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Bimetallic zeolite imidazolate framework for enhanced lithium storage boosted by the redox participation of nitrogen atoms

基于氮原子氧化还原的双金属沸石咪唑框架用于高性能锂离子电池负极

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Abstract

In this work, a bimetallic zeolitic imidazolate framework (ZIF) CoZn-ZIF was synthesized via a facile solvothermal approach and applied in lithium-ion batteries. The as-prepared CoZn-ZIF shows a high reversible capacity of 605.8 mA h g−1 at a current density of 100 mA g−1, far beyond the performance of the corresponding monometallic Co-ZIF- 67 and Zn-ZIF-8. Ex-situ synchrotron soft X-ray absorption spectroscopy, X-ray diffraction, and electron paramagnetic resonance techniques were employed to explore the Li-storage mechanism. The superior performance of CoZn-ZIF over Co- ZIF-67 and Zn-ZIF-8 could be mainly attributed to lithiation and delithiation of nitrogen atoms, accompanied by the breakage and recoordination of metal nitrogen bond. Morever, a few metal nitrogen bonds without recoordination will lead to the amorphization of CoZn-ZIF and the formation of few nitrogen radicals.

摘要

本文首次水热合成了一种双金属沸石咪唑有机框架(CoZn-ZIF)并将其用于锂离子电池负极. 该材料在以100 mA g−1电流充放电时, 具有605.8 mA h g−1的可逆容量, 远远大于同类单金属材料(Co-ZIF-67和Zn-ZIF-8). 为了探知该高容量来源, 我们进行了一系列非原位实验, 包括同步辐射软线、 粉末衍射、 透射电镜以及顺磁共振. 研究表明该双金属高容量主要得益于配位氮原子参与锂化反应, 在这一过程中还伴随了金属氮配位键的打开与重新配合. 另外, 少量金属氮配位键的不可逆反应会导致该材料晶体的无序化以及一些氮自由基的生成. 这种高活性双金属的设计思路和反应机理可推广到包括催化、 气体吸附等的其他应用中.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China for Excellent Young Scholars (21522303), the National Natural Science Foundation of China (21373086), the Basic Research Project of Shanghai Science and Technology Committee (14JC1491000), the Large Instruments Open Foundation of East China Normal University, the National Key Basic Research Program of China (2013CB921800) and the National High Technology Research and Development Program of China (2014AA123401). We acknowledge the support from the National Synchrotron Radiation Laboratory (NSRL) for the sXAS experiments. We also thank Dr. Jiahui Yang from Bruker for the support of EPR measurements and analysis.

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Authors and Affiliations

  1. State Key Laboratory of Precision Spectroscopy, Shanghai Key Laboratory of Magnetic Resonance, Institute of Functional Materials, School of Physics and Materials Science, East China Normal University, Shanghai, 200062, China

    Xiaobing Lou  (娄霄冰), Yanqun Ning  (宁艳群), Chao Li  (李超), Xiaoshi Hu  (胡小诗), Ming Shen  (沈明) & Bingwen Hu  (胡炳文)

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  1. Xiaobing Lou  (娄霄冰)
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  2. Yanqun Ning  (宁艳群)
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  3. Chao Li  (李超)
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  4. Xiaoshi Hu  (胡小诗)
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  5. Ming Shen  (沈明)
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  6. Bingwen Hu  (胡炳文)
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Corresponding author

Correspondence to Bingwen Hu  (胡炳文).

Additional information

Xiaobing Lou is a PhD student at the East China Normal University. His research interests are design of metal organic frameworks and their electrochemical application, with a specific focus on the mechanism research by means of magnetic resonance technique.

Bingwen Hu received his PhD degree in 2009 from National High field NMR Center, Université Lille 1, France. After that, he returned to East China Normal University and started his career as a research scientist. Now, he is a professor scientist at the Shanghai Key Laboratory of Magnetic Resonance and adjunct professor at the State Key Laboratory of Precision Spectroscopy at East China Normal University. His research interests include new method development in solid state NMR, and the application of NMR and EPR for batteries. He has published more than one hundred papers in refereed journals.

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Bimetallic zeolite imidazolate framework for enhanced lithium storage boosted by the redox participation of nitrogen atoms

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Lou, X., Ning, Y., Li, C. et al. Bimetallic zeolite imidazolate framework for enhanced lithium storage boosted by the redox participation of nitrogen atoms. Sci. China Mater. 61, 1040–1048 (2018). https://doi.org/10.1007/s40843-017-9200-5

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