金属有机框架在固态聚合物电解质中的研究

       固态聚合物电解质（ SPE）柔韧性好、易于加工且成本低廉，有望实现
市场化应用。 然而， 目前 SPE 仍面临着室温离子电导率低、 Li+迁移数低、
电化学窗口窄等问题。 研究表明， 在 SPE 中添加填料可有效提高其综合性
能。填料的成分和结构是影响 SPE 性能的关键因素。本文以金属有机框架
（ MOF）作为功能性填料，利用其比表面积高、孔隙率高及表面极性大等特
性对 SPE 性能进行优化， 成功制备出具有高离子电导率、高 Li+迁移数及高
稳定性的 SPE，并探究了 MOF 成分及结构与 SPE 性能间的构效关系。
        本文先以配位饱和的钴基 MOF（ ZIF-67） 作为填料， 探究了 ZIF-67 对
SPE 性能的影响。结果显示 ZIF-67 可有效地促进锂盐解离、 降低聚合物基
底结晶度、 提高聚合物链段运动能力，增加 SPE 体系中 Li+浓度与迁移位点
密度， 进而提高 SPE 的离子电导率。在此基础上，对填料的成分及结构进一
步优化，即采用富含开放金属位点的铁基 MOF（ Fe-MIL-88B-NH2） 为初始
材料，利用静电纺丝技术制备 Fe-MIL-88B-NH2 基纤维作为填料， 用以制备
SPE。研究表明 Fe-MIL-88B-NH2 基纤维可选择性吸附阴离子并促进 Li+迁移，
有效提高 Li+迁移数及离子电导率； 此外， 纤维表面富含-NH2 基团，能够提
高 SPE 的电化学稳定性。得益于以上优势，组装的软包全电池表现出优异的
循环稳定性。最后，本文探究了原位聚合技术对 SPE 及电池性能的提升作
用。研究表明原位聚合可有效优化 SPE/电极界面， 从而显著提升电池循环稳
定性。
        本文选用 MOF 作为功能性填料，制备系列 MOF 基 SPE。 通过调整 MOF
的成分及结构， 优化“ MOF-聚合物”、“ MOF-锂盐”间相互作用，进而提高
SPE 的离子电导率、 Li+迁移数以及电化学稳定性。 本文为固体填料的结构和
成分设计及高性能 SPE 的性能优化提供了理论指导， 对推动高比能固态锂
电池及相关产业的发展具有重要的意义和价值。
 

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