循环100次以后,放电比容量为130.2 mA·h/g,容量保留率为91.1%。     

Phase transition of lithiated-spinel Li2Mn2O4 at high temperature

1 Introduction Lithium manganese oxides are the most attractive cathode materials for rechargeable lithium-ion batteries because of their low-cost and less toxicity when compared with either cobaltates or nickelates[1?3]. Among these oxides, the spinel-fr…     

锂离子电池正极材料第一原理计算研究

利用第一原理计算方法可分析和预测锂-金属氧化物电池正极材料在Li离子嵌入脱出过程中的电势和稳定性等性能。本文详细介绍了第一原理计算方法的理论背景以及目前LiCoO2正极材料计算研究的现状。利用此方法对LiNiO2及多组分材料掺杂进行研究是今后工作的重点。     

LiFePO4基正极材料容量的温度敏感特性及交流阻抗谱研究

采用原位碳包覆法制备了锂离子二次电池用LiFePO4／C复合正极材料。考察了环境温度对LiFePO4/C电池容量的影响，得到容量与绝对温度之间符合Arrhenius关系。运用交流阻抗谱分析了温度与电池电化学特性的关系，并对电极基于电荷和质量传递控制过程给出了一种新的模拟等效电路，通过Zview拟合软件得到了各个模拟元件的数值及变化趋势，从而定量地解释LiFePO4／C复合电极容量与温度的关系。     

Synthesis and electrochemical properties of Th-doped LiMn2O4 powders for lithium-ion batteries

To improve the cycle performance of eco-friendly and cost-effective spinel LiMN2O4 as the Li secondary batteries, the Th-doped LiThxMn1-xO4 spinel powers were synthesized by solid-state method. The starting materials, Li2CO3,MnO2 and Th(NO3)4·4H2O, were mixed uniformly using a traditional ball milling, which resulted in a uniform particle size distribution in the mixed powers. Tests of X-ray diffraction, SEM, impedance spectra and charge-discharge were carried out for LiThxMn1-xO4 cathode materials. Results show that the synthesized LiTh0.01Mn1.99O4 material exhibits standard spinel structure, regular particle morphology and excellent property of charge-discharge for big current. The capacity retention of the material modified by doping Th is more than 85.1% of the first discharge specific capacity of 111.5 mAh·g -1 after 20 cycles at the current rate 1C, while the pristine LiMN2O4 is only 57% of the first discharge specific capacity of 110.2 mAh·g-1 after the same cycles at the same current rate.     

In situ synchrotron X-ray studies on copper-nickel 5 V Mn oxide spinel cathodes for Li-ion batteries

Partial substitution of Mn in lithium manganese oxide spinel materials by Cu and Ni greatly affects the electrochemistry and the cycle life characteristics of the cathode. Substitution with either metal or a combination of both metals in the spinel lattice structure reduces the 3.9-4.2 V potential plateaus associated with the conversion of Mn³⁺ to Mn⁴⁺. Higher potential plateau associated with oxidation of the substituted transition elements is also observed. These substituents also significantly alter the onset of Jahn-Teller distortions in the 3 V potential plateau. Synchrotron based in situ X-ray absorption (XAS) was used to determine the exact nature of the oxidation state changes in order to explain the overall observed capacities at different potential plateaus. The studies on LiCu_0.5Mn_1.5O₄ show single phase behavior in the 4-5 V potential region with a good cycle life. Lower cycle life characteristic observed in cycling LiNi_0.5Mn_1.5O₄ and LiNi_0.25Cu_0.25Mn_1.5O₄ versus Li metal are ascribed to coexistence of several phases in this potential region. However, LiCu_0.5Mn_1.5O₄ shows onset of Jahn-Teller distortions in the 3 V potential plateau, in contrast to LiNi_0.5Mn_1.5O₄ and LiNi_0.25Cu_0.25Mn_1.5O₄ cathode materials.     

Electrochemical properties of carbon-coated CaWO4 versus Li

Carbon-coated CaWO₄ nano-crystalline phases have been synthesized by ambient temperature solution precipitation method, characterized by X-ray diffraction, SEM and thermogravimetry and their electrochemical properties were studied versus Li metal. Galvanostatic cycling at a current of 60 mA/g in the voltage range 0.005-3.0 V on the 5 wt.% C-coated CaWO₄ gave a reversible capacity of 230 ± 5 mAh/g corresponding to 2.5 mol of Li, which is almost stable from 20 to 50 cycles. Under the same conditions, the 10 wt.% C-coated CaWO₄ showed a capacity of 355 ± 5 mAh/g (3.8 mol of Li) during the initial cycles, but the capacity degraded at a rate of 1.6 mAh/g per cycle in the range 5-100 cycles. A good operating voltage range was found to be 0.005-3.0 V with average discharge and charge potentials being 0.6 and 1.3 V, respectively. Coulombic efficiency in all cases was 96-98%. Cyclic voltammograms compliment the galvanostatic results. Impedance spectral data on the 10 wt.% C-coated CaWO₄ at different voltages during the first and 20th discharge-charge cycle have been interpreted in terms of the variations in the bulk and charge-transfer resistances of the composite electrode. A reaction mechanism involving the formation/decomposition of the oxide bronze, ‘Li_xWO_y’ has been proposed to explain the electrochemical cycling.