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膨胀石墨/硫-氟化气相沉积碳纤维双层正极

马朝勇 欧云 姚琛琪 唐智勇 刘龙飞 王艳 成娟娟

马朝勇, 欧云, 姚琛琪, 等. 膨胀石墨/硫-氟化气相沉积碳纤维双层正极[J]. 复合材料学报, 2023, 40(5): 2722-2730. doi: 10.13801/j.cnki.fhclxb.20220705.002
引用本文: 马朝勇, 欧云, 姚琛琪, 等. 膨胀石墨/硫-氟化气相沉积碳纤维双层正极[J]. 复合材料学报, 2023, 40(5): 2722-2730. doi: 10.13801/j.cnki.fhclxb.20220705.002
MA Chaoyong, OU Yun, YAO Chenqi, et al. Expanded graphite/sulfur-fluorinated vapor-deposited carbon fiber bilayer cathode[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2722-2730. doi: 10.13801/j.cnki.fhclxb.20220705.002
Citation: MA Chaoyong, OU Yun, YAO Chenqi, et al. Expanded graphite/sulfur-fluorinated vapor-deposited carbon fiber bilayer cathode[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2722-2730. doi: 10.13801/j.cnki.fhclxb.20220705.002

膨胀石墨/硫-氟化气相沉积碳纤维双层正极

doi: 10.13801/j.cnki.fhclxb.20220705.002
基金项目: 湖南省教育厅科技项目(20 B225);湖南省自然科学基金项目(2020 JJ4288;2021 JJ30257);国家自然科学基金项目(11972157);新能源储存与转换先进材料湖南省重点实验室开放基金(2018 TP1037-202002)
详细信息
    通讯作者:

    成娟娟,博士,讲师,硕士生导师,研究方向为锂硫电池 E-mail: jjcheng@hnust.edu.cn

  • 中图分类号: TB332

Expanded graphite/sulfur-fluorinated vapor-deposited carbon fiber bilayer cathode

Funds: Science and Technology Project of Hunan Provincial Department of Education (20 B225); Natural Science Foundation of Hunan Province (2020 JJ4288; 2021 JJ30257); National Natural Science Foundation of China (11972157); Hunan Provincial Key Laboratory of Advanced Materials for New Energy Storage and Conversion Open Fund (2018 TP1037-202002)
  • 摘要: 对于高性能储能设备的迫切需求,使得理论能量密度达到2600 W·h/kg的锂硫电池(LSBs)变得极具吸引力。然而,低的容量可逆性和硫自身绝缘性的天然缺陷制约了其商业化进程。为了有效改善硫的导电性能,同时抑制多硫化物的穿梭效应,达到提高LSBs电化学性能的目的。本文采用逐层涂覆法在膨胀石墨(EG)/硫(S)复合正极极片表面涂覆氟化气相沉积碳纤维(FVGCF),通过首次放电至2.5 V实现FVGCF嵌锂,在EG/S正极极片表面形成LiF和FVGCF复合层。电化学性能测试和形貌表征结果表明:采用FVGCF新型正极材料具有最佳的循环寿命,EGS-FVGCF在1 C电流密度下的初始放电比容量为691.8 mA·h/g,100次循环之后剩余比容量为549.5 mA·h/g。相对于EGS涂覆的单层结构,在EGS上面涂覆FVGCF的双层电池性能具备极大应用优势,放电过程中生成的LiF能够抑制多硫化物从正极到负极的穿梭。同时,放充电后的电极形貌表征发现FVGCF层的加入减少了极片表面的裂纹,表明FVGCF层在一定程度上缓冲了硫正极的体积膨胀。这种简单易操作的复合结构为开发高性能LSBs提供了一定参考。

     

  • 图  1  电池结构示意图

    PP—Polypropylene; FVGCF—Fluorinated vapor-deposited carbon fiber

    Figure  1.  Battery structure diagram

    图  2  FVGCF (a)、膨胀石墨(EG)/硫(S)化合物(EGS) (b)、EGS/FVGCF (c)、EGS-FVGCF双层平面(d)与截面(e)的SEM图像

    Figure  2.  SEM images of FVGCF (a), expanded graphite (EG)/sulfur (S) composite (EGS) (b), EGS/FVGCF (c), EGS-FVGCF bilayers in plane (d) and cross-section (e)

    图  3  EGS/FVGCF复合材料、EGS、EGS/FVGCF和EGS-FVGCF放电后极片的XRD图谱

    Figure  3.  XRD patterns for EGS/FVGCF composite, EGS, EGS/FVGCF and EGS-FVGCF electrodes after discharge

    图  4  EGS-FVGCF、EGS、EGS/FVGCF正极的电池电化学性能特性;(a)首次放充电曲线;(b) EGS-FVGCF在0.2 C电流密度的第1、10、50、100次循环放/充电曲线;(c) 0.1 mV·s−1扫描速率下的循环伏安曲线;(d)阻抗曲线;(e) 0.2 C电流密度下100次循环性能;(f) 1 C电流密度下循环100圈性能及相应库伦效率

    Figure  4.  Battery electrochemical performance characteristics of EGS-FVGCF, EGS, EGS/FVGCF cathodes: (a) First discharge and charge curves; (b) EGS-FVGCF at the 1st, 10th, 50th and 100th cycle discharge/charge curves at 0.2 C current density; (c) Cyclic voltammetry curve at 0.1 mV·s−1 scan rate; (d) Impedance curve; (e) 100 cycle performance at 0.2 C current density; (f) 100 cycle performance and corresponding coulombic efficiency at 1 C current density

    图  5  进行1次放充电的EGS (a)、EGS/FVGCFF (b)和EGS-FVGCF (c)的SEM图像

    Figure  5.  SEM images of EGS (a), EGS/FVGCFF (b) and EGS-FVGCF (c) subjected to one charge and discharge

    表  1  本文与文献报道的部分上集流体材料性能对比

    Table  1.   Properties of fluid materials in this study compared with those reported in the literature

    Upper current collector materialSulfurSulfur load/(mg·cm–1)Current density/(mA·g–1)Specific capacity/(mA·h·g–1)Ref.
    VGCF S 2 50 1100 (First cycle) [33]
    Fe3O4/RGO CSC/S 1.0 500 434 (400 cycles) [39]
    Carbon paper S 1.7 335 631 (200 cycles) [40]
    Fe-N-C KB/S 1.0 335 428 (500 cycles) [41]
    M-S-LTO S 1.3 335 960 (200 cycles) [42]
    Waste cotton cloth S 3.05 335 423 (200 cycles) [43]
    FVGCF EGS 1.1 1675 549.5 (100 cycles) This work
    Notes: VGCF—Vapor grown carbon fiber; RGO—Reduced graphene oxide; Fe-N-C—Fe-N-doped carbon; M—Multi-walled carbon nanotubes; LTO—Li4Ti5O12; CSC—Coconut shell charcoal; KB—Ketjen black.
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  • 收稿日期:  2022-05-16
  • 修回日期:  2022-06-13
  • 录用日期:  2022-06-24
  • 网络出版日期:  2022-07-06
  • 刊出日期:  2023-05-15

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