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SCIENCE CHINA Materials, Volume 61, Issue 8: 1040-1048(2018) https://doi.org/10.1007/s40843-017-9200-5

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

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  • ReceivedNov 7, 2017
  • AcceptedDec 28, 2017
  • PublishedJan 25, 2018

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.


Funded by

the National Natural Science Foundation of China for Excellent Young Scholars(21522303)

the National Natural Science Foundation of China(21373086)

Basic Research Project of Shanghai Science and Technology Committee(14JC1491000)

the Large Instruments Open Foundation of East China Normal University

National Key Basic Research Program of China(2013CB921800)

the National High Technology Research and Development Program of China(2014AA123401)


Acknowledgment

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.


Interest statement

The authors declare no conflict of interest.


Contributions statement

Hu B proposed and guided the whole project. Lou X designed the experiment and wrote the manuscript. Ning Y performed the experiments. Li C polished the manuscript. Hu X helped characterize the materials. Shen M helped analyze the data. All authors participated in the project discussion and reviewed the manuscript.


Author 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 the National High field NMR Center, Université Lille 1, France. After that, he returned to the East China Normal University and started his career as a research scientist. Now, he is a professor scientist at Shanghai Key Laboratory of Magnetic Resonance and adjunct professor at the State Key Laboratory of Precision Spectroscopy at the 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.


Supplement

Supplementary Information

Supplementary data are available in the online version of the paper.


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  • Figure 1

    FTIR spectra (a), XRD patterns (b) and TG curves (c) of Zn-ZIF-8, Co-ZIF-67, and CoZn-ZIF, respectively. The FTIR spectrum of 2-methylimidazole is also involved for reference.

  • Figure 2

    SEM micrographs of Zn-ZIF-8 (a, d), Co-ZIF-67 (b, e), and CoZn-ZIF (c, f) at different magnifications.

  • Figure 3

    (a) Cyclic performance of CoZn-ZIF at a current density of 100 mA g−1. The discharge and coulombic efficiency curves of Zn-ZIF-8 and Co-ZIF-67 are also provided for comparison. (b) Rate performance of CoZn-ZIF at different current densities ranging from 100 to 2,000 mA g−1.

  • Figure 4

    Ex situ N K-edges (a) and Co L-edges (b) sXAS spectra of the corresponding ZIF electrodes at different states-of-charge. (c) High-resolution Zn 2p XPS spectra of the corresponding ZIF electrodes at different states-of-charge.

  • Figure 5

    Ex-situ XRD patterns of fresh electrode, discharged electrode (0.01 V) and charged electrode (3.0 V) for (a) Zn-ZIF-8, (b) Co-ZIF-67 and (c) CoZn-ZIF.

  • Figure 6

    Microstructures evolutions (ex-situ TEM images) of fresh electrode, discharged electrode (0.01 V), and charged electrode (3.0 V) for CoZn-ZIF.

  • Figure 7

    Ex situ EPR spectra of CoZn-ZIF electrodes at different states-of-charge. Pure Super-P and pristine CoZn-ZIFs are also plotted for comparison. Insert: high-resolution EPR spectrum from selected region and schematic illustration of nitrogen radicals. Other EPR spectra are displayed in Fig. S6. Here, CoZn-ZIF-fresh is the sample with Super-P while CoZn-ZIF is not.

  • Figure 8

    (a) Nyquist plots of the three electrodes at the fresh state. (b) Nyquist plots of the CoZn-ZIF electrodes at fresh state, after 1 cycle and 100 cycles.

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