能源短缺与环境恶化是21世纪全球可持续发展的两大挑战。为了应对这两大难题，世界各国在太阳能、氢能、风能及地热能等清洁能源开发领域都投入了大量的研究资源。在开发这些清洁能源的同时，随之而来的问题是如何高效地存储这些清洁能源。作为一种有效的能源存储技术，二次电池在最近30年里得到了快速发展。在各种二次电池中，锂离子电池技术因其能量密度高及循环寿命长等优点而备受关注。商业化的锂离子电池技术主要是以金属氧化物(LiCoO₂， LiMn₂O₄等)或者金属磷酸盐(LiFePO₄)为正极，石墨化的碳材料为负极构筑的储能器件。目前的电池技术基本上实现了这些电极材料的理论容量，但是仍不能满足日益增长的能源存储需求。此外，大量具有毒性的重金属离子的使用对自然环境也造成了巨大压力。更重要的是，锂资源的有限性和分布不均性严重限制了锂离子电池技术的发展。鉴于此，开发绿色高性能的新型电极材料不仅能够促进二次电池技术的发展，而且对于应对不断恶化的能源与环境问题也具有重大意义。相对于传统的无机电极材料，具有氧化还原活性的聚合物电极材料具有环境友好、可再生性、结构易调控及成本低等特点，有望成为下一代绿色高性能的电极材料。 本博士论文主要围绕有机微孔聚合物的设计、合成、结构调控及其电化学性能开展研究工作。设计合成了系列新型的有机微孔聚合物，并系统研究了聚合物的化学组成与结构、孔性能、能级带宽及电子结构对电化学性能的影响。研究工作主要包括以下四个方面： (一)噻吩基共轭微孔聚合物锂离子电池负极材料研究 设计合成了线型和三维交联结构的系列聚噻吩电极材料，对比研究了线型和三维交联结构聚噻吩的电化学性能；并考察了三维聚噻吩的比表面积及噻吩含量对锂离子电池性能的影响。研究表明，三维交联聚噻吩相对于线型聚噻吩具有更高的电化学活性；同时，高的比表面积和高的噻吩含量均有利于噻吩基共轭微孔聚合物表现出高的储锂能力。由于制备的P33DT聚合物具有高的比表面积(696㎡／g)和高的噻吩含量(100％)，其在45 mA／g的电流密度下表现出高达1215 mAh／g的储锂容量，在500 mA／g的电流密度下充放电1000周后仍能保持初始容量的80％左右，表现出优良的循环稳定性。 (二)共轭微孔聚合物电子结构的调控及其钾离子电池性能研究 通过构建模块的选择，设计合成了具有不同电子结构的共轭微孔聚合物，考察了聚合物的电子结构对钾离子电池性能的影响。研究表明，低的LUMO能级、窄的能隙宽度和均匀的LUMO轨道分布均有利于共轭微孔聚合物表现出高的储钾能力。其中，以芘和苯并噻二唑构筑的共轭微孔聚合物负极材料在50 mA／g电流密度下表现出高达428 mAh／g的可逆容量。 (三)三苯胺基有机微孔聚合物锂离子电池正极材料研究 以三苯胺衍生物为反应单体，通过选用不同的聚合方法，设计合成了系列具有不同比表面积的三苯胺类有机微孔聚合物，研究了制备材料用作锂离子电池正极材料的电化学性能，考察了聚合物的比表面积对锂离子电池性能的影响。研究表明，高度交联的多孔结构和高的比表面积有利于提高三苯胺基有机微孔聚合物电极材料的电化学活性和倍率性能。其中，以Yarnamoto聚合反应制备的聚合物具有较高的比表面积(1512 ㎡／g)，其可逆容量接近理论值。 (四)芘基共轭微孔聚合物氯化锌水溶液电池性能研究 选用具有不同可聚合官能团数目的的芘基单体，设计合成了具有不同比表面积的芘基共轭微孔聚合物，考察了芘基共轭微孔聚合物的结构与电化学性能之间的关系。研究表明，聚合物的比表面积越高，其氧化还原活性也越高。其中，比表面积为1216 ㎡／g的聚合物在氯化锌水溶液电解液中表现出高达147 mAh／g的比容量和25000周的超长循环能力。 关键词：有机微孔聚合物，比表面积，电子结构，电化学能源存储

 Energy crisis and ever-worse environment are the two main challenges for the sustainable development of our society. To solve the energy- and environment-related problems, most countries are paying more attention on developing clean energy sources, such as solar energy, nuclear energy, hydrogen energy, wind energy and geothermal energy. What follows developing cleaning energy sources is how to effectively strore the developed clean energy. In the recent 30 years, great progress has been achieved on rechargeable batteries, which is a kind of reliable energy storage technique. Among all kinds of rechargeable batteries, lithium-ion batteries (LIBs) have attracted great attention due to their high energy density and long cycling life, in which metal oxides (LiCoO₂, LiMnO₂ etc.) or phousphates (LiFePO₄, Li₃V₂(PO₄)₃) are employed as the cathodes and graphic carbons as the anodes. However, the current technology of commercial LIBs has realized the theoretical capacity of these electrode materials, which still can not meet the ever-increasing energy-storage requirements. In addiotion, the usage of expensive and heavy-metal elements also raises great concerns. Moreover, the uneven distribution as well as low abundance of lithium element makes it urgent to develop the altanatives of LIBs. As known, the development of rechargaeable batteries mainly rely on the progress of electrode materials. Consequently, it is highly desiable to develop green, low cost and high performance elecrodes for the next generation of recharable batteries. Compared with inorganic electrode materials, redox polymer electrodes show some features of environmental friendliness, resources renewability, and low cost, enabling these redox polymers as competive electrodes for the next generation of “green batteries”. Herein, we focus on the structure design, synthesis, structure optimization and electrochemical performances of microporous orgainc polymer (MOP) electrodes for high performance rechargeable batteries. The effects of structure, component, porosity and electronic structure on the electrochemical performance were systemically investigated. This research project mainly includes the four parts as bellow (1)The electrochemical performance of thiophene-containing CMPs as anode materials in LIBs Both linear and crosslinked thiophene-containing polymers were prepared through FeCl₃-catalyzed oxidative coupling reaction. The influence of BET surface area and thiophene content on the electrochemical performance of these thiophene-containing CMPs was studied by tuning the crosslinked degree and thiophene content of the monomers. It reveals that the crosslinked polythiophene shows higher performance than the linear polythiophtene. In addition, the higher the BET surface area and the thiophene content, the higher the redox activity of thiophene-containing CMPs. The crosslinked polythiophene with high surface area of 696 ㎡/g and 100% thiophene content can deliver a extremely high Li ion storage capability of 1215 mAh/g and a long cycling life of 1000 cycles at 500 mA/g with capacity retention of 79.9%. (2)CMPs with tunable electronic structure as high performance anodes for potassium-ion batteries (KIBs) Two seies of CMPs were designed and synthysized, in which the electronic structure was finely tuned by varying their building blocks. The structure-performances relationship of CMPs demonstrates that low LUMO energy level, narrow band gap and even distribution of LUMO benefits the CMPs to show high redox activity. When working as an anode in a KIB, the CMP consisting of pyrene and benzothiadiazole units with highly delocalized LUMO delivers a high reversible capacity of 428 mAh/g for the storage of K ions. (3)Micorporous poly(triphenylamine) as cathode material for dual-ion batteries The surface area of poly(triphenylamine) can be tuned through different polymerization reactions of the deriatives of triphenylamine. The nickel-catalyzed Yamamoto cross coupling reaction endows poly(triphenylamine) with the highest BET surface area, followed by palladium-catalyzed Suzuki reactions and FeCl₃-catalyzed oxiditation cross-coupling polycondensation. The structure-performance relationship revealed in this project demonstrates that the higher the surface area of poly(triphenylene) the higher the redox activity. The poly(triphenylene) prepared Yamamoto delivers a high capacity of 105.7 mAh/g at 50 mA/g, which is very close to its theoretical capacity of 109 mAh/g. (4)Microporous polypyrenes with different surface area as cathode materials for dual-ion aqueous Zn-metal batteries The BET surface area of polypyrenes can be tuned by selecting different polymerization reactions of pyrene derivatives. The influence of BET surface on the redox activity of polypyrenes in aequeous 30 m ZnCl₂ electrolyte was investigated. The comparative study announces that the the higher the surface area, the higher the redox activity of polypyrene. The conjugated microporous polypyrene with high surface area of 1216 ㎡/g is able to deliver a high specific capacity of 147 mAh/g when working as a cathode in a dual-ion Zn-metal battery. Keywords: microporous organic polymers, surface area, electronic structure, electrochemical performance