石墨烯化聚合物的合成和应用

Synthesis and Applications of Graphenal Polymer

石墨烯是由纯粹的sp2碳组成的二维蜂窝状结构,具有良好的导电导热性;聚合物是由某些小分子结构单元组成的链状或网状大分子,包含大量氢,氧,氮等杂原子或大量功能基团.由于石墨烯具有超大比表面积和优异的电学性能,国内外学者投入了大量精力开发基于石墨烯的高性能储能器件,包括锂离子电池和超级电容器.同时,由于微孔聚合物具有高度可控的结构和超大比表面积,这种新型的聚合物可望广泛应用于气体存储、催化及传感领域.近年来,结构介于石墨烯和聚合物之间的一系列过渡型材料受到广泛关注,迅速成为能源等领域特别是储存领域的研究热点.这类材料同时具有石墨烯单元结构和聚合物片段及功能.但与传统的石墨烯/聚合物复合材料比较,这类材料中的石墨烯结构是由聚合物前驱体及聚合物本身在较高的温度下经过脱氢、重构、稠环化等苯环化学的成键反应逐渐长大而形成的;或者通过石墨烯的化学打孔、化学功能化、化学片段化逐渐形成的石墨烯与聚合物共存的独特结构.这些形成的石墨烯单元被有机链或片段相互连接,形成各式各样的带有化学功能的多孔结构与网络结构,这种独特的结构同时拥的良好的电子传输通道和离子传输通道,是二者的有机结合体,在能源储存等领域表现出极大的应用潜力.本文将这种具有独特结构的石墨烯片段与聚合物片段共同组成的结合体称之为石墨烯化聚合物(graphenal polymer),名称的准确与否还要聚合物界前辈与同仁一起决定.本文结合本课题组这几年来在这一领域的工作思路以及其他的部分本领域同行报道的一些工作进展,集中讨论石墨烯化聚合物的合成方法及其在储能领域的潜在应用.

Graphene is a two dimensional honeycomb-like framework constructed by pure sp2-carbon atoms which exhibits extraordinary electronic and heat transport properties. Meanwhile, polymers are chain-like or network-like macromolecules formed by a series of monomers containing numerous heteroatoms （e. g. , H, O, N） and also functional groups. Due to the large specific surface area and excellent electrical properties of graphene,various high-performance graphene-based energy storage devices including lithium ion batteries and supercapaeitors have been frequently demonstrated. Whilst, thanks to controllable structures and ultra-high surface areas,microporous polymers show potential in applications such as gas storage, catalysis and sensing. Recently, numerous transitional intermediates lying between graphene and polymers have attracted intense interest, being a new star in energy storage applications. Within this kind of nanomaterials, numerous graphenelike subunits are organically interconnected by small organic and/or polymeric fractions, forming diverse porous structures. With such structural characteristics, they are of well-designed combination of electron transport channels and ion transport channels, showing great potential in energy storage applications. Combined with recent progress made by our group and also others,we outline two representative approaches （bottom-up and top-down） for the synthesis of these novel materials （ denoted as graphenal polymers） , as well as exemplify their potential applications.