Novel Polymer Solid Electrolytes prepared from Polyurethane Cationomers

为了制备具有良好离子导电性的新型聚合物固体电解质，本研究对离子弹性体的离子链段进行了分子设计。作为固体电解质的基质，高分子链的迁移率很重要，因为可移动链段有利于离子传导，柔性链使基质与电极之间有很好的粘附性。因此，弹性体有望成为聚合物中最好的固体电解质。此外，从回收和加工性的角度来看，热塑性弹性体作为聚合物固体电解质的基质具有几个优点。这是因为该弹性体在没有化学交联剂的情况下在室温下表现出橡胶的弹性。因此，通过四氢呋喃的活性阳离子聚合，合成了新型的聚氨酯阳离子单体和离子烯弹性体。特别是合成了新型齐聚离子多元醇，用于制备聚氨酯阳离子单体。所得离子弹性体的力学性能和热性能均表现出优异的固体电解质性能。由于离子弹性体的形态不仅反映了性能，还反映了官能化程度，通过动态力学分析、差示扫描量热法和小角X射线散射法研究了结构与性能之间的关系。结果发现，由二甲基氨基和聚氧四亚甲基组成的新型脂肪族离子烯弹性体的离子链段聚集度小于已报道的阳离子型离子烯弹性体。这表明离子物种在脂肪族离子烯弹性体基质中的衍射率可能很高。用阻抗分析仪测量了在基质中掺杂高氯酸锂后所得弹性体的离子电导率。

In order to prepare novel polymer solid electrolytes with an excellent ionic conductivity, the molecular design of ionic segment for ionic elastomer was carried out in this study. As a matrix of the solid electrolytes, the mobility of polymer chain is important because the mobile segments are preferable for ionic conduction and the flexible chains give a good adhesion between the matrix and electrode. Therefore, an elastomer is expected as a best polymer solid electrolyte among the polymers. Additionally, a thermoplastic elastomer has several advantages as a matrix for polymer solid electrolyte from the viewpoints of recycling and processability. It is because the elastomer shows the rubber elasticity at room temperature without chemical crosslinking. Thus, novel polyurethane cationomer and ionene elastomer were synthesized by using a living cationic polymerization of tetrahydrofuran. Especially, the new oligomeric ionic polyols were synthesized for the preparation of polyurethane cationomers. The mechanical properties and thermal properties of obtained ionic elastomers were found to be excellent as a solid electrolyte. Since the morphology of ionic elastomers reflected not only the performance but also the functionality, the relationship between the structure and properties was investigated by dynamic mechanical analysis, differential scanning calorimetry and small-angle X-ray scattering measurements. Consequently, the degree of aggregation of ionic segments of a novel aliphatic ionene elastomer composed of dimethyl ammonium group and poly (oxytetramethylene) was found to be smaller than those of dicationic type ionene elastomers reported. This observation suggests that the diffraction of ionic species in the matrix of aliphatic ionene elastomer may be high. The measurement of ionic conductivity of the obtained elastomers is conducting after doping the lithium perchlorate in the matrix using the impedance analyzer.