Thermal and electrochemical properties of polybenzimidazole-modified biphenyl polyimide electrospun lithium-ion battery separator
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摘要: 为了改善商业隔膜孔隙率和吸液率不高、耐热性和热尺寸稳定性不佳的问题，通过选用聚苯并咪唑(PBI)预聚体对聚酰亚胺(PI)进行改性，采用高压静电纺丝法制备了质量比PBI∶PI=0.3∶1.0的复合纤维隔膜。研究了复合纤维隔膜的微观形貌、孔隙率、吸液率、热性能、电化学性能及电池性能，并将PBI∶PI=0.3∶1.0的复合纤维隔膜、PI纤维隔膜及聚丙烯(Celgard 2400，PP)隔膜进行了性能对比。结果表明，PBI∶PI=0.3∶1.0的PBI/PI复合纤维隔膜孔隙率达82%，吸液率达618%；在空气气氛中，300℃无尺寸收缩，在N2气氛中，分解温度在400℃以上，800℃时残重大于50%；离子电导率达1.29×10−3 S/cm，较PP隔膜几乎提高了1个数量级；界面阻抗为489.34 Ω，较PP隔膜降低了17%；电化学稳定窗口提高到5.05 V，为PP隔膜的119%；以PBI∶PI=0.3∶1.0的复合纤维隔膜组装的CR 2032型电池表现出优异的电池性能，经大电流放电后电池性能稳定，初始放电容量达130.01 mA·h/g，在1 A/s循环100次后容量保持率高达98.91%，均优于Celgard 2400隔膜电池。Abstract: In order to improve the problems of low porosity, low electrolyte uptake of commercial separators, poor heat resistance and thermal dimensional stability, Polybenzimidazole (PBI) was used to modify polyimide (PI). The PBI∶PI=0.3∶1.0 (mass ratio) composite fiber separator was prepared by the method of high-voltage electrostatic spinning. The microscopic morphology, porosity, electrolyte uptake, thermal performance, electrochemical performance and battery performance of the composite fiber separator were studied. The performance of composite fiber separator with mass ratio of PBI∶PI=0.3∶1.0, PI fiber separator and polypropylene (Celgard 2400, PP) separator were compared. The results show that the composite fiber separator with PBI∶PI=0.3∶1.0 has a porosity of 82% and electrolyte uptake of 618%; in an air atmosphere, there is no size shrinkage at 300℃; in a nitrogen atmosphere, the decomposition temperature is above 400℃, and the residual mass at 800℃ is more than 50%. The ionic conductivity reaches 1.29×10−3 S/cm, which is almost an order of magnitude higher than PP separatos; the interface impedance is 489.34 Ω, which is 17% lower than PP separator; the electrochemical stability window is increased to 5.05 V, which is 19% of the PP separator; CR 2032 battery assembled with PBI∶PI=0.3∶1.0 composite fiber separator shows excellent battery performance. After high current discharged, cells properties remain stable, initial discharge capacity is 130.01 mA·h/g, capacity retention rate is 98.91% after 100 cycles of 1 A/s, which is better than PP separator cells.
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Key words:
- electrospinning /
- polybenzimidazole /
- biphenyl type polyimide /
- lithium-ion cells /
- separator
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图 1 聚酰亚胺(PI) (a) 纤维隔膜和聚苯并咪唑(PBI)/PI (b)复合纤维隔膜的SEM图像
Figure 1. SEM images of polyimide (PI) (a) and polybenzimidazole (PBI)/PI (b) composite fiber separator
图 2 PBI/PI复合纤维隔膜，PI纤维隔膜和PP隔膜在25℃、100℃、200℃和300℃处理后的热收缩照片
Figure 2. Photos of PBI/PI composite fiber separators, PI fiber separators and PP separators after treatment at 25℃, 100℃, 200℃ and 300℃
图 3 PBI/PI复合纤维隔膜和PI纤维隔膜热失重曲线
Figure 3. Thermal mass loss curves of PBI/PI composite fiber separators and PI fiber separators
图 4 PBI/PI复合纤维隔膜、PI纤维隔膜和PP隔膜的交流阻抗谱图
Figure 4. Nyquist plots of PBI/PI composite fiber separators, PI fiber separators and PP separators
图 5 PBI/PI复合纤维隔膜、PI纤维隔膜和PP隔膜的界面阻抗图谱
Figure 5. Electrochemical impedance spectra of PBI/PI composite fiber separators, PI fiber separators and PP separators
图 6 PBI/PI复合纤维隔膜、PI纤维隔膜和PP隔膜的电化学稳定窗口曲线
Figure 6. Electrochemical stability window of PBI/PI composite fiber separators, PI fiber separators and PP separators
图 7 PBI/PI复合纤维隔膜，PI纤维隔膜和PP隔膜在1 A/s的充放电曲线
Figure 7. Charge-discharge curves PBI/PI, PI fiber separators and PP separators at 1 A/s
图 8 PBI/PI复合纤维隔膜、PI纤维隔膜和PP隔膜在1 A/s下进行100个循环的放电容量
Figure 8. Discharge stability of PBI/PI, PI fiber separators and PP separators batteries with a high current density at 1 A/s after 100 cycles
图 9 PBI/PI复合纤维隔膜、PI纤维隔膜和PP隔膜在不同倍率下的放电容量
Figure 9. Dischrge capability of PBI/PI, PI fiber separators and PP separators batteries at different discharge rates
表 1 PBI/PI复合纤维隔膜、PI纤维隔膜、聚丙烯(PP)隔膜的孔隙率和吸液率
Table 1. Porosity and electrolyte uptake of PBI/PI composite fiber separators, PI and polypropylene (PP) separators
Sample Porosity/% Electrolyte uptake/% PBI/PI 82 618 PI 76 565 PP (Celgard 2400) 42 150 Note: Celgard 2400 is a single-layer PP separator with a thickness of 25 μm. 
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