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二维苯并咪唑醋酸锌MOF功能化聚丙烯腈复合隔膜用于实现无枝晶锂金属电池

翟云云 琚莹 刘海清 李蕾

翟云云, 琚莹, 刘海清, 等. 二维苯并咪唑醋酸锌MOF功能化聚丙烯腈复合隔膜用于实现无枝晶锂金属电池[J]. 复合材料学报, 2024, 41(5): 2585-2598. doi: 10.13801/j.cnki.fhclxb.20230825.003
引用本文: 翟云云, 琚莹, 刘海清, 等. 二维苯并咪唑醋酸锌MOF功能化聚丙烯腈复合隔膜用于实现无枝晶锂金属电池[J]. 复合材料学报, 2024, 41(5): 2585-2598. doi: 10.13801/j.cnki.fhclxb.20230825.003
ZHAI Yunyun, JU Ying, LIU Haiqing, et al. 2D Zn(Bim)OAc MOF functionalized polyacrylonitrile composite separator for Li+ redistribution to achieve dendrite-free lithium metal batteries[J]. Acta Materiae Compositae Sinica, 2024, 41(5): 2585-2598. doi: 10.13801/j.cnki.fhclxb.20230825.003
Citation: ZHAI Yunyun, JU Ying, LIU Haiqing, et al. 2D Zn(Bim)OAc MOF functionalized polyacrylonitrile composite separator for Li+ redistribution to achieve dendrite-free lithium metal batteries[J]. Acta Materiae Compositae Sinica, 2024, 41(5): 2585-2598. doi: 10.13801/j.cnki.fhclxb.20230825.003

二维苯并咪唑醋酸锌MOF功能化聚丙烯腈复合隔膜用于实现无枝晶锂金属电池

doi: 10.13801/j.cnki.fhclxb.20230825.003
基金项目: 浙江省自然科学基金项目(LGF21E030003;LTGC23B050004);国家自然科学基金青年基金项目(51503079);嘉兴市科技计划项目(2021AD10012)
详细信息
    通讯作者:

    刘海清,博士,教授,硕士生导师,研究方向为功能纤维复合材料 E-mail: liuhaiqing@mail.zjxu.edu.cn;

    李 蕾,学士,教授,硕士生导师,研究方向为微纳功能材料与分析检测技术 E-mail: lei.li@zjxu.edu.cn

  • 中图分类号: TB332;TQ340.64

2D Zn(Bim)OAc MOF functionalized polyacrylonitrile composite separator for Li+ redistribution to achieve dendrite-free lithium metal batteries

Funds: Zhejiang Provincial Natural Science Foundation of China (LGF21E030003; LTGC23B050004); National Natural Science Foundation of China (51503079); Program of Science, Technology Bureau of Jiaxing (2021AD10012)
  • 摘要: 锂沉积/剥离过程中的枝晶形成生长和库仑效率降低导致电池循环寿命缩短,限制了锂金属电池(LMBs)的商业应用。通过静电纺丝结合真空过滤技术成功制备了具有调节Li+通量和提高Li+迁移数(tLi+)的二维苯并咪唑醋酸锌MOF功能化聚丙烯腈(Zn(Bim)OAc-PAN)复合隔膜,Zn(Bim)OAc纳米片的引入固定了阴离子,提高了离子电导率(2.13 mS/cm)和Li+迁移数(0.67)。同时,Zn(Bim)OAc纳米片上的孔隙和纳米片之间堆叠形成的纳米流体通道协同构筑了微纳孔道结构,降低了复合隔膜的孔径,使通过隔膜的Li+流分布均一,促进Li+在锂金属表面均匀沉积。因此,Zn(Bim)OAc-PAN隔膜组装的Li|LiFePO4电池表现出了更高的初始容量(146.6 mA·h/g)和更好的循环稳定性(300次循环后容量保留率为96.3%)。此外,Zn(Bim)OAc-PAN复合隔膜组装的Li|Li电池实现了在1 mA/cm2下长达1000 h的稳定循环,循环后的锂金属表面没有明显的锂枝晶生长。本文为通过隔膜调节Li+通量来提高锂金属电池性能提供了一种可行的策略。

     

  • 图  1  苯并咪唑醋酸锌(Zn(Bim)OAc)纳米片的SEM图像(a)、TEM图像((b), (c))、EDS元素分布图谱((d)~(g))、XRD图谱(h)及Zn(Bim)OAc-聚丙烯腈(PAN)和Zn(Bim)OAc的FTIR图谱(i)

    Figure  1.  SEM image (a), TEM images ((b), (c)), corresponding EDS elemental mapping ((d)-(g)) and XRD patterns (h) of the benzimidazole zinc acetate (Zn(Bim)OAc) nanosheets, FTIR spectra (i) of Zn(Bim)OAc-polyacrylonitrile (PAN) and Zn(Bim)OAc

    图  2  PAN (a)和Zn(Bim)OAc-PAN纤维膜(b)的SEM图像;(c) 相关隔膜的孔径分布

    Figure  2.  SEM images of PAN (a) and Zn(Bim)OAc-PAN fibrous membrane (b); (c) Pore size distribution of the relevant separators

    图  3  Celgard (a)、PAN (b)和Zn(Bim)OAc-PAN (c)隔膜表面的液体电解质接触角;相关隔膜的交流阻抗谱(d)及高频区交流阻抗谱图(e)

    Figure  3.  Contact angles of liquid electrolyte on the surface of Celgard (a), PAN (b), Zn(Bim)OAc-PAN separators (c); AC impedance spectra (d) and plots at high-frequency for corresponding AC impedance spectra (e) of relevant separators

    图  4  Celgard (a)、PAN (b)、Zn(Bim)OAc-PAN (c)隔膜组装的Li|Li电池的计时电流法曲线(插图为极化前后对应的交流阻抗谱)

    tLi+—Li+ migration number

    Figure  4.  Chronoamperometry profiles of Celgard (a), PAN (b), Zn(Bim)OAc-PAN (c) separator assembled Li|Li cell (Insets are the corresponding AC impedance spectra before and after polarization)

    图  5  (a) Zn(Bim)OAc和相关隔膜的TGA曲线;相关隔膜在 220℃加热1 h前(b)和后(c)的光学照片;相关隔膜的应力-应变曲线(d)和LSV曲线(e)

    Figure  5.  (a) TGA curves of Zn(Bim)OAc and the relevant separators; Optical photos before (b) and after (c) heating at 220℃ for 1 h; Stress-strain curves (d) and LSV curves (e) of the relevant separators

    图  6  (a) 使用相关隔膜的Li|LiFePO4 (LFP)电池的倍率能力;(b) 使用Zn(Bim)OAc-PAN隔膜的Li|LFP电池在不同倍率下的充放电曲线;(c) 使用相关隔膜的Li|LFP电池在2 C时的放电容量;在300 次循环前(d)和后(e)的EIS (插图是等效电路);(f) Li|LFP电池的界面阻抗Rint拟合结果的比较

    Rs—Solution resistance; Rct—Charge transfer resistance; CPE—Constant phase angle element

    Figure  6.  (a) Rate capability of Li|LiFePO4 (LFP) cells using relevant separators; (b) Charge-discharge curves of Li|LFP cell using Zn(Bim)OAc-PAN separator at different rates; (c) Discharge capacity at 2 C of the cells using relevant separators; EIS of before (d) and after (e) 300 cycles (Insets is the equivalent circuit); (f) Comparison of interface impedance Rint fitting results of the Li|LFP cells

    图  7  Zn(Bim)OAc-PAN和PAN隔膜组装的Li|LFP电池300次循环后金属Li的F1s (a)和Li1s (b)的XPS图谱

    Figure  7.  XPS spectra of F1s (a) and Li1s (b) of Li metal after 300 cycles of the Li|LFP cells with Zn(Bim)OAc-PAN和PAN separators

    图  8  相关隔膜组装的Li|Cu电池的库伦效率(CE)随循环圈数的对比(a)、第50次(b)和第100次(c)的电压曲线;(d)相关隔膜组装的Li|Li对称电池的循环性能;(e) Zn(Bim)OAc-PAN隔膜组装的Li|Li电池特定周期的电压曲线

    Figure  8.  Comparison of coulombic efficiency (CE) with number of cycles (a), voltage profiles of Li|Cu cells at 50th (b) and 100th (c) of Li|Cu cells with relevant separators; (d) Cycle performance of Li|Li symmetric cells with relevant separators; (e) Voltage profiles for specific cycles of the Li|Li cell with as-prepared Zn(Bim)OAc-PAN separator

    图  9  Celgard ((a), (b))、PAN ((c), (d))和Zn(Bim)OAc-PAN ((e), (f))隔膜组装的Li|Li电池拆卸后的金属锂表面SEM图像

    Figure  9.  SEM images of Li surface disassembled from Li|Li cells with Celgard ((a), (b)), PAN ((c), (d)) and Zn(Bim)OAc-PAN ((e), (f)) separators after cycling

    图  S1  沉积在云母片上的Zn(Bim)OAc纳米片的AFM图像(a)及其相应的高度轮廓(b)

    Figure  S1.  AFM image (a) and its corresponding height profile (b) of Zn(Bim)OAc nanosheets deposited on mica sheets

    图  S2  Zn(Bim)OAc纳米片的横截面SEM图像(a)及其Zn元素的EDS分布图(b)

    Figure  S2.  Cross sectional SEM image (a) and EDS mapping of Zn element (b) of Zn(Bim)OAc nanosheets

    图  S3  不同LiPF6质量比的LiPF6-Zn(Bim)OAc悬浮液的Zeta电位

    Figure  S3.  Zeta potential of LiPF6-Zn(Bim)OAc suspension with different LiPF6 mass ratio

    图  S4  不同隔膜组装的Li|Cu电池在电流密度为2 mA/cm2、面积容量为2 mA·h/cm2时的库仑效率

    Figure  S4.  Coulombic efficiencies of the Li|Cu cells with relevant separators at the current density of 2 mA/cm2 with an area capacity of 2 mA·h/cm2

    图  S5  相关隔膜组装的Li|Li对称电池在面积容量为1 mA·h/cm2下的倍率性能曲线

    Figure  S5.  Rate performance curves of Li|Li symmetric batteries assembled with relevant separators with an area capacity of 1 mA·h/cm2

    表  1  相关隔膜的物理特性

    Table  1.   Physical properties of relevant separators

    SamplePorosity/%Uptake/wt%Bulk resistance/ΩIonic conductivity/(mS·cm−1)
    Celgard411171.270.78
    PAN752632.101.26
    Zn(Bim)OAc-PAN845831.052.13
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  • 收稿日期:  2023-06-28
  • 修回日期:  2023-08-06
  • 录用日期:  2023-08-10
  • 网络出版日期:  2023-08-28
  • 刊出日期:  2024-05-01

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