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Carbon-coated Fe2O3 hollow sea urchin nanostructures as high-performance anode materials for lithium-ion battery

中空海胆状结构的碳包覆Fe2O3用作锂离子电池的高性能负极材料

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Abstract

Fe2O3 has become a promising anode material in lithium-ion batteries (LIBs) in light of its low cost, high theoretical capacity (1007 mA h g−1) and abundant reserves on the earth. Nevertheless, the practical application of Fe2O3 as the anode material in LIBs is greatly hindered by several severe issues, such as drastic capacity falloff, short cyclic life and huge volume change during the charge/discharge process. To tackle these limitations, carbon-coated Fe2O3 (Fe2O3@MOFC) composites with a hollow sea urchin nanostructure were prepared by an effective and controllable morphology-inherited strategy. Metal-organic framework (MOF)-coated FeOOH (FeOOH@-MIL-100(Fe)) was applied as the precursor and self-sacrificial template. During annealing, the outer MOF layer protected the structure of inner Fe2O3 from collapsing and converted to a carbon coating layer in situ. When applied as anode materials in LIBs, Fe2O3@MOFC composites showed an initial discharge capacity of 1366.9 mA h g−1 and a capacity preservation of 1551.3 mA h g−1 after 200 cycles at a current density of 0.1 A g−1. When increasing the current density to 1 A g−1, a reversible and high capacity of 1208.6 mA h g−1 was obtained. The enhanced electrochemical performance was attributed to the MOF-derived carbon coating layers and the unique hollow sea urchin nanostructures. They mitigated the effects of volume expansion, increased the lithium-ion mobility of electrode, and stabilized the as-formed solid electrolyte interphase films.

摘要

Fe2O3 由于成本低廉, 储量丰富和理论比容量高(1007 mA h g−1)等特点, 在锂离子电池负极材料的应用中极具发展前景. 然而一些问题仍然存在, 如: 充放电过程中比容量的迅速衰减, 不可逆的体积膨胀以及较短的循环寿命等. 这些问题严重制约了Fe2O3在锂离子电池中的实际应用. 为了突破这些局限, 本文以金属-有机骨架(MOFs)包覆的FeOOH(FeOOH@MIL-100(Fe))作为前驱体和自牺牲模板, 通过高温热处理制备得到一种能良好继承前驱体形貌的中空海胆状碳包覆的Fe2O3(Fe2O3@MOFC)复合材料. 在热处理过程中, 外部的MOF层很好地保护了内部Fe2O3结构的完整性, 并以原位转化的方式衍生为均匀分布在纳米粒子外部的碳涂层. 在 0.1 A g−1 的电流密度下, Fe2O3@MOFC可提供高达1366.9 mA h g−1的初始放电容量, 且充放电循环200次后, 仍能保持大约1551.3 mA h g−1的高放电容量. 在1 A g−1的高电流密度下循环300次后, 其比容量仍可保持在1208.6 mA h g−1.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (2017YFA0403402 and 2019YFA0405601), the National Natural Science Foundation of China (21773222, U1732272 and U1932214), the DNL Cooperation Fund, and Chinese Academy of Sciences (DNL180201).

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Authors and Affiliations

  1. National Synchrotron Radiation Laboratory, Department of Chemical Physics and Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei, 230029, China

    Yuge Feng  (冯雨歌) & Junfa Zhu  (朱俊发)

  2. Hefei National Research Center for Physical Science at the Microscale CAS Key Laboratory of Materials for Energy Conversion & Department of Materials Science and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Na Shu  (束娜), Jian Xie  (谢兼) & Yanwu Zhu  (朱彦武)

  3. Department of Applied Chemistry and State Key Laboratory of Tea Plant Biology and Utilization, Anhui Agricultural University, Hefei, 230026, China

    Fei Ke  (柯飞)

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  1. Yuge Feng  (冯雨歌)
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  2. Na Shu  (束娜)
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  3. Jian Xie  (谢兼)
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  4. Fei Ke  (柯飞)
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  5. Yanwu Zhu  (朱彦武)
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  6. Junfa Zhu  (朱俊发)
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Contributions

Author contributions Feng Y designed and engineered the samples; Shu N and Xie J performed the electrochemical experiments; Feng Y wrote the paper with support from Zhu J, Ke F and Zhu Y. All authors contributed to the general discussion.

Corresponding author

Correspondence to Junfa Zhu  (朱俊发).

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

Additional information

Yuge Feng is a PhD student at the National Synchrotron Radiation Laboratory, University of Science and Technology of China (USTC). Her research interests mainly focus on synthesis and characterization of metal-organic frameworks (MOFs) for energy applications.

Junfa Zhu received his PhD in physical chemistry from USTC in 1999. After several years working in the Institute of Experimental Physics, Johannes-Kepler-Universität Linz (Austria), Lehrstuhl für Physikalische Chemie II, Friedrich-Alexander-Universität Erlangen-Nürnberg (Germany), Department of Chemistry, University of Washington (USA), he returned to USTC in December, 2006, and became a professor at the National Synchrotron Radiation Laboratory, USTC under the support of “Hundred Talent Program” of Chinese Academy of Sciences. His research interests mainly focus on in-situ studies of surface chemistry and catalysis, surface/interface structures and properties of functional materials, and surface coordination chemistry.

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Feng, Y., Shu, N., Xie, J. et al. Carbon-coated Fe2O3 hollow sea urchin nanostructures as high-performance anode materials for lithium-ion battery. Sci. China Mater. 64, 307–317 (2021). https://doi.org/10.1007/s40843-020-1437-2

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