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Covalently bonded metal-organic groups anodes for high-performance potassium-ion batteries

具有共价键特征的金属-有机基团促进高性能钾离子电池

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Abstract

A key challenge in potassium ion batteries (PIBs) is the design of anode materials with advanced structures that can enable fast charge transport to enhance potassium storage performance. The use of iron carbodiimide (FeNCN) as the anode, containing a considerable number of covalent bonds and a stable structure at the molecular level, enables the achievement of excellent electrochemical performance of potassium storage systems. The FeNCN anode exhibits high electrical conductivity with a band gap close to 0 eV and decent structural stability owing to its covalently bonded structure. In addition, the amorphous reaction products provide multiple pathways to facilitate ion diffusion. Consequently, the FeNCN anode demonstrated a high reversible specific capacity (600 mA h g−1 at a current density of 50 mA g−1), remarkable rate capability, and long cycle life (a reversible specific capacity of 400 mA h g−1 at a current density of 500 mA g−1 over 300 cycles). The conversion mechanism between Fe2+ and K+ was revealed by theoretical simulation, in situ X-ray diffraction analysis, and X-ray photoelectron spectroscopy. Moreover, the as-assembled FeNCN//perylene-3,4,9,10-tetracarboxylic dianhydride full cell demonstrated a high energy density of 184.7 W h kg−1 (the highest among all iron-based PIBs) with a power density of 198.6 W kg−1, which is superior to the previously reported values for PIBs or potassium-ion hybrid capacitors.

摘要

钾离子电池(PIBs)面临的一个关键问题是设计具有先进结构的负极材料, 以实现快速电荷传输以提高钾的存储性能. 采用碳二亚胺铁(FeNCN)作为阳极, 由于其含有一定数量的共价键且在分子水平上具有稳定的结构, 使得储钾系统能够实现优异的电化学性能. FeNCN阳极具有高导电性, 带隙接近0 eV, 并且由于其共价键结构具有良好的结构稳定性. 此外, 无定形反应产物也为离子扩散提供了多种途径. 因此, FeNCN阳极表现出高可逆比容量(在50 mA g−1电流密度下具有600 mA h g−1比容量), 显著的倍率性能和长寿命循环(电流密度为500 mA g−1时拥有400 mA h g−1比容量且超过300次循环). 通过理论模拟、 X射线原位衍射分析和X射线光电子能谱分析揭示了Fe2+和K+之间的转化反应机理. 此外, 将FeNCN负极与苝-3,4,9,10-四羧酸二酐正极材料匹配, 组装成的全电池在198.6 W kg−1的功率密度下实现了184.7 W h kg−1的超高能量密度, 明显高于以往所有铁基负极的PIBs或钾离子混合电容器.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (52074113, 22005091 and 22005092), Hunan University Outstanding Youth Science Foundation (531118040319), the Science and Technology Innovation Program of Hunan Province (2021RC3055), Changsha Municipal Natural Science Foundation (43184), the CITIC Metals Ningbo Energy Co., Ltd. (H202191380246), Chongqing Talents: Exceptional Young Talents Project (CQYC202105015), and Shenzhen Virtual University Park Basic Research Project of Free exploration (2021Szvup036).

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Authors and Affiliations

  1. College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, College of Physics and Electronics, Hunan University, Changsha, 410082, China

    Xinxin Jia  (贾鑫鑫), Shengyang Li  (李胜阳), Song Chen  (陈嵩), Hongli Deng  (邓弘立), Yizhi Yuan  (袁艺智), Licai Fu  (符立才), Jian Zhu  (朱建) & Bingan Lu  (鲁兵安)

  2. MOE Key Laboratory of Low-grade Energy Utilization Technologies and Systems, School of Energy & Power Engineering, Chongqing University, Chongqing, 400044, China

    Lei Wang  (王磊)

  3. The Harold & Inge Marcus Department of Industrial & Manufacturing Engineering, Materials Research Institute (MRI), The Pennsylvania State University, University Park, Pennsylvania, 16802, USA

    Hongtao Sun  (孙洪涛)

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  1. Xinxin Jia  (贾鑫鑫)
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  2. Shengyang Li  (李胜阳)
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  6. Yizhi Yuan  (袁艺智)
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  8. Licai Fu  (符立才)
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Contributions

Author contributions Zhu J conceived the idea and directed the study. Jia X performed the main experiments. Jia X and Li S discussed the experiments and data. Jia X and Chen S, Wang L, Sun H, Fu L, and Zhu J drafted the manuscript. Deng H and Yuan Y participated in the sample preparation and characterization. All authors participated in the interpretation of the data and preparation of the final manuscript.

Corresponding authors

Correspondence to Licai Fu  (符立才) or Jian Zhu  (朱建).

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

Additional information

Jian Zhu received a PhD degree in 2017 from Hunan University. Now, he is a professor and doctoral supervisor at Hunan University. He mainly investigates the application of functional nanomaterials in electrochemical energy storage.

Xinxin jia is pursuing her doctoral degree at the College of Materials Science and Engineering, Hunan University. Her research interest is anode materials and their applications in PIBs.

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Jia, X., Li, S., Chen, S. et al. Covalently bonded metal-organic groups anodes for high-performance potassium-ion batteries. Sci. China Mater. 66, 3827–3836 (2023). https://doi.org/10.1007/s40843-023-2532-x

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