Enhanced cycling performance and high energy density of LiFePO4 based lithium ion batteries

LiFePO4 attracts a lot of attention as cathode materials for the next generation of lithium ion batteries. However, LiFePO4 has a poor rate capability attributed to low electronic conductivity and low density. There is seldom data reported on lithium ion batteries with LiFePO4 as cathode and graphite as anode. According to our experimental results, the capacity fading on cycling is surprisingly negligible at 1664 cycles for the cell type 042040. It delivers a capacity of 1170 mAh for 18650 cell type at 4.5C discharge rate. It is confirmed that lithium ion batteries with LiFePO4 as cathode are suitable for electric vehicle application. (c) 2007 Elsevier B.V. All rights reserved.

The structure and electrochemical characteristics of La0.67Mg0.33 (Ni0.8Co0.1Mn0.1)(x) (x=2.5-5.0) multiphase alloys for nickel-metal hydride batteries

This paper presents results concerning structure and electrochemical characteristics of the La0.67Mg0.33 (Ni0.8Co0.1Mn0.1) (x) (x=2.5-5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5-3.5 is LaMg2Ni9 phase with a PuNi3-type rhombohedral structure, but the main phase of the alloys with x=4.0-5.0 is LaNi(5)phase with a CaCu5-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg2Ni9 phase and the LaNi5 phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g (x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I-0) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability of the alloy electrodes.

Irreversible capacity loss of graphite electrode in lithium-ion batteries

The irreversible capacity loss of the carbon electrode in lithium-ion batteries at the first cycle is caused mostly by surface film growth. We inspected an unknown irreversible capacity loss (UICL) of the natural graphite electrodes. The charge/discharge behavior of graphite and meso-phase carbon microbeads heat-treated at 2800 degrees C (MCMB28) as the materials of the carbon anode in the lithium-ion battery were compared. It was found that the capacity loss of the natural graphite electrode in the first cycle is caused not only by surface film growth, but also by irreversible lithium-ion intercalation on the new formed surface at the potential range of lithium intercalation, while the capacity loss of the MCMB28 electrode is mainly originated from surface film growth. The reason for the difference of their irreversible capacity losses of these two kinds of carbon material was explained in relation to their structural characteristics. (C) 1997 Published by Elsevier Science S.A.

A study of cokes used as anodic materials in lithium ion rechargeable batteries

A variety of cokes pretreated at different temperatures are used as anodic materials and their electrochemical characteristics are examined by cyclic voltammetry. It is found that for some cokes such as petroleum coke (preheated at 1300 degrees C), pitch coke (1300 degrees C), needle coke (1900 degrees C), metallurgical coke (1900 degrees C), high capacity and cyclic efficiency are achieved. Needle coke (1900 degrees C) and metallurgical coke (1900 degrees C) in particular give a capacity of over 200 mAh/g and a cyclic efficiency of nearly 100%, whereas poor performance is exhibited by those pretreated at higher or lower temperatures, e.g., petroleum cokes (500 degrees C, 2800 degrees C), pitch coke (500 degrees C) and needle coke (2800 degrees C). The cyclic voltammograms show two electrochemical processes, one at about 0.1 V vs. Li+/Li which is electrochemically reversible, and may be attributed to the intercalation/deintercalation of lithium ions while the other, at about 0.6 V vs. Li+/Li, is electrochemically irreversible and may be assigned to the decomposition of the electrolyte solvent, which leads to formation of the passive film on the anode surface. The experimental results strongly suggest that the pretreatment temperature of cokes and of the solvent are determining factors for the growth, structure and properties of the passive film.

Carbon materials for lithium ion batteries

The preliminary work indicated that passive film is the most important factor influencing cell performance of carbon anode, and the carbon and solvent used govern cell performance by forming the passive film of different properties. A in situ XRD result is also presented.

DEVELOPMENT OF CYLINDRICAL SECONDARY LITHIUM POLYANILINE BATTERIES

The cylindrical 'D'-size batteries were fabricated by polyaniline paste cathode and lithium foil anode sandwiched with microporous polypropylene separator. The electrolyte used was LiClO4 dissolved in a mixed solvent of propylene carbonate and dimethoxyethane. The results of charge/discharge curves, charge/discharge cycles, the short-circuit current, the open-circuit voltage storage and the change of discharge capacity with temperature, discharge current are reported.

回转窑热解处理废锌锰电池试验研究

我国电池生产量已经达到209亿节（2003年），多年来一直占据世界第一大电池生产国的地位，其中锌锰电池占大多数。废锌锰电池丢弃后，其中的重金属物质会逐渐渗透到地下，污染土壤和水体。重金属在生物体内富集，会使生物体致畸或致变。但同时，废锌锰电池中也含有大量有用的资源如锌、二氧化锰等。应对其进行回收利用，变废为宝。本文介绍了废锌锰电池回收处理的主要技术及研究进展，不同的处理技术回收废锌锰电池时的目标产物各不相同，但一般可分为以下几种：以单质形式回收锌、锰和汞；以合金的形式回收锌和锰；回收锌和二氧化锰；回收各金属元素制备复合微量元素肥料；回收锌、锰元素制备锰锌铁氧体；回收锌、锰元素制备硫酸锌和碳酸锰等。本文对一些废锌锰电池回收处理技术的优缺点从无害化程度、资源化程度、产品等级、工艺要求以及二次污染五个方面进行了分析和比较。在对国内外废锌锰电池回收处理技术进行分析比较的基础上提出了一种成本较低、可操作性较强的处理技术：先以干法除去废锌锰电池中的汞，然后以湿法除去其它的有害重金属并进一步加工制备有机螯合微量元素肥料。 本文以回转窑中物料停留时间的经验公式和传热学的知识设计和计算了回转窑的长度和内径尺寸、电热丝的功率以及外围的保温材料厚度等参数。用保温材料和润滑油相结合的方式对回转窑的连接部分实行密封。通过调整回转窑的转速和回转窑支架两端高度差的方式控制物料在回转窑中的停留时间，从而调节热解时间的长短。利用自动控制设备调节电热丝的功率从而调节试验中的热解温度。利用该回转窑在不同条件下对热解处理废锌锰电池进行了试验研究，热解过程中产生的尾气和颗粒物用一系列吸收液进行吸收和固定。 在热解试验中改变影响热解过程的三种因素：热解温度、热解时间和载气流速并按三因素四水平的正交方法安排试验。改变废锌锰电池热解过程中的热解温度、热解时间和载气流速三种因素进行正交试验并利用正交统计学的方法分析了这三种因素对热解除汞率的影响。利用ICP检测仪测定了各吸收液中汞的含量，并分析热解气体产物经过系列吸收液时汞被吸收的情况以及汞的形态分布。利用气相色谱仪对尾气成分进行了测定，并对热解过程中产气的过程和规律进行了分析。用X射线衍射测试的方法研究了热解前后锌锰电池的物质形态变化情况。对除汞率的正交统计分析表明，合适的热解条件为：热解温度690℃，热解时间100min，载气流速0.06m3/h，在这种试验条件下热解处理废锌锰电池的除汞率达到100%。同时还得到：热解时间对除汞效果影响最大，热解温度次之，载气流速的影响较小。ICP测试的结果表明：热解尾气在经过试验中设置的吸收瓶后，其中的汞被完全吸收，尾气中95%以上的汞以单质的形式存在。气相色谱分析的结果表明，热解开始后，废锌锰电池中的有机质迅速分解，其产物为C2H4、CH4和H2等。一段时间后，有机质的分解量大幅度减少，同时废电池中的石墨碳和高价金属氧化物发生氧化还原反应，生成CO气体。对废锌锰电池原料以及热解残渣的X射线衍射分析表明，当热解温度为350℃时，X射线衍射图谱上2θ值为35°附近的区域有新峰出现，但不明显，说明有结晶体形成但量不大。500℃时上述峰明显增强，这是由于ZnO和FeO形成了结晶体，同时在2θ值为41°附近有新峰出现，这是高价锰氧化物与石墨碳发生氧化还原反应生成了MnO并形成了结晶体。650℃时，2θ值在41°附近的峰显著增强，且热解过程中形成的峰稳定下来，基本上不再有新的结晶体生成。热解后，高价锰氧化物的相对含量从32.2%下降到4.6%，而MnO的相对含量则从6.4%上升到38.6%。热解后的残渣中晶体物质含量大，金属元素大多以低价态存在，适合于制备有机螯合微量元素肥料。

聚合物锂离子电池和生物燃料电池的相关研究

本论文分为两个部分研究了铿离子电池和生物燃料电池中的关键材料，主要的创新点和结论如下。采用聚合物电解质是提高铿二次电池性能的有效方法之一。聚合物电解质良好电导率、高铿离子迁移数、宽电化学窗口以及好的机械性能是其应用于铿二次电池中的关键。论文的第一部分主要讨论了聚合物、增塑剂和无机纳米粒子等对复合电解质体系的化学和物理性质的影响。我们采用溶液浇注一浸渍法制备了各种纳米复合聚合物电解质，例如开发出基于PVDFHFP或梳状聚合物基体的全固态以及聚合物和碳酸醋形成的胶体聚合物电解质体系。首次制备了具有较高离子电导率的单离子聚合物电解质。考察了两类纳米粒子填充物对体系的影响：一种是“惰性”发烟硅；另一种是“活性”蒙脱土。比较了全固态和胶体聚合物电解质体系电化学性质的不同之处。采用电化学交流阻抗，示差扫描量热法，X衍射，拉曼光谱，红外光谱，扫描电镜，循环伏安等方法详细研究了聚合物电解质中各组分对体系离子电导率和机械性能的影响。研究结果表明，纳米复合物为开发具有特定电化学和机械性能的电解质提供了一种有效的途径，它对聚合物电解质的物理性质影响明显。纳米粒子的加入增强了体系的机械性能，同时也使体系对溶剂的吸附能力增加。在全固态聚合物电解质中加入增塑剂，形成胶体态聚合物电解质，体系的电导率大大增加。所制备的胶体复合物电解质的室温电导率可以达到10-3s cm-1的数量级，机械强度好，阳离子迁移数高。指出选择合适的添加剂及复合方法，控制界面的结构和形态，形成尽可能多的高导电的界面，是获得电导率高和机械性能良好的聚合物电解质的有效途径。并讨论了聚合物电解质在铿离子电池中的应用。 近年来，针对生物燃料电池的研究得到了广泛关注，其中实现蛋白质酶分子和电极之间的直接电子传递是研究中的热点。论文的第二部分主要研究了生物燃料电池中的酶电极。通过对碳纳米管（MWNTs）进行预处理，使其表面带有功能性官能团，从而可以实现酶分子在碳纳米管表面的固定，同时还保持了其生物活性。采用吸附法将微过氧化物酶-11（MP-11）或葡萄糖氧化酶（GOx）等生物分子固定到MWNTs上制成酶修饰电极，研究MWNTs对酶和电极之间电子传递的促进作用。当酶分子（MP-11，GOX）固定到MWNTs表面后，循环伏安结果显示出一对可逆的氧化还原峰，对应酶分子的直接电子转移。研究结果表明这种方法可以扩展到固定其他生物酶分子以及实现蛋白质酶分子和电极之间的直接电化学，可以获得一系列氧化还原酶分子的电化学参数，如反应速率常数等。同时，我们还研究了酶修饰电极对其底物的电催化反应。研究结果表明，该修饰电极对底物的电化学反应表现出较好的催化活性。我们还研究了酶分子在MWNTs修饰铂微电极上的电化学行为。这些研究为研制生物燃料电池提供了一种固定酶以及制备电极材料较好的方法。

Preparation of Microporous Membranes by Swift Heavy Ion Irradiation and Impedance Characterization

Polypropylene (PP) microporous membranes were successfully prepared by swift heavy ion irradiation and track-etching. Polypropylene foils were irradiated with Au-197 ions of kinetic energy 11.4 MeV.u(-1) (total energy of 2245.8 MeV) and fluence 1x10(8) ions.cm(-2) at normal incidence. The damaged regions produced by the gold ions along the trajectories were etched in H2SO4 and K2Cr2O7 solutions leading to the formation of cylindrical pores in the membranes. The pore diameters of the PP microporous membranes increased from 380 to 1610 nm as the etching time increased from 5 to 30 min. The surface and cross-section morphologies of the porous membranes were characterized by scanning electron microscopy (SEM). The micropores in the membranes were found to be cylindrical in shape, homogeneous in distribution, and equal in size. Some mathematical relations of the porosity of the PP microporous membranes were established by analytic derivation. The microporous membranes were used in lithium-ion batteries to measure their properties as separators. The electrical conductivity of the porous membrane immersed in liquid electrolyte was found to be comparable to that of commercial separators by electrochemical impedance spectroscopy (EIS). The results showed that the porosity and electrical conductivity were dependent on the ion fluence and etching time. By adjusting these two factors, microporous membranes with good porosity and electrical conductivity were made that met the requirements for commercial use.

Crystallographic and electrochemical characteristics of melt-spun Ti-Zr-Ni-La alloys

Ti-based icosahedral quasicrystalline phase (I-phase) exhibited excellent hydrogen storage property for special structure. Unfortunately, the application as the negative electrode material of the nickel-metal hydride batteries was limited due to the poor electrochemical kinetics. Meanwhile, rare-earth element was beneficial to the electrochemical properties of Ti, Zr-based alloy.

Structures and electrochemical characteristics of Ti0.26Zr0.07V0.24Mn0.1Ni0.33Mox (x=0-0.1) hydrogen storage alloys

Microstructures and electrochemical properties of Ti0.26Zr0.07V0.21Mn0.1Ni0.33Mox (x=0,0.025,0.05,0.075, 0.10) electrode alloys have been investigated. The results of XRD analysis show that the alloys are mainly composed of V-based solid solution phase with body centered cubic (bcc) structure and C14 Laves phase with hexagonal structure. The addition of Mo element can imp ove the activation characteristics, maximum discharge capacity and cyclic durability for the electrode alloys

Dynamic mechanical properties of gel polymer electrolytes containing ionic liquid

The copolymer of acrylonitrile (AN), methyl methacrylate (MMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) is synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF(4)). The dynamic mechanical properties of the resulting gel polymer electrolytes containing ionic liquid are measured.

Effect of La-Mg-based alloy addition on structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy

Effect of La-Mg-based alloy (AB(5)) addition on Structure and electrochemical characteristics of Ti0.10Zr0.15V0.35Cr0.10Ni0.30 hydrogen storage alloy has been investigated systematically. XRD shows that the matrix phase structure is not changed after adding AB(5) alloy, however, the amount of the secondary phase increases with increasing AB(5) alloy content. The electrochemical measurements show that the plateau pressure Ti0.10Zr0.15V0.35Cr0.10Ni0.30 + x% La0.85Mg0.25Ni4.5Co0.35Al0.15 (X = 0, 1, 5, 10, 20) hydrogen storage alloys increase with increasing x, and the width of the pressure plateau first increases when x increases from 0 to 5 and then decreases as x increases further, and the maximum discharge capacity changes in the same trend.