新型长效阻醇加成型聚降冰片烯基碱性阴离子交换膜的制备机理及其离子传输、阻醇、长期稳定性强化机制

The development of high resistance alcohol as well as long-term stable effect polymer alkaline anion-exchange membrane is expected to resolve the present problem of high methanol permeability and high cost that exsist in direct methanol fuel cell(DMFC) application. And realize its realitive commercial application. In this project, a novel crosslinking structure and organic-inorganic alcohol resistance hybrid membrane, which is suitable for DMFC long-term using,is innovtive designed and prepared by using the high-performance addition polynorbornene as polymer backbone material.And their structure-effect relationships, ion transport mechanism, alcohol resistance mechanism and its enhance regulation and controllable method will be also studied. New preparation method for high-effect and resistance alcohol polymer alkaline anion-exchange membrane will be established and developed by combination coordination polymerization with in-situ sol-gel crosslinking techniques. And finally realize the membrane material structure controllabe preparation and its properties regulation by studying the membrane materials synthesis method and its structure-effect relationships.By investigating the influence of hydrophilic/hydrophobic micro-phase separation formed by the polymer main chain and functional side chain on ion transport nano channel formation and its ion transport properties, probe the formation mechanism of nano channel and realize the efficient ion transport channel construction and enhance controllable regulation. We will probe the influence rule of the crosslinked network structure and inorganic nanoparticles on long-term stability of hybrid membrane and formation mechanism of resistance alcohol layer and establish the constructive and regulative strategy of efficient resistance alcohol layer and evaluate the application performance of hybrid membrane and the long-term stability in DMFC using. The mechanism of ionic conduction, alcohol resistance and enhance mechanism will be also illustrated through ion and methanol molecular dynamics simulation studying.

发展高阻醇性和长期稳定高效的聚合物阴离子交换膜有望解决目前直接甲醇燃料电池存在高甲醇渗透和高成本等难题，实现真正意义上的商业化应用。本项目以高性能加成聚降冰片烯为基材，创新性地设计制备适于直接甲醇燃料电池长期稳定使用的交联有机无机杂化阻醇膜，并研究其构效关系、离子传输、阻醇、长期稳定性强化机制。通过对膜材料的合成方法和构效关系研究，建立通过配位聚合和原位溶胶凝胶交联技术创制高效阻醇聚合物阴离子交换膜新方法，实现膜材料结构可控制备及性能调控；研究主侧链形成亲/疏水微相分离对纳米通道形成及离子传输性能影响，探讨纳米通道形成机制，实现高效离子传输通道的构筑与强化调控。探讨交联网络结构和无机纳米粒子对杂化膜长期使用稳定性影响及纳米阻醇层形成机制，建立高效阻醇层构筑与调控方法，评价膜材料在直接甲醇燃料电池使用中的应用性能及长期稳定性。通过离子和甲醇分子传输过程动力学模拟研究，阐明离子传导、阻醇机制。

发展高阻醇性和长期稳定高效的聚合物阴离子交换膜有望解决目前直接甲醇燃料电池存在高甲醇渗透和高成本等难题，实现真正意义上的商业化应用。本项目以高性能加成聚降冰片烯为基材，创新性地设计了制备适于直接甲醇燃料电池长期稳定使用的交联有机无机杂化阻醇膜，并研究了其构效关系、离子传输、阻醇、长期稳定性强化机制。通过对膜材料的合成方法和构效关系的研究，建立了通过配位聚合和原位溶胶凝胶交联技术创制高效阻醇聚合物阴离子交换膜新方法，实现了膜材料结构可控制备及性能调控；研究了主侧链形成亲/疏水微相分离对纳米通道形成及离子传输性能影响，探讨了纳米通道形成机制，实现了高效离子传输通道的构筑与强化调控。探讨了交联网络结构和无机纳米粒子对杂化膜长期使用稳定性影响及纳米阻醇层形成机制，建立了高效阻醇层构筑与调控方法，评价了膜材料在直接甲醇燃料电池使用中的应用性能及长期稳定性，并阐明了离子传导、阻醇机制。使极性功能化聚环烯烃的分子设计及开发高阻醇性和长期稳定高效的聚合物阴离子交换膜，理论上得到了合理的聚合机理，实践上能做到了结构、形貌与性能的调控。相关研究成果在Polym. Chem. Journal of Polymer Science, Part A: Polymer Chemistry、RSC Advances、Polymer Engineering & Science等国际高水平SCI源刊物上发表学术研究论文11篇。部分研究成果申请并获授国家发明专利1项，参加国内相关的学术会议6人次。本研究成果不仅拓宽了阴离子交换膜设计合成的思路，丰富了聚合物阴离子交换膜的种类，而且拓宽聚合物阴离子交换膜在直接甲醇燃料电池新能源领域的应用，扩大了功能环烯烃共聚物的应用前景。