Recently, the interest in charged polymers has been rapidly growing due to their uses in energy storage and transfer devices. Yet, polymer electrolyte-based devices are not on the immediate horizon because of the low ionic conductivity. In the present study, we developed a methodology to enhance the ionic conductivity of charged block copolymers comprising ionic liquids through the electrostatic control of the interfacial layers. Unprecedented reentrant phase transitions between lamellar and A15 structures were seen, which cannot be explained by well-established thermodynamic factors. X-ray scattering experiments and molecular dynamics simulations revealed the formation of fascinating, thin ionic shell layers composed of ionic complexes. The ionic liquid cations of these complexes predominantly presented near the micellar interfaces if they had strong binding affinity with the charged polymer chains. Therefore, the interfacial properties and concentration fluctuations of the A15 structures were crucially dependent on the type of tethered acid groups in the polymers. Overall, the stabilization energies of the A15 structures were greater when enriched, attractive electrostatic interactions were present at the micellar interfaces. Contrary to the conventional wisdom that block copolymer interfaces act as “dead zone” to significantly deteriorate ion transport, this study establishes a prospective avenue for advanced polymer electrolyte having tailor-made interfaces.

最近，由于带电聚合物在能量存储和传输设备中的应用，人们对带电聚合物的兴趣迅速增长。然而，由于离子电导率较低，基于聚合物电解质的器件还没有出现在眼前。在本研究中，我们开发了一种通过界面层的静电控制来增强包含离子液体的带电嵌段共聚物的离子电导率的方法。层状结构和 A15 结构之间出现了前所未有的重入相变，这无法用既定的热力学因素来解释。 X射线散射实验和分子动力学模拟揭示了由离子络合物组成的迷人的薄离子壳层的形成。如果这些复合物的离子液体阳离子与带电聚合物链具有强结合亲和力，则它们主要出现在胶束界面附近。因此，A15结构的界面性质和浓度波动很大程度上取决于聚合物中束缚酸基团的类型。总体而言，当胶束界面处存在富集且有吸引力的静电相互作用时，A15 结构的稳定能更大。与嵌段共聚物界面作为“死区”而显着恶化离子传输的传统观点相反，这项研究为具有定制界面的先进聚合物电解质建立了一条前瞻性途径。