【作者】 徐国祥；

【导师】 唐致远；

【作者基本信息】 天津大学 ， 应用化学， 2004， 博士

【摘要】 本人在博士期间的工作内容主要为大容量聚合物电极材料在二次锂电池中的应用研究，在本论文中，按照研究工作的顺序分别讨论了氨基蒽醌聚合物电极材料、锂硫电池体系、硫化交联聚氯乙烯电极材料、多硫代环戊二烯聚硫化物电极材料、聚硫化物锂离子电池等不同体系。在本文中首次介绍了聚1-氨基蒽醌与聚1,5-二氨基蒽醌作为二次锂电池阴极材料使用的情况，作为一种新型的储能物质，上述聚合物具有高于普通锂离子电池阴极材料的能量密度和较好的循环能力，由于具有电化学氧化还原活性的苯醌基团同能够起到催化作用的导电聚苯胺骨架位于聚合物分子的同一个重复单元中，使得聚苯胺对苯醌的电化学催化作用得以在分子内部进行，从而避免了活性基团在电解液中溶解、迁移现象的出现。在不同电解液中的测试结果表明氨基蒽醌聚合物电极的放电容量基本都在200mAh·g-1的级别，具有较强的应用潜力。对于存在历史长久的锂硫电池体系，本文从新的角度考察了不同因素对电池电化学性能的影响，分别从制作工艺、工作温度、添加剂问题等不同角度研究了锂硫电池的优化条件，得到具有高能量密度和较好循环性能的锂硫电池系统，此外，本文首次结合实验在理论上分析了商品化锂离子电池电解液体系与锂硫电池不相匹配的原因，指出了对锂硫电池电解液系统选择的基本原则。考虑到在环境保护意识逐渐提高的今天绿色合成化学的重要性，本文首次尝试了温和条件下硫化交联聚氯乙烯材料的溶液合成，得到具有较高交联程度的梯形聚硫化物电极材料，实验测试表明，使用与锂硫电池相当的电解液，硫化交联聚氯乙烯材料的放电容量要高于常规锂离子电池正极材料，在此基础上，本文确定了提高本材料循环性能的若干方法。本文研究了不同含硫量的多硫代环戊二烯以及多硫代环戊二烯-丙烷复合聚合物电极材料在不同电解液体系中的电化学行为，通过一系列的测试研究了材料硫化程度与电化学性能的相互关系，得到放电容量与循环能力都比较优秀的聚硫化物锂电池体系，并预测了不同聚合物材料的凝胶点，对上述聚合物的合成条件进行了优化。在上述工作的基础上，本文还首次尝试了以电化学合成碳化锂LiC6作为负极的聚硫化物锂离子电池的测试，并分析验证了影响电池性能的各种因素。对上述不同电池体系的研究表明，大容量聚合物电极材料具有较高的研究价值和应用潜力，因此被认为是最有可能取代现有锂离子电池电极材料的候选物质之一，本文将在以后的工作中继续努力以期得到更大的进展。更多还原

【Abstract】 The research work emphasized on the application of polymer electrode with high capacity which used in secondary lithium batteries. This dissertation discussed different systems which include poly(aminoanthraquinone), Li/S battery, cross linked poly(chloroethylene) sulfide, poly(cyclopentadiene sulfide) and lithium-ion batteries which use polysulfide as cathode material.The poly(1-aminoanthraquinone) and poly(1,5-diaminoanthraquinone) are introduced for the first time. As new cathode materials, they revealed excellent capacity and good cycle ability. The groups of quinone and polyaniline existed in the same molecular, so polyaniline can catalyze quinone inside the molecular and the active material can not dissolve in electrolytes or transfer into negative electrode. Tested in different electrolytes it can be confirmed that poly(aminoanthraquinone) of 200mAh·g-1 discharge capacity has strong potential application.The influence of different factors on the system of lithium/sulfur battery was studied with a new point of view. We have optimized the properties of Li/S battery by changing production techniques, operating temperature and the kind of additives of it. According to the result of experiment we have found the theoretic reason that the common lithium-ion battery electrolytes can not be used in the Li/S battery. On the basis of study we pointed out the essential rules about how to choose the suitable electrolytes for Li/S batteries.Considering the importance of friendly environmental chemical synthesis, we synthesized the cross linked poly(chloroethylene) sulfide in a mild solution for the first time, and got a highly cross linked polysulfide which has higher discharge capacity than common cathode materials. Some methods that can improve their cycle life have been obtained. We have studied the electrochemical behavior of poly(cyclopentadiene sulfide) and the poly-(cyclopentadiene-propylene sulfide) in different electrolyte solution. Through different tests we studied the relation between the property and the sulfur content and gained the Li/polysulfide battery system with excellent capacity and cycle property. We also optimized the synthesis condition by forecasting their gel-point.Finally, we have tested the electrochemical property of polysulfide lithium-ion batteries with LiC6 anode. We will enhance the property of these materials in the future just because they are the most promising candidates for today’s cathode materials.更多还原