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Semi-ionic C-F bond inducing fast ion storage and electron transfer in carbon anode for potassium-ion batteries

半离子C-F键在钾离子电池碳负极中诱导快速离子储存和电子转移

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Abstract

Fluorine (F)-heteroatom-functionalized carbon anodes can effectively increase the potassium (K) storage capacity by forming more defect sites; however, the mechanism behind the improvement in electrochemical performance remains unclear, and the fundamental understanding of which kind of C-F bond profoundly determines K storage properties is still lacking. Hence, we report a series of F-doped carbon and demonstrate that it is a semi-ionic C-F bond rather than an ionic C-F bond, and carbonization temperature has a substantial impact on the defect level. Moreover, numerous defects induced by the high percentage of semi-ionic C-F bonds can function as active sites to adsorb many K-ions associated with capacitive behavior, which not only lengthens the cycle lifespan, but is also positively correlated with rate capacity at a high current density. Density functional theory calculations confirm that the existence of a semi-ionic C-F bond can improve the K-ion adsorption capability of carbon and simultaneously increase electronic conductivity, leading to a high capacity and rate. Furthermore, both K adsorption energy and conductivity are optimized by coupling semi-ionic C-F and pyridinic N bonds, resulting in superior capacity (245.2 mA h g−1) and exceptional rate capacity in a K-half battery and high energy density (143.9 W h kg−1) in a K-full battery.

摘要

氟(F)杂原子功能化的碳负极可以形成更多的缺陷位点, 从而有效提高钾的存储容量. 然而, 提高电化学性能的机制尚不清楚, 尤其是对何种C-F键深入影响钾储存性能仍缺乏基本认识. 本文报道了一系列F掺杂的碳, 并证明了C-F是半离子键而不是离子键; 碳化温度对缺陷程度有显著影响. 并且, 高比例半离子C-F键诱导的丰富缺陷可以作为活性位点来吸附大量与电容行为相关的钾离子, 不仅有利于长循环寿命, 而且提升了在高电流密度下的倍率容量. 密度泛函理论计算证实半离子C-F键的存在可以提高碳基体对钾离子的吸附能力并同时提高电子电导率, 有利于高容量和倍率. 此外, 通过耦合半离子C-F键和吡啶N键, 钾吸附能和电导率被进一步提升, 这使得半电池实现了优异的容量(245.2 mA h g−1) 和倍率, 并且组装的全电池具有高能量密度(143.9 W h kg−1).

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51974188), the Key Research and Development Program of Hebei Province (20310601D and 205A4401D), the Natural Science Foundation of Hebei Province (B2021208061, B2022208006 and E2022208023), the Science Foundation of University of Hebei Province (BJ2020053 and BJ2021001), and Liaoning Revitalization Talents Program (XLYC2008014).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Shenyang University of Technology, Shenyang, 110870, China

    Fei Yuan  (袁飞) & Yu-Sheng Wu  (吴玉胜)

  2. Hebei Key Laboratory of Flexible Functional Materials, School of Materials Science and Engineering, Hebei University of Science and Technology, Shijiazhuang, 050018, China

    Fei Yuan  (袁飞), Wei Song  (宋薇), Di Zhang  (张迪), Zhaojin Li  (李昭进), Huan Wang  (王欢), Qiujun Wang  (王秋君) & Bo Wang  (王波)

  3. School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing, 100083, China

    Wei Wang  (王伟)

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  1. Fei Yuan  (袁飞)
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  9. Bo Wang  (王波)
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Contributions

Author contributions Yuan F, Wu YS, Wang W, and Wang B designed the experiments. Yuan F, Song W, and Zhang D performed the characterizations. Yuan F wrote the paper with support from Wang B and Wu YS. Li Z, Wang H, and Wang Q performed the calculation. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Yu-Sheng Wu  (吴玉胜), Wei Wang  (王伟) or Bo Wang  (王波).

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Conflict of interest The authors declare no conflict of interest.

Additional information

Fei Yuan is a PhD candidate of Shenyang University of Technology and studies at Hebei University of Science and Technology as a joint PhD student. He received his BS degree in 2017 and MS degree in 2020 from Hebei University of Science and Technology. His current research is focused on crucial electrode materials for potassium-ion batteries.

Yu-Sheng Wu received his PhD degree from the Northeastern University. He is currently a professor at the School of Materials Science and Engineering, Shenyang University of Technology. His current research is mainly focused on the preparation and characterization of advanced powder materials.

Bo Wang received his PhD degree from the Northeastern University (2009). He is now a professor at the School of Materials Science and Engineering, Hebei University of Science and Technology. His current research interests include advanced energy storage materials: anode and cathode electrode materials for high-specific-energy LIBs, new micro-nanostructure alkali metal ion battery electrode materials, all vanadium flow batteries, all solid lithium batteries, and fuel cell membrane electrode materials.

Wei Wang is a professor at the School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing. He received his PhD degree in 2016 from the State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, and studied at the University of Cambridge as a joint PhD student. His research mainly focuses on renewable energy conversion and storage technology.

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Yuan, F., Song, W., Zhang, D. et al. Semi-ionic C-F bond inducing fast ion storage and electron transfer in carbon anode for potassium-ion batteries. Sci. China Mater. 66, 2630–2640 (2023). https://doi.org/10.1007/s40843-022-2419-4

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