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Energy Materials and Devices 2023, 1(1): 9370007 https://doi.org/10.26599/EMD.2023.9370007
Research Article | Open Access | Issue | Published: 08 October 2023

Unlocking high-performance organic cathodes: tailoring active group densities in covalent frameworks for aqueous zinc ion batteries

Show Author's Information Meilin Li1,2,†,  Fanbin Zeng1,2,†,  Senlin Li1,2( ),  Sanlue Hu1,2,  Qingming Liu3,  Tengfei Zhang3,  Jun Zhou3( ),  Cuiping Han1,2( )
Faculty of Materials Science and Energy Engineering/Institute of Technology for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
Shenzhen Key Laboratory of Energy Materials for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
Towngas Energy Academy, Shenzhen 518000, China

† Meilin Li and Fanbin Zeng contributed equally to this work.

Keywords:
organic electrode materials, covalent organic frameworks, aqueous zinc ion batteries, active group density modulation
Cite this article:
Li M, Zeng F, Li S, et al. Unlocking high-performance organic cathodes: tailoring active group densities in covalent frameworks for aqueous zinc ion batteries. Energy Materials and Devices, 2023, 1(1): 9370007. https://doi.org/10.26599/EMD.2023.9370007
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Abstract Full text Electronic supplementary material About this article

Aqueous zinc ion batteries (AZIBs) are a promising energy storage technology due to their cost-effectiveness and safety. Organic materials with sustainable and designable structures are of great interest as AZIBs cathodes. However, small molecules in organic cathode materials face dissolution problems and suboptimal cycle life, whereas large molecules suffer from a low theoretical capacity due to their inert carbon skeletons. Here, we designed two covalent organic framework (COF) materials (benzoquinoxaline benzoquinone-based COF (BB-COF) and triquinoxalinylene benzoquinone-based COF (TB-COF)) with the same structure and number of energy storage groups to investigate the correlation between the densities of active sites and electrochemical performance. We conclude that the electrochemical behavior of organic conjugate-based energy storage materials lacks a linear correlation with active site quantity. Adjusting active site densities is crucial for material advancement. BB-COF and TB-COF with dual active sites (C=O and C=N) exhibit distinct characteristics. TB-COF, which has dense active groups, shows a high initial capacity (222 mAh g−1). Conversely, BB-COF, which features a large conjugated ring diameter, presents superior rate performance and enduring cycle stability. It even maintains stable cycling for 2000 cycles at −40 ℃. In-situ electrochemical quartz crystal microbalance tests reveal the energy storage mechanism of BB-COF, in which H+ storage is followed by Zn2+ storage.


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About this article

Unlocking high-performance organic cathodes: tailoring active group densities in covalent frameworks for aqueous zinc ion batteries

Show Author's information Meilin Li1,2,†, Fanbin Zeng1,2,†, Senlin Li1,2( ), Sanlue Hu1,2, Qingming Liu3, Tengfei Zhang3, Jun Zhou3( ), Cuiping Han1,2( )
Faculty of Materials Science and Energy Engineering/Institute of Technology for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
Shenzhen Key Laboratory of Energy Materials for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
Towngas Energy Academy, Shenzhen 518000, China

† Meilin Li and Fanbin Zeng contributed equally to this work.

Abstract

Aqueous zinc ion batteries (AZIBs) are a promising energy storage technology due to their cost-effectiveness and safety. Organic materials with sustainable and designable structures are of great interest as AZIBs cathodes. However, small molecules in organic cathode materials face dissolution problems and suboptimal cycle life, whereas large molecules suffer from a low theoretical capacity due to their inert carbon skeletons. Here, we designed two covalent organic framework (COF) materials (benzoquinoxaline benzoquinone-based COF (BB-COF) and triquinoxalinylene benzoquinone-based COF (TB-COF)) with the same structure and number of energy storage groups to investigate the correlation between the densities of active sites and electrochemical performance. We conclude that the electrochemical behavior of organic conjugate-based energy storage materials lacks a linear correlation with active site quantity. Adjusting active site densities is crucial for material advancement. BB-COF and TB-COF with dual active sites (C=O and C=N) exhibit distinct characteristics. TB-COF, which has dense active groups, shows a high initial capacity (222 mAh g−1). Conversely, BB-COF, which features a large conjugated ring diameter, presents superior rate performance and enduring cycle stability. It even maintains stable cycling for 2000 cycles at −40 ℃. In-situ electrochemical quartz crystal microbalance tests reveal the energy storage mechanism of BB-COF, in which H+ storage is followed by Zn2+ storage.

Keywords: organic electrode materials, covalent organic frameworks, aqueous zinc ion batteries, active group density modulation

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Publication history

Received: 02 September 2023
Revised: 16 September 2023
Accepted: 19 September 2023
Published: 08 October 2023
Issue date: September 2023

Copyright

© The Author(s) 2023. Published by Tsinghua University Press.

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 22279160 and 22109134), Guangdong Basic and Applied Basic Research Foundation (2022A1515010920), the Outstanding Youth Basic Research Project of Shenzhen (RCYX20221008092934093), the China Postdoctoral Science Foundation (2023M733670) and Special Research Assistant Funding Project of the Chinese Academy of Sciences. The computing work associated with this paper was supported by the public computing service platform provided by SIAT.

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