Charge transport, thermodynamics, and hydrodynamics in side-chain and main-chain polymerized ionic liquids

新型材料，如聚合离子液体，被认为是具有高传输和存储能力的器件的潜在候选者，目前是深入研究的重点。目前的项目涉及形态学对几种新合成的聚合离子液体及其结构相关单体化合物的电荷输运、量热和颗粒流的影响。特别注意聚合程度、阴离子类型和阳离子在聚合链中的位置所起的作用。提出的研究结合了通过线性和非线性介电光谱，流变学，量热学和核磁共振获得的结果。这些结果将补充目前稀少的文献，试图确定理论和现象学的基础，能够描述这类新出现的聚合物的迷人行为。特别是，我们的研究将包括沿聚合主链的阳离子碎片聚合物，这与侧基聚合离子液体的常见情况不同。通过这种方法，人们将能够通过流变学或量热法探测的片段重排来识别阳离子的动力学。结合在宽频率范围内从不同技术获得的结果，将提供机会访问聚合物基质的个体动力学和自由迁移电荷的动力学，从而研究这些材料中机械稳定性和离子迁移率之间相互关系的本质。我们相信，在这个项目中获得的结果将为更深入地理解聚合物熔体中的电荷动力学，特别是高浓度非晶电解质中的电荷动力学开辟新的领域。

Novel materials such as polymerized ionic liquids, regarded as potential candidates for devices with high transport and storage capabilities, are nowadays in the focus of intensive research. The current project deals with the influence of morphology on charge transport, calorimetry, and particle flow in several newly synthesized polymerized ionic liquids and their structurally-related monomeric compounds. Particular attention is paid to the role played by the degree of polymerization, the type of anions, and the position of the cations within the polymeric chains. The proposed research combines results to be obtained via linear and nonlinear dielectric spectroscopy, rheology, calorimetry, and nuclear magnetic resonance. The results will complement the currently sparse literature trying to identify the theoretical and phenomenological grounds able to describe the fascinating behavior of this newly emerging class of polymers. In particular, our investigations will include polymers with cationic fragments located along the polymeric backbone, distinct from the common situation for side-groups polymerized ionic liquids. By such means one will be able to identify the dynamics of the cations with the segmental rearrangements probed by rheology or calorimetry. Combining results to be obtained from different techniques in a broad frequency range will provide the opportunity to access the individual dynamics of the polymeric matrix and that of the freely migrating charges, thus to investigate the nature of the interrelation between the mechanical stability and the ionic mobility in these materials. We believe that the results to be obtained in this project will open new venues for a deeper understanding of charge dynamics in polymeric melts in particular and highly concentrated amorphous electrolytes in general.