甲基丙烯酸类聚合物修饰的聚乙烯隔膜在锂离子电池中的应用

doi:10.7503/cjcu20190309

摘要/Abstract

摘要：

将环状碳酸酯基团引入到聚甲基丙烯酸甲酯(PMMA)侧链上, 制备了聚(2,3-环碳酸甘油酯)甲基丙烯酸酯(PDOMMA), 并用其修饰锂离子电池聚乙烯隔膜. 通过热重分析、差示扫描量热分析及接触角和吸液率测试等研究了PDOMMA的热稳定性及其修饰的聚乙烯隔膜对电解液的浸润性和吸液率的影响, 并通过恒流充放电、交流阻抗、倍率性能测试及扫描电子显微镜观测等研究了修饰隔膜对锂离子电池性能的影响. 结果表明, 与未修饰隔膜相比, 修饰隔膜对电解液浸润性更优异(20 s内便完全浸润), 吸液率更高(440%), 电池循环性能更好(放电比容量提高了12.3%).

关键词: 甲基丙烯酸类聚合物, 锂离子电池, 聚乙烯隔膜, 浸润性

Abstract:

Cyclic carbonate group was introduced into the side-chain of polymethyl methacrylate(PMMA) to prepare poly(2-oxo-1,3-dioxolan-4-yl) methyl methacrylate(PDOMMA), which was then coated on polyethylene separator of lithium ion battery. The thermal stability of PDOMMA and the effect of modification on wettability and electrolyte uptake ability of separator were studied by thermogravimetry(TG), differential scanning calorimetry(DSC), static contact angle test and electrolyte uptake rate test. Moreover, the effect of the modified separator on the performance of lithium ion battery was studied by galvanostatic charge and discharge test, alternating current(AC) impedance test, rate capability test and scanning electron microscopy(SEM). The results show that compared to the unmodified separator, the modified separator has an improved wettability with the electrolyte(the complete wetting is reached by 20 s), a higher uptake rate of electrolyte(440%), and better cycle performance of the related battery(discharge specific capacity increased by 12.3%).

Key words: Methyl acrylic polymer, Lithium ion battery, Polyethylene separator, Wettability

中图分类号:

O646

TrendMD:

吴为, 刘玉春, 朱冠存, 安佳钰, 窦广鹏, 王雨雁, 刘靖, 孙冬兰, 郭也平. 甲基丙烯酸类聚合物修饰的聚乙烯隔膜在锂离子电池中的应用. 高等学校化学学报, 2019, 40(11): 2332.

WU Wei, LIU Yuchun, ZHU Guancun, AN Jiayu, DOU Guangpeng, WANG Yuyan, LIU Jing, SUN Donglan, GUO Yeping. Application of Polyethylene Separator Modified by Methyl Acrylic Polymer in Lithium Ion Battery ^†. Chem. J. Chinese Universities, 2019, 40(11): 2332.

图/表 8

Fig.1 DSC(A) and TG-DTG(B) curves of PDOMMA with a heating rate of 10 ℃/min and under a nitrogen atmosphere with a flow rate of 50 mL/min

Fig.2 Photographs of static contact angle of 1 mol/L LiPF6 in EC+DMC(volume ratio 1:1) liquid electrolyte on uncoated separator initial(A) and after 15 min(B) and on coated separator initial(A') and after 20 s(B'), respectively

Fig.3 Electrolyte uptake ability of the uncoated separator and coated separator with liquid electrolyte 1 mol/L LiPF6 in EC+DMC(volume ratio 1:1)

Fig.4 SEM images of uncoated(A) and coated(B) separators Acceleration voltage: 20 kV.

Fig.5 Alternating current impedance curve of uncoated and coated separator at room temperature SS/separator/SS cells, frequency range 1.0 MHz — 0.01 Hz, amplitude 10 mV.

Fig.6 Discharge specific capacity(A) and coulombic efficiency(B) of the Li/MCMB cells with uncoated or coated separator under 0.2C rate between the voltage ranges of 0.005—1.5 V at room temperature for 50 cycles and discharge specific capacity of Li/MCMB cells with uncoated or coated separator at various rates cycling(C)

Fig.7 Alternating current impedance curves of the Li/MCMB cells with the uncoated and coated separators after 2 cycles(A) and after 20 cycles(B) Frequency range: 1.0 MHz—0.01 Hz, amplitude 10 mV.

Fig.8 SEM images of MCMB electrodes (A) Fresh MCMB electrode; (B) MCMB electrode of Li/MCMB cell with uncoated separator after 50 cycles; (C) MCMB electrode of Li/MCMB cell with coated separator after 50 cycles. Acceleration voltage: 20 kV.

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