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One-step synthesis of dual-ligand 2D conductive metal-organic framework for high-performance lithium storage

双配体基二维导电金属-有机框架的一步合成及其储 锂性能研究

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Abstract

Two-dimensional conductive metal-organic frameworks (2D c-MOFs) are emerging as promising electrode materials for lithium-ion batteries (LIBs). However, 2D c-MOFs with binary redox-active organic ligands are rare and suffer from complicated synthesis procedures. Herein, a facile one-step method is developed for the synthesis of a dual-ligand-based 2D c-MOF Cu3(HHTP)(THQ) (HHTP = 2,3,6,7,10,11-hexahydroxytriphenyl, THQ = tetrahydroxy-1,4-benzoquinone) by using the ethylenediamine regulator. The resulting Cu3(HHTP)(THQ) possesses good conductivity, abundant active sites, and excellent chemical stability. As an anode material for LIBs, Cu3(HHTP)(THQ) exhibits high specific capacity, good rate performance, and long-term cycling stability. Comprehensive experimental studies and theoretical calculations reveal that CuO4 units and aromatic benzene rings in Cu3(HHTP)(THQ) are involved in lithium storage, thereby optimizing the lithium storage performance. This work provides a new way for the construction of dual-ligand 2D c-MOFs and high-performance LIB electrode materials.

摘要

基于双氧化还原活性有机配体的二维导电金属-有机框架(2D c-MOFs)是极具潜力的锂离子电池(LIBs)电极材料. 然而, 双配体竞争配 位导致该类材料合成具有极大挑战性. 本文以乙二胺为调节剂, 发展了 一步法合成双配体基2D c-MOF Cu3(HHTP)(THQ) (HHTP = 2,3,6,7,10,11-六羟基三亚苯, THQ = 四羟基-1,4-苯醌). 所得 Cu3(HHTP)(THQ)具有良好的导电性、丰富的活性位点和优异的化学 稳定性, 其作为LIBs负极材料展现出高比容量、良好的倍率性能和长 循环稳定性. 实验结果和理论计算表明, Cu3(HHTP)(THQ)中CuO4活 性位点和苯环单元均参与了锂存储, 从而优化了储锂性能. 该工作为构 筑双配体基2D c-MOFs和高性能LIBs电极材料提供了新的途径.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22035003 and 21905142) and the Programme of Introducing Talents of Discipline to Universities (B18030).

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Authors and Affiliations

  1. School of Materials Science and Engineering, National Institute for Advanced Materials, Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin, 300350, China

    Jia-Cheng Yin  (尹佳成), Zhi-Gang Li  (李志刚), Mingren Cheng  (程明仁), Ming Liu  (刘明), Wei Li  (李伟) & Xian-He Bu  (卜显和)

  2. State Key Laboratory of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, China

    Yin-Qiang Zhang  (张印强), Na Li  (李娜) & Xian-He Bu  (卜显和)

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  1. Jia-Cheng Yin  (尹佳成)
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  6. Wei Li  (李伟)
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  7. Na Li  (李娜)
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  8. Xian-He Bu  (卜显和)
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Contributions

Author contributions Yin JC designed this study, conducted the experiments, performed the data analysis, and wrote the paper; Zhang YQ, Cheng M and Liu M provided some testing support; Li ZG and Li W provided some theoretical computation support; Li N and Bu XH directed the study and polished the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Na Li  (李娜) or Xian-He Bu  (卜显和).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Jia-Cheng Yin received his BS degree (2017) from Hubei University and PhD degree (2023) from Nankai University supervised by Prof. Xian-He Bu and is now a postdoctoral fellow in the same group. His research interest focuses on the controlled synthesis of MOFs and their applications in electrochemical energy storage and conversion devices.

Na Li obtained her PhD degree in inorganic chemistry in 2018 from Nankai University under the supervision of Prof. Xian-He Bu. Then, she joined Prof. Bu’s group as a postdoctoral fellow at Nankai University. In 2022, she was promoted to special associate research fellow. Her recent research focuses on the design and controlled synthesis of new porous materials for energy and environmental science.

Xian-He Bu is a professor at Nankai University and a member of Chinese Academy of Sciences. He obtained his BS and PhD degrees from Nankai University in 1986 and 1992, respectively, under the supervision of Prof. Yun-Ti Chen. He now serves as the dean of the School of Materials Science and Engineering. His current research focuses on the synthesis and applications of multifunctional coordination compounds, crystal engineering, magnetic materials, etc.

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Yin, JC., Zhang, YQ., Li, ZG. et al. One-step synthesis of dual-ligand 2D conductive metal-organic framework for high-performance lithium storage. Sci. China Mater. 66, 4566–4574 (2023). https://doi.org/10.1007/s40843-023-2626-0

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