基于容量参数的二次电池嵌入型电极材料固相扩散系数的测定方法

介绍了一种以容量参数为主变量的测定锂二次电池中电极材料固相扩散系数的方法.该方法只需颗粒半径这一辅助参数,通过球型扩散模型建立了恒流-恒压充电容量(RPG)比,进一步发展成为容量间歇滴定技术(CITT).采用RPG法可在较宽的电压范围内测定嵌入型电极材料的平均固相扩散系数,实验结果重现性好.由RPG法测得0～1.5 V时锂离子在石墨电极中的平均固相扩散系数值为1.055×10-10cm2/s.由CITT技术测得锂离子在LiMn2 O4中的固相扩散系数在3.95 V和4.12 V左右存在个两个极小峰,且随着循环次数的增加,扩散系数值逐渐增大.     

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。     

Effect of annealing treatment on electrochemical property of LiNi0.5Mn1.5O4 spinel

LiNi0.5Mn1.5O4 was prepared under different cooling conditions. The electrochemical properties of LiNi0.5Mn1.5O4 prepared under different cooling conditions were investigated. The results show that LiNi0.5Mn1.5O4 synthesized with or without annealing treatment has similar X-ray diffraction patterns that can be indexed to cubic spinel structure. The mass loss occurring above 650℃ during the heating process can be mostly gained during the cooling process. LiNi0.5Mn1.5O4 synthesized with an annealing treatment exhibits almost one voltage plateau at around 4.7 V and higher capacity with a quick fading upon cycling, whereas LiNi0.5Mn1.5O4 synthesized without annealing treatment shows two voltage plateaus at around 4.1 and 4.7 V and superior capacity retention upon cycling both at rates of 1/7C and 1 C, though the capacity is not high.     

Synthesis of nano Sb-encapsulated pyrolytic polyacrylonitrile composite for anode material in lithium secondary batteries

A novel process was proposed to synthesize nano Sb-encapsulated pyrolytic polyacrylonitrile composite for anode material in lithium secondary batteries. The preparation started with the dissolution of SbCl₃ and polyacrylonitrile (PAN) in dimethylformamide (DMF) solution, followed by the addition of KBH₄ to reduce Sb³⁺ in the solution. The Sb composite was obtained by pyrolysis of the Sb/PAN mixture that precipitated out when the DMF solution was added by plentiful water. The TEM analysis showed that about 100-200 nm Sb particles were embedded by the pyrolyzed PAN, which provided a conductive matrix to relieve the morphological change of Sb during electrochemical cycling. As-prepared composite presented good cycleability for lithium storage. The proposed process paves an effective way to prepare high performance alloy based composite anode materials for high performance lithium-ion batteries.     

废旧电池中有价金属回收利用探讨

随着中国经济的稳步发展和投资环境的不断优化,中国已成为电池的制造和消费大国,每年产生数亿只废旧电池。对废旧电池的回收利用已成为全社会关注的问题。介绍了废旧电池中有价金属的回收利用方法,着重介绍了锂离子二次电池正极材料有价金属的回收利用方法。指出,中国商品化的正极材料只有钴酸锂（LiCoO2）,这种正极材料钴含量高,且钴价值高,并且回收工艺可行,因此,从钴酸锂正极材料中回收钴等有价金属,对发展中国的循环经济具有重要意义。同时介绍了锂离子二次电池正极材料的研究现状。     

A study of the Fe(III)/Fe(II)-triethanolamine complex redox couple for redox flow battery application

The electrochemical behavior of the Fe(III)/Fe(II)-triethanolamine(TEA) complex redox couple in alkaline medium and influence of the concentration of TEA were investigated. A change of the concentration of TEA mainly produces the following two results. (1) With an increase of the concentration of TEA, the solubility of the Fe(III)-TEA can be increased to 0.6 M, and the solubility of the Fe(II)-TEA is up to 0.4 M. (2) In high concentration of TEA with the ratio of TEA to NaOH ranging from 1 to 6, side reaction peaks on the cathodic main reaction of the Fe(III)-TEA complex at low scan rate can be minimized. The electrode process of Fe(III)-TEA/Fe(II)-TEA is electrochemically reversible with higher reaction rate constant than the uncomplexed species. Constant current charge-discharge shows that applying anodic active materials of relatively high concentrations facilitates the improvement of cell performance. The open-circuit voltage of the Fe-TEA/Br₂ cell with the Fe(III)-TEA of 0.4 M, after full charging, is nearly 2.0 V and is about 32% higher than that of the all-vanadium batteries, together with the energy efficiency of approximately 70%. The preliminary exploration shows that the Fe(III)-TEA/Fe(II)-TEA couple is electrochemically promising as negative redox couple for redox flow battery (RFB) application.     

Improvement of structural stability and electrochemical activity of a cathode material LiNi0.7Co0.3O2 by chlorine doping

In the process of Li⁺ intercalation-deintercalation, electron removal is accompanied simultaneously. Oxygen was found to compensate electron removal both in theoretical calculations and practical experiments. Chlorine addition to LiNi_0.7Co_0.3O₂ was expected to exchange electrons in that Cl⁻ was easier to lose electrons than O²⁻. LiNi_0.7Co_0.3O_2−xCl_x was identified as a pure hexagonal lattice of α-NaFeO₂ type by X-ray diffraction. X-ray photoelectron spectroscopy was used to analyze the influence of chlorine substitution on the oxidation state of transition-metal ions. Charge-discharge experiments and cyclic voltammetry confirmed that chlorine addition was an effective way to improve reversible capacity and structural stability in cycles.     

掺杂型尖晶石Li_(1.05)Mg_xMn_(2-x)O_4的合成及性能研究

采用高温固相法制备了尖晶石正极材料L iMxMn2-xO4(X=0.04,0.06,0.08,0.10),并用XRD、SEM、ICP-AES、充放电测试等手段研究了其组成、结构、表观形貌和电化学性能。结果表明:该法制备的尖晶石正极材料L iMxMn2-xO4为单一尖晶石结构,粒径分布均匀,其比容量和循环性能较未掺杂尖晶石L iMn2O4有显著的提高。     

隔膜中残油量对锂电池性能的影响

锂离子电池隔膜在锂离子电池中主要起隔绝正负极防止短路和允许锂离子导通的作用[1],因此,锂离子电池隔膜品质的优劣直接影响到锂离子电池的应用性能。在锂电池隔膜制备的过程中,以石蜡油作为造孔剂,用热致相分离法制备聚乙烯微孔膜,石蜡油的残留不可避免。本文研究了隔膜中石蜡油的残留量对电池自放电、倍率放电、高温存储、循环性能等应用性能的影响。研究结果表明,残油量越低锂电池的应用性能越优。     

锂离子电池固态聚合物电解质研究进展

电解质是制备高功率密度和高能量密度、长循环寿命的锂离子电池的重要材料之一,而聚合物电解质是实现全固态锂离子电池的关键技术.总结近几年来为提高聚合物电解质电导率所作研究的新进展,并提出了今后的研究方向.