时间分辨及二维相关红外光谱在快离子导体离子迁移微观动力学中的研究

Dynamic information regarding coordination and dissociation effects deriving from the migration of ions under an external DC electric field has been extensively studied by time-resolved and generalized two-dimensional correlation Fourier transform infrared spectroscopy (TR-FTIR and 2D FTIR COS) at different temperatures. The results show that the migration of both lithium cations and ClO4-1 anions is a complicated process accompanying the change of both the form and appearance sequence of carriers under the electric field, which is apparently different from that without electric field. The ionic conduction of PEO-based SPEs under the electric field can be divided into the dissociation of coordinated ions and the diffusion of free carriers, and the activation energy of dissociation (Ei) and diffusion (Ed) is the function of perturbation, temperature, and forms of ligands.

采用具有纳秒（ns）分辨率本领的时间分辨红外光谱与二维相关光谱联用技术研究了外电场作用下聚氧化乙烯基聚合物固体电解质（SPE）中锂离子载流子的传导行为，详细研究了离子载流子迁移瞬间过程所属时间域及迁移微观动力学的相关信息，丰富了整个离子导电机理理论。

采用时间分辨及二维相关红外联用技术系统地研究了PEO/LiClO4及丙烯酸羟乙酯共聚物（co-HEA）/双马来酸硼酸锂（LiBMB）电解质体系在外电场作用下的动态离子迁移行为及迁移机理，阐明了不同电解质体系中微观离子（Li+）在外加电场作用下迁移的动力学特征，进一步丰富了离子跃迁的时间及空间信息。具有纳秒时间分辨红外光谱的使用，首次确定了锂离子在外电场作用下迁移的精确信息及迁移行为所属的时间域，对快速充电电池、超级电容器等新能源设备的开发具有重要的指导意义。