2D Zn(Bim)OAc MOF functionalized polyacrylonitrile composite separator for Li+ redistribution to achieve dendrite-free lithium metal batteries
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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。Abstract: The dendrite formation and growth during Li plating/stripping process, as well as the reduced coulomb efficiency, result in a shortened cycle life of lithium metal batterie (LMB), restricting its commercial application. 2D Zn(Bim)OAc MOF functionalized polyacrylonitrile (Zn(Bim)OAc-PAN) composite separator with regulating Li+ flux and increasing Li+ migration number was successfully prepared by electrospinning combined with vacuum filtration technology. The introduction of Zn(Bim)OAc nanosheets can fix the anion, improve the ionic conductivity (2.13 mS/cm) and Li+ migration number (0.67). Meanwhile, the pores on Zn(Bim)OAc nanosheets and the nanofluid channels between the stacked nanosheets synergistically construct a micro/nano pore structure, reducing the pore size, resulting in uniform Li+ flux distribution and promoting uniform Li+ deposition on the lithium metal surface. Therefore, as-prepared Zn(Bim)OAc-PAN separator assembled Li|LiFePO4 cells can also exhibit higher initial capacity (146.6 mA·h/g) and better cycle stability (96.3% capacity retention after 300 cycles) at 2 C. Besides, as-prepared Zn(Bim)OAc-PAN separator based Li|Li achieves a stable cycle up to 1000 h under 1 mA/cm2, and there was no obvious lithium dendrite growth on the Li anode surface after cycling. The reported approach provides a feasible strategy to improve the LMB performance by regulating the Li+ flux through separators.
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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
表 1 相关隔膜的物理特性
Table 1. Physical properties of relevant separators
Sample Porosity/% Uptake/wt% Bulk resistance/Ω Ionic conductivity/(mS·cm−1) Celgard 41 117 1.27 0.78 PAN 75 263 2.10 1.26 Zn(Bim)OAc-PAN 84 583 1.05 2.13 
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