物理化学学报 >> 2018, Vol. 34 >> Issue (9): 1074-1079.doi: 10.3866/PKU.WHXB201801231

所属专题: 石墨炔

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石墨炔-有机共轭分子复合材料的制备及其储锂性能

陈彦焕1,2,李教富1,2,刘辉彪1,2,*()   

  1. 1 中国科学院化学研究所, 有机固体院重点实验室, 中国科学院分子科学科教融合卓越中心, 北京 100190
    2 中国科学院大学, 北京 100049
  • 收稿日期:2017-12-29 发布日期:2018-04-09
  • 通讯作者: 刘辉彪 E-mail:liuhb@iccas.ac.cn
  • 基金资助:
    国家重点基础研究发展计划(2016YFA0200104);中国科学院重点项目(QYZDY-SSW-SLH015);国家自然科学基金(21790050);国家自然科学基金(21790051);国家自然科学基金(51573191);国家自然科学基金(21373235)

Preparation of Graphdiyne-Organic Conjugated Molecular Composite Materials for Lithium Ion Batteries

Yanhuan CHEN1,2,Jiaofu LI1,2,Huibiao LIU1,2,*()   

  1. 1 CAS Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, CAS Research/Education Center for Excellence in Molecular Sciences, Beijing 100190, P.R.China
    2 University of Chinese Academy of Sciences, Beijing 100049, P.R.China
  • Received:2017-12-29 Published:2018-04-09
  • Contact: Huibiao LIU E-mail:liuhb@iccas.ac.cn
  • Supported by:
    the National Key Basic Research and Development Project of China(2016YFA0200104);the Key Program of the Chinese Academy of Science(QYZDY-SSW-SLH015);the National Natural Science Foundation of China(21790050);the National Natural Science Foundation of China(21790051);the National Natural Science Foundation of China(51573191);the National Natural Science Foundation of China(21373235)

摘要:

发展了基于超分子化学的新方法实现了对石墨炔的原位氮掺杂,通过利用石墨炔与有机共轭分子间强的ππ作用,原位制备了石墨炔/卟吩复合材料薄膜,并用作锂离子电池的负极材料,其比容量增加到了1000 mAh∙g−1,该复合材料表现出优良的倍率性能和循环稳定性,为可控制备掺氮石墨炔复合材料提供了新的思路。

关键词: 石墨炔, 卟吩, ππ作用, 氮掺杂, 锂离子电池

Abstract:

Graphdiyne(GDY) is a novel carbon allotrope containing sp-and sp2-hybridized carbon atoms.Because of GDY's special structure, theoretical studies have predicted Li storage as dense as 744 mAh∙g−1 in the form of LiC3, representing twice the specific capacity of graphite.Previous studies have reported that GDY film, bulk GDY, N-doped graphdiyne, and similar materials exhibit high specific capacity, excellent rate performance, and long cycle life when used as anode materials in lithium ion batteries(LIBs).The flat(sp2-and sp-hybridized) carbon networks endow GDY with extensive π-conjunction and uniformly distributed pores, which allow ππ interactions between GDY and organic conjugated molecules to construct a GDY/organic conjugated molecule hybrid material for high-performance anodes with in LIBs.Anode materials with higher specific capacity, better rate performance, and longer cycle life still present an important challenge in LIBs.Nitrogen doping of GDY is one of the effective ways to improve the performance of LIBs.Nitrogen doping of GDY has been achieved by annealing at high temperature in an ammonia atmosphere.The resulting material shows enhanced electrochemical properties due to the creation of numerous heteroatomic defects and active sites.Herein, we have developed a new method based on supramolecular chemistry for preparing N-doped GDY(graphdiyne/porphine) with ππ interactions between graphdiyne and organic conjugated molecules.As opposed to previously reported graphdiyne films, the as-prepared graphdiyne/porphine film can be used as an anode for LIBs without any binders or conducting agents.The resulting anode delivers a high capacity of 1000 mAh∙g−1 and exhibits excellent performance and cycle stability, suggesting that the high rate capability and long cycle life are due to the large amount of active sites provided by porphine for lithium storage.Galvanostatic measurements were performed for 5 cycles each, and retentions of 915.4, 778.9, 675.9, 553.6, and 375.2 mAh∙g−1 were obtained at current densities of 100, 200, 500, 1000, and 2000 mA∙g−1, respectively.When the current density was reset to 50 mA∙g−1, the capacity reached 900 mA∙g−1, indicating excellent structural stability during the high-rate measurements.Excellent cyclic stability with a retention of 1000 mAh∙g−1 at 50 mA∙g−1 after 50 cycles was obtained for LIB applications, which results from the unique hierarchical porosity due to the presence of butadiyne linkages.The unique hierarchical structure of the GDY/porphine film was not destroyed after 50 charge/discharge cycles at 50 mA∙g−1, which suggested high structural stability.The competitive lithium storage values provide promising potential for the development of high-performance LIBs.This strategy opens an avenue for designing N-doped graphdiyne with tunable electronic properties under mild conditions.

Key words: Graphdiyne, Porphine, ππ interaction, N-doping, Lithium ion battery

MSC2000: 

  • O646