类高分子三维交联石墨烯宏观体相材料的制备及其应用研究

Though two dimensional graphene has a series of excellent intrinsic properties, its large-scale applications haven’t been realized. The main bottleneck is how to conveniently and low-costly prepare the macroscopic graphene bulk material retaining the intrinsic properties of the individual graphene sheets. And numerous superior intrinsic properties of graphene will be manifested on a macroscopic scale. To this end, this proposal will study and develop the principle, method and technique for the convenient, low-cost and controllable preparation of polymer-like three-dimensional cross-linked graphene bulk material, in which the building units are independent and individual single-layer graphene sheets covalently self-cross-linked together through the chemical bonds located mostly on the graphene sheets edges. Then we will study to understand the influencing mechanism for material preparation of different graphene sheets under different technique conditions. Furtherly, the optimization and control of the macroscopic graphene bulk material’s performance will be achieved through the adjustment and control of macro/micro-structure and morphology of the material. Based on the above graphene bulk material, we will comprehensively study the relationship between the intrinsic properties of individual graphene sheets and the performance of the macroscopic graphene bulk material. Many application researches, especially unconventional catalysis, optoelectronic application and energy storage, will furtherly be carried out based on the material’s special optoelectronic properties, mechanical properties, etc.

二维石墨烯具有一系列优异的本征性质，然而其大规模应用目前仍没有实现，主要瓶颈在于如何方便且低成本地获得石墨烯宏观体相材料又同时维持单片石墨烯的本征性质，从而在宏观尺度上获得石墨烯的本征性能。针对这一问题，本课题拟研究发展以相互独立的单层石墨烯作为结构（聚合）单元通过边缘自交联的方式，便利、低成本和可控地制备类高分子三维交联石墨烯宏观体相材料的原理、方法和工艺；理解和掌握多种石墨烯（单元的）结构和工艺条件对材料制备的影响机制；实现对石墨烯宏观体相材料的宏观/微观结构及形貌的调控，从而达到优化和调控其性能的目的。在此材料基础上系统研究石墨烯宏观体的性能和本征石墨烯性质之间的相互关系，进一步开展这种材料的应用研究，特别是重点开展基于其特别的光电性能和机械性能等在非常规催化、光电、储能等方面的应用研究。

石墨烯作为一种具有极大应用潜力的新型二维纳米材料，自被发现起一直备受关注，然而至今尚未实现大规模应用，主要原因在于其本身强烈的π-π相互作用产生聚集导致体相材料无法体现石墨烯优异的本征性质。本项目的研究目的就是通过在石墨烯片层间实现三维化学交联从而使体相材料能维持单片石墨烯的本征性质，从而在宏观尺度上获得石墨烯的本征性能。围绕项目计划目标，我们在类高分子三维交联石墨烯宏观体相材料的宏量可控制备、构效关系、力学性质、光致热电子催化及光电性能、能源转化与存储等方面取得了系列突破性进展。建立和发展了类高分子三维交联石墨烯宏观体材料的宏量可控制备技术,成功发展了结构与性能可控的不同尺度以及形貌的石墨烯宏观体材料的宏量可控制备方法和工艺，研究了石墨烯片层和边缘结构对三维石墨烯材料相关性质的影响；揭示了类高分子三维交联石墨烯结构单元协同效应产生的超压缩弹性的温度不变性、宽频光电响应等性能。通过石墨烯片层之间的化学交联，实现了石墨烯自身优异性质从微观到宏观的有效转移；利用三维交联石墨烯材料独特的光发射电子原理，发展了铁基三维石墨烯复合催化体系Fe@3DG，实现了200度条件下实现合成氨反应；基于类高分子三维交联石墨烯的光电探测器实现了可见-近红外的宽频响应和高响应度；三维交联石墨烯光热转换器件海水淡化光热转化效率87%；通过构建银纳米线/石墨烯（类石墨烯MXene）三维交联网络骨架结构，实现了高容量、高倍率、长寿命的锂金属电极材料，并开发出相应的3D打印制备工艺；同时实现了基于石墨烯-银纳米线复合纳米材料的微型超级电容器及其阵列的制备与集成。