基于大π共轭配体的导电配位聚合物超薄纳米片的设计与合成

Conductive coordination polymer nanosheets have shown great application prospects as lithium ion anode materials due to their adjustable structure, good stability and large storage capacity. However, the reported conductive coordination polymers generally have poor conductivity and are difficult to exfoliate, especially the oversized particles (or blocks) will cause active surface sites to be blocked, thereby reducing the conductivity. In this project, we intend to design and synthesize a series of large π-conjugated organic ligands, select metal ions to form two-dimensional conductive coordination polymers, and prepare ultrathin nanosheets by surfactant-assisted solvothermal method and exfoliation strategy. We will investigate the effects of aromatic ring nitrogen heteroatoms, different substituents and different coordination groups on conductivity and exfoliation performance of the target coordination polymers, exploring the oriented synthesis method of ultrathin nanosheets with high charge transport performance, revealing the structure-activity relationship between structure and performance, and laying a material foundation for the application of conductive coordination polymer nanosheets in lithium ion batteries, which is of great significance to the revolution of new energy technology.

导电配位聚合物纳米片由于其结构可调、稳定性较好、储存容量大等优点，作为锂离子负极材料已表现出巨大的应用前景。然而，已报道的导电配位聚合物普遍导电性较差、难剥离，尤其是颗粒（或块体）尺寸过大会导致其表面活性位点受阻，从而降低其导电性能。本项目拟设计合成一系列大π共轭的有机配体，选择金属离子配位形成二维导电配位聚合物，采用表面活性剂辅助的溶剂热法和剥离策略制备出超薄纳米片。重点考察有机配体中芳环氮杂原子、不同取代基和不同配位基团对目标配位聚合物导电和剥离性能的影响，探索出具有高效电荷传输性能的超薄纳米片定向合成方法，揭示结构与性能之间构效关系规律，为导电配位聚合物纳米片应用于锂离子电池打下坚实的物质基础，这对新能源技术的革命具有极其重要的意义。

导电配位聚合物纳米片由于其结构可调、稳定性较好、储存容量大等优点，作为电子器件关键材料已表现出巨大的应用前景。本项目成功合成大π共轭有机配体，选择与金属离子制备出二维配位聚合物，通过结构模拟和测试表征验证其层状二维金属-配体配位层结构。使用乳化分散机在液相中对配位聚合物进行剪切剥离得到超薄二维纳米片，利用多种表征验证配位结构的高稳定性和高结晶性，并表征其形貌和成分。测试其电子电导率、电化学阻抗谱，结果表明实现了合成高导电性能的超薄配位聚合物纳米片的有效方法。通过电化学测试和理论计算研究了配体大π共轭结构、氮原子和配位硫原子对共轭平面电子传输的影响。基于配位聚合物的优异性能，还研究了质子传导、光催化、传感等方面的应用研究。项目实施期间发表SCI学术论文12篇，包括Adv. Funct. Mater.、Chem. Commun.、Top. Curr. Chem.、J. Mater. Chem. C等，申请发明专利5项，其中已授权1 项。