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In-situ observation of electrolyte-dependent interfacial change of the graphite anode in sodium-ion batteries by atomic force microscopy

ZHANG Xin-ren YANG Jia-ying REN Zeng-ying XIE Ke-yu YE Qian XU Fei LIU Xing-rui

张馨壬, 杨佳迎, 任增英, 谢科予, 叶谦, 徐飞, 刘兴蕊. 原位AFM探索钠离子电池溶剂依赖型石墨界面演绎过程. 新型炭材料(中英文), 2022, 37(2): 371-380. doi: 10.1016/S1872-5805(22)60601-2
引用本文: 张馨壬, 杨佳迎, 任增英, 谢科予, 叶谦, 徐飞, 刘兴蕊. 原位AFM探索钠离子电池溶剂依赖型石墨界面演绎过程. 新型炭材料(中英文), 2022, 37(2): 371-380. doi: 10.1016/S1872-5805(22)60601-2
ZHANG Xin-ren, YANG Jia-ying, REN Zeng-ying, XIE Ke-yu, YE Qian, XU Fei, LIU Xing-rui. In-situ observation of electrolyte-dependent interfacial change of the graphite anode in sodium-ion batteries by atomic force microscopy. New Carbon Mater., 2022, 37(2): 371-380. doi: 10.1016/S1872-5805(22)60601-2
Citation: ZHANG Xin-ren, YANG Jia-ying, REN Zeng-ying, XIE Ke-yu, YE Qian, XU Fei, LIU Xing-rui. In-situ observation of electrolyte-dependent interfacial change of the graphite anode in sodium-ion batteries by atomic force microscopy. New Carbon Mater., 2022, 37(2): 371-380. doi: 10.1016/S1872-5805(22)60601-2

原位AFM探索钠离子电池溶剂依赖型石墨界面演绎过程

doi: 10.1016/S1872-5805(22)60601-2
基金项目: 国家自然科学基金(51972270,21603175);陕西省自然科学基金(2020JZ-07);陕西省重点研发项目(2019TSLGY07-03);凝固技术国家重点实验室研究基金资助项目(2021-TS-03);固体润滑国家重点实验室研究基金项目(LSL-2007)
详细信息
    通讯作者:

    谢科予,博士,教授. E-mail:kyxie@nwpu.edu.cn

    徐 飞,博士,研究员. E-mail:feixu@nwpu.edu.cn

    刘兴蕊,博士,助理研究员. E-mail:liuxingrui@nwpu.edu.cn

  • 中图分类号: TQ127.1+1

In-situ observation of electrolyte-dependent interfacial change of the graphite anode in sodium-ion batteries by atomic force microscopy

Funds: This work was supported by the National Natural Science Foundation of China (51972270, 21603175), Natural Science Foundation of Shaanxi Province (2020JZ-07), the Key Research and Development Program of Shaanxi Province (2019TSLGY07-03), the Research Fund of the State Key Laboratory of Solidification Processing (NPU), China (2021-TS-03), and the Research Fund of the State Key Laboratory of Solid Lubrication (CAS), China (LSL-2007)
More Information
  • 摘要: 石墨在碳酸酯基电解液中储钠活性很低,因此被认为不合适作为钠离子电池负极材料。而最近的研究表明,在以线性醚为溶剂的钠离子电解液中,石墨具有高的储钠容量和首圈库伦效率。因此,探索这种溶剂依赖型的石墨界面演绎过程具有重要的意义。本研究采用原位原子力显微镜(Atomic force microscopy,AFM)实时观测石墨在碳酸酯基和线性醚基电解液下的界面微观动态过程。结果表明:在线性醚溶剂下,石墨电极界面没有固体电解质界面膜(Solid electrolyte interphase,SEI)形成,且溶剂化钠离子可以在石墨层间进行可逆的插入和脱出,AFM结果从界面角度解释了其具有高初始库伦效率的内在原因。然而在碳酸酯溶剂中,可以观察到石墨电极表面出现明显的沉积物,对应SEI的生长;并且在充电过程中SEI逐渐减少,表明碳酸酯溶剂下形成的SEI不稳定,造成不可逆的容量损失和低库伦效率。此外,石墨表面未出现明显的台阶变化,反映了没有钠离子的脱嵌过程。上述研究结果为石墨负极界面反应动态过程提供了见解,从微观尺度揭示了溶剂依赖的石墨负极储钠行为及其界面反应机理,为高性能钠离子电池体系的设计与发展提供了理论依据。
  • FIG. 1401.  FIG. 1401.

    FIG. 1401.. 

    Figure  1.  Galvanostatic discharge-charge curves of the graphite electrode in (a) carbonate and (b) diglyme electrolytes, at the current density of 100 mA g−1. (c) Long-term cycling performance and Coulombic efficiency of diglyme electrolyte at 100 mA g−1. (d) CV curves in diglyme electrolyte at 0.1 mV s−1.

    Figure  2.  (a) Schematic of the in situ AFM setup. (b-j) In situ AFM images of HOPG electrode in 1 mol L−1 diglyme electrolyte during the first discharging cycle from 1.84 to 0.51 V. The long white arrows indicate the scan directions.

    Figure  3.  (a-i) In situ AFM images of HOPG electrode in 1 mol L−1 diglyme electrolyte during the first charging cycle from 0.02 to 1.96 V.

    Figure  4.  (a) 3D AFM morphology images of HOPG surface in 1 mol L−1 diglyme electrolyte. (b) Schematic of the in situ Raman setup and in situ Raman spectra of graphite electrode in diglyme electrolyte during cycling.

    Figure  5.  (a-l) In situ AFM images of HOPG electrode in 1 mol L−1 diglyme electrolyte during the first discharging cycle from 0.80 to 0.16 V. Height cross-section profiles of cracke (h’) A and (i’) B.

    Figure  6.  In situ AFM images of HOPG electrode in 1 mol L−1 carbonate electrolyte (a) during the first discharging cycle from 2.54 to 0.09 V and (b) during the first charging cycle from 0.01 to 2.50 V.

    Figure  7.  (a) Schematic of interfacial and internal mechanism of graphite electrode during the first charge and discharge process for SIBs. (b) Interfacial behaviors of graphite electrode in different electrolytes for LIBs.

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出版历程
  • 收稿日期:  2021-10-26
  • 修回日期:  2021-12-17
  • 网络出版日期:  2022-02-28
  • 刊出日期:  2022-03-30

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