CAS-Climate: Ion and Interfacial Dynamics in Polymerized Ionic Liquids

非技术综述：如果不开发新型、高性能、清洁的能源转换和储存设备，我们社会日益增长的能源需求就无法满足。电解液是这些装置的关键组件，因为这些材料是选择性传输目标电活性物质的媒介。然而，在许多最先进的电解液中，安全性、稳定性和选择性问题一直是一个令人担忧的问题。目前该项目的一个独特的焦点是研究通过限制和界面相互作用来增强聚合离子液体中电荷传输的新方法，这将使它们适合作为电解液。从计划中的研究中获得的基本理解将为为电池、燃料电池和超级电容器等许多与可持续发展相关的技术应用精心设计和优化聚合物提供基础，在这些技术应用中，界面在决定整体功能方面发挥着重要作用。此外，从该项目中获得的关于与聚合物接触的固体表面化学的影响、聚合物的类型、限制程度和样品制备条件的知识将有益于聚合物科学和工程界。该项目的一个重要组成部分还涉及几项综合教育活动。该项目将通过研究生和本科生积极参与这项研究，促进聚合物纳米技术和材料科学专家的培训和教育。技术概要：聚合离子液体是一类新型的功能性聚合物电解质，它结合了分子离子液体的独特物理化学性质(如不可燃性、宽的电化学窗口、可忽略的蒸汽压和离子传导)和聚合物的突出机械特性。这些材料有望用于各种清洁能源应用，包括染料敏化太阳能电池、便携式电池、致动器、场效应晶体管和电致变色器件。然而，在电化学能量应用的背景下，它们的离子电导率是最关键的性质之一，与聚合时的低分子量对应物相比，它们的离子电导率下降了许多个数量级。在拟议的项目中，将探索一种新的方法，以发展对合理设计具有高离子导电性和其他理想电化学性质的聚合离子液体的基本认识。这项计划研究的总体目标是利用纳米尺度的限制和界面力来开发设计具有增强离子传导性的聚合离子液体的基本框架。计划工作的主要目标是：(I)基本了解纳米尺度的限制程度(由平均孔径和聚合物膜厚度反映)对受限聚合离子液体中聚合动力学、离子传输和动力学的影响，(Ii)揭示聚合物/孔壁相互作用对聚合动力学、离子动力学和电荷传输的作用，(Iii)研究聚合离子液体的分子结构(化学)对其离子动力学和纳米孔中电荷传输的影响，以及(Iv)阐明限制的维度(类型)对聚合动力学的影响。受限聚合离子液体中的离子输运和动力学。从这个项目中获得的对纳米尺度限制的影响的详细的基本了解将为设计与许多技术的可持续性和独特性能相关的功能聚合物提供科学框架，包括适合用于电化学电源和设备的聚合物电解液。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

NON-TECHNICAL SUMMARY:The rising energy needs of our society cannot be met without development of novel, high-performance, clean-energy conversion and storage devices. Electrolytes are a critical component of these devices, as these materials are the media for selective transport of the target electroactive species. However, safety, stability, and selectivity issues are an on-going concern in many state-of-the-art electrolytes. A unique focus of the current project is the investigation of novel approaches to enhance charge transport in polymerized ionic liquids by taking advantage of confinement and interfacial interactions, which would make them suitable as electrolytes. The fundamental understanding obtained from the planned research will provide a basis for deliberate and optimal design of polymers for many sustainability-relevant technological applications, such as batteries, fuel cells, and supercapacitors, where interfaces play a significant role in determining the overall functionality. In addition, the knowledge gained from this project concerning the impact of the chemistry of solid surfaces in contact with polymers, the type of polymer, extent of confinement and sample preparative conditions will be of benefit to the polymer science and engineering communities. An important component of this project also involves several integrated educational activities. The project will contribute to training and education of specialists in polymer nanotechnology and materials science through active involvement of graduate and undergraduate students in this research. The proposed program emphasizes work with underrepresented groups and research experiences for high school students.TECHNICAL SUMMARY:Polymerized ionic liquids are a class of novel functional polymer electrolytes that combines the unique physicochemical properties of molecular ionic liquids (e.g. non-flammability, wide electrochemical windows, negligible vapor pressures, and ionic conduction) with the outstanding mechanical characteristics of polymers. These materials are promising for a variety of clean-energy applications including dye-sensitized solar cells, portable batteries, actuators, field-effect transistors and electrochromic devices. However, their ionic conductivity, which is one of the most critical properties in the context of electrochemical energy applications, drops by many orders of magnitude in comparison to their low molecular weight counterparts upon polymerization. In the proposed project, a new approach to developing fundamental understanding for rational design of polymerized ionic liquids with high ionic conductivity and other desirable electrochemical properties will be investigated. The overall goal of the planned research is to employ nanoscale confinement and interfacial forces to develop a fundamental framework for designing polymerized ionic liquids with enhanced ionic conduction. The major objectives of the planned work are to: (i) develop a fundamental understanding of the impact of the extent of nanoscale confinement (as reflected by the mean pore diameters and polymer film thicknesses) on polymerization kinetics, ion transport and dynamics in confined polymerized ionic liquids, (ii) unravel the role of polymer/pore-wall interactions on polymerization kinetics, ion dynamics and charge transport, (iii) investigate the effect of molecular structure (chemistry) of polymerized ionic liquids on their ion dynamics and charge transport in nanopores, and (iv) elucidate the impact of the dimensionality (type) of confinement on polymerization kinetics, ion transport and dynamics in confined polymerized ionic liquids. The detailed fundamental understanding of the impact of nanoscale confinement gained from this project will provide a scientific framework for the design of functional polymers with relevance to sustainability and unique properties for numerous technologies, including polymer electrolytes suitable for use in electrochemical power sources and devices..This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.