共轭微孔聚合物(CMPs)具有高度交联结构、大比表面积、优良的化学稳定性以及π-共轭骨架等优点,不塌陷的永久孔道使其在锂离子电池(LIBs)中具有广阔的应用前景。采用螺双芴和共轭长度不同的对苯二胺(PA)、联苯胺(BPA)通过席夫碱缩合反应制备了2种共轭微孔聚合物CMPs-PA和CMPs-BPA。其中,CMPs-BPA具有更优良的微孔性质,这是由于使用共轭长度较长的联苯胺增大了聚合物孔径,有助于提高其交联度和增加比表面积,而大比表面积和丰富的微孔结构有助于增大Li+与电解液的接触面积,缩短Li+的扩散距离,促进电荷快速转移。将CMPs用作LIBs负极材料时,CMPs-BPA表现出可逆的氧化还原活性和增强的电化学性能,包括高循环稳定性,在电流密度100mA/g条件下循环500次后,容量保持率仍能达到30.2%。
Conjugated microporous polymers (CMPs) have great application prospects in lithium-ion batteries (LIBs) due to their advantages such as highly cross-linked structure,large specific surface area,excellent chemical stability and π-conjugated skeleton.Herein,two conjugated microporous polymers,CMPs-PA and CMPs-BPA were prepared by Schiff base condensation using spirodifluorene and p-phenylenediamine (PA) and benzidine (BPA) with different conjugation lengths.Among them,CMPs-BPA showed better microporous properties compared with CMPs-PA.The cross-linking degree and specific surface area of the conjugated microporous polymer CMPs-BPA were improved by using long conjugated benzidine that increased the pore size.The large specific surface area and abundant microporous structure helped to increase the contact area between Li+ and the electrolyte,shorten the diffusion distance of Li+,and promote rapid charge transfer.When CMPs were applied as anode materials for LIBs,CMPs-BPA exhibited reversible redox activity and enhanced electrochemical performance,including high cyclic stability,with a capacity retention of 30.2% after 500 cycles at a current density of 100mA/g.
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