Mechanism modulating the redox chemistry of hexaazatriphenylene-based small molecules by push–pull electron effect for zinc-ion batteries

Zhi-Qiang Wang (Co-first Author), Jing-Wei Liu (Co-first Author), Jing-Jing Chen, Yong-Cong Huang, Iftikhar Hussain, Wen Luo, Hui-Min Yuan, Jing Hu, Zhen-Yu Wang, Ming-Yang Yang, Ying-Zhi Li, Gui-Yu Liu*, Shuai Gu*, Kai-Li Zhang*, Zhou-Guang Lu*

*Corresponding author for this work

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

Abstract

Organic compounds are promising electrode materials for aqueous zinc-ion batteries (AZIBs) but largely suffer from poor rate and cycling performance. This work reports that the push–pull electron effect of organic compounds could be used to tune the electrochemical performance of AZIBs. Hexaazatriphenylene-based (HATN) small molecules with different withdrawing or donating groups were synthesized and used as electrodes for AZIBs. Compared to the hydrogen atoms and electron-donating methyl groups, the electron-withdrawing fluorine atoms endow HATN-based small molecule (HATN-6F) with a much-improved redox platform, rate performance and cycling stability. The fluorinated electrode HATN-6F potently amplifies and stabilizes the kinetics of cation co-(de)insertion reactions, concurrently enhancing the conductivity and electron affinity, resulting in improved rate performance and enhanced cycling stability. The combination of theoretical calculations and experimental characterization confirms that the fluorine-rich peripheral environment effectively modifies the distribution of conjugated electrons in HATN, enhancing its affinity for zinc ions and improving its capacity for cations zinc storage. This work demonstrates a new avenue for the design and synthesis of organic electrode with excellent electrochemical performance for ZIBs. © Youke Publishing Co.,Ltd 2025.
Original languageEnglish
Article number155868
JournalRare Metals
Online published31 Mar 2025
DOIs
Publication statusOnline published - 31 Mar 2025

Funding

This work was financially supported by the Guangdong-Hong Kong-Macau Joint Innovation Fund (No.2024A0505040001), Basic Research Project of the Science and Technology Innovation Commission of Shenzhen (No. JCYJ20220818100418040), and the National Natural Science Foundation of China (Nos. 92372114, 21875097 and 22409216), the Guangdong Basic and Applied Basic Research (No. 2023A1515010035), and the Jiangyin-SUSTech Innovation Fund (No. OR2404014). H NMR, Raman, FT-IR, ICP, XPS, and XRD data were obtained using equipment maintained by the Southern University of Science and Technology Core Research Facilities. DFT calculations were supported by the Center for Computational Science and Engineering at the Southern University of Science and Technology.

Research Keywords

  • Fluorine-rich material
  • Organic π-conjugated molecules
  • Push–pull electron effect
  • Zinc-ion batteries

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