易位聚合构筑自修复型单锂离子聚电解质及其性能研究

In light of the fact that the ionic homopolymers possessed poor mechanical properties, and their dry ionic conductivity values were far below the target that is required for current battery applications, we propose this project focused on the fundamental studies about the construction of self-healing single lithium-ion conducting materials via metathesis polymerization methodology and their properties. Utilizing the properties that the structure, especially the microstructure of polymers could be precisely controlled by metathesis polymerization methodology, and the distinguishing properties of ionic and nonionic segments, hydrogen-bond interaction , as well as the introduction of SiO2, the self-assemble morphology could be adjusted to form well-defined nanostructures channel for ions transformation, where the resulting material can possess orthogonal properties of excellent mechanical properties as well as high conductivity. Via the investigation of the preparation, self-assembly behavior and properties of this class of ionic block copolymers, we expected to master the efficient synthetic approach of self-healing ionic block copolymers electrolyte materials by metathesis polymerization methodology. The main objective of this research is not only to obtain a self-healing, solution-processing, good stability, excellent mechanical properties as well as high ionic conductivity, but also gain the relationship between the component, microstructure, self-assemble morphology and the functionality, and finally to provide full and accurate evidence for further optimizing the structure and functionality of conductive polymers.

基于离子化均聚物力学性能欠佳，且室温干态离子电导率尚未达到电池应用的要求等问题，拟开展关于易位聚合方法构筑自修复型单锂离子导电材料及其性能的基础研究。利用易位聚合方法对聚合物结构（尤其是微结构）的精确控制、离子与非离子嵌段性质的差异性、氢键作用、纳米SiO2的引入，调节组装体形态，形成离子传输通道，在提高其导电性同时，赋予材料优异的力学性能。通过此类离子化嵌段共聚物的合成、自组装与性能研究，掌握易位聚合构筑自修复型离子化嵌段共聚物电解质材料的方法。研制出可溶液加工、稳定性好、力学性能与导电性能优异的自修复导电高分子材料，获得关于聚合物组成、微结构、组装形态与功能性相互关系的信息，为进一步优化此类导电聚合物结构和性能提供翔实的依据。

项目从聚合方法上研究了不同类型聚合物电解质材料的制备与性能。易位聚合方法得到的聚烯烃主链上仍然存在大量的不饱和键，为材料的后功能化提供可能性，这是其他聚合方法所不具备的。利用开环易位聚合，将稳定性好的三氮唑离子与聚降冰片烯侧链相连，并引入支化离子侧基，实现了支化三氮唑离子功能化易位嵌段共聚物的可控合成，得到了结构明确的电解质材料，并利用三唑啉二酮基团与双键的Alder-ene点击化学反应构建了网状聚合物导电体系，并探索了该体系的导电性；利用ROMP反应的活性可控的特点，制备嵌段共聚物，并引入含氢键作用的基团，构筑了自修复聚合物电解质材料；通过点击化学反应，利用含刚性结构的单体的聚合，制备出了溶解性好、可溶液加工、成膜性好的超支化聚合物，材料制备方法简便，并对锂离子与锌离子掺杂后的聚合物电化学性能进行探索，发现其在保证较好电导率的同时具备良好的电化学稳定性；开发了一类新型离子液体电解质材料，电化学窗口宽，以此为基础的电池充放电性能好，尤其是在高温时的电池性能优异，为高温聚合物电解质基电池的开发提供参考。