Nanostructured block copolymer gel electrolytes based on polyethers

该项目的目标是设计纳米结构嵌段共聚物凝胶，用于聚合物基电池和双层电电容器的电解质。这些材料还具有自愈特性，因此设计的纳米结构可以在机械损伤后恢复功能特性。为此，基于两亲性聚醚的ABC三嵌段三元聚合物将与（共价）可交联的嵌段a（用于diols - alder反应的糠醛基部分或用于铜催化叠氮-炔化学的炔）一起使用，嵌段B可溶于有机和水电解质，提供离子迁移性（例如聚（甲基缩水甘油醚））。以及带电荷重复单元的嵌段C，用于基于羧基和氨基部分的组合或可选的两性离子单体的可逆（非共价）交联。水介质中的自组装将导致核-壳-电晕胶束，其中核形成块A可以通过共价键交联以进一步增强纳米结构形状，而C块允许基于静电吸引的进一步交联；在这里，ABC三嵌段三元聚合物胶束携带，例如，C嵌段中的阴离子羧基基团，意图与拮抗胶束结合，其类似地具有C嵌段中的阳离子氨基。这些离子相互作用一方面可能导致形成一个明确的网络或凝胶，另一方面它们的动态性质将成为期望的自愈机制的基础。此外，中间的B区将使离子通过凝胶扩散，这应确保在损伤前和愈合后处于相当的水平。该合成将通过对各自的缩水甘油醚单体进行序活阴离子聚合来完成（例如，对a段进行呋喃基或炔基缩水甘油醚聚合，例如，对B段进行甲基缩水甘油醚聚合，对C段进行烯丙基缩水甘油醚聚合），然后使用巯基点击化学对C段进行侧链修饰以实现带电重复单元。表征将在本项目中发挥重要作用，从ABC三嵌段三元聚合物的综合分析到各自凝胶的制备，包括交联效率的研究和稳定性的探测，以及形态学研究。此外，应该准确地了解凝胶的功能，即离子电导率，以及离子的扩散，以评估最终的自愈进展。最后，凝胶电解质将用于测试电池，作为新电解质材料的原理证明。

The goal of this project is to design nanostructured block copolymer gels for use as electrolytes in polymer-based batteries and electric double-layer capacitors. These materials also feature self-healing properties, whereby the designed nanostructure additionally enables the restoration of the functional properties after mechanical damage. For this purpose, amphiphilic polyether-based ABC triblock terpolymers will be utilized with a (covalently) crosslinkable block A (furfuryl moieties for Diels-Alder reactions or alkynes for copper-catalyzed azide-alkyne chemistry), a block B being soluble in both organic and aqueous electrolytes providing ion mobility (e.g., poly(methyl glycidyl ether)), and a block C carrying charged repeating units for reversible (non-covalent) crosslinks based on combinations of carboxyl and amino moieties or alternatively, zwitterionic comonomers. Self-assembly in aqueous media will then lead to core-shell-corona micelles, wherein the core-forming block A can be crosslinked to further enhance the nanostructured shape by covalent bonds whereas the C block allows for further crosslinks based on electrostatic attractions; here, an ABC triblock terpolymer micelle carrying, for example, anionic carboxyl moieties in the C block is intended to be combined with the antagonistic micelles, which analogously possess cationic amino groups in the C block. These ionic interactions might on the one hand lead to the formation of a defined network or gel, and on the other their dynamic nature will be the basis for the desired self-healing mechanism. Furthermore, the middle B block will enable the diffusion of ions through the gel, which should be ensured at a comparable level before damage and after healing.The synthesis will be accomplished using a combination of sequential living anionic polymerization of the respective glycidyl ether monomers (i.e. furfuryl or alkynyl glycidyl ether for block A, e.g., methyl glycidyl ether for block B, allyl glycidyl ether ether for block C) followed by side chain modification of the C block using thiol-ene click chemistry to realize the charged repeating units. The characterization will play an important role in this project starting from the comprehensive analysis of the ABC triblock terpolymers towards the preparation of the respective gels, including investigations of crosslinking efficiencies and probing the stability besides morphological studies. Furthermore, the functionality, i.e. the ionic conductivity, of the gels should be precisely understood with regard to the diffusion of ions, to evaluate the self-healing progress in the end. Finally, the gel electrolytes will be used in test batteries as proof-of-principle for new electrolyte materials.