PEO基固态聚合物电解质膜的静电纺丝制备及性能

doi:10.11868/j.issn.1001-4381.2021.001125

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摘要

PEO基固态聚合物电解质被认为是目前固态锂电池领域极具产业化前景的固态电解质。为适应工业化生产，采用静电纺丝技术制备PEO/LiClO₄固态聚合物电解质（SPE），研究纺丝电压、纺丝液质量浓度和锂盐含量对SPE纤维膜形貌和直径的影响。通过扫描电子显微镜观察SPE中纤维的形貌，利用Image J软件分析SPE纤维的直径。通过DSC，XRD，FTIR-ATR和拉伸测试等手段对静电纺丝制备的SPE纤维膜的组成、结构、性能等进行研究。结果表明：当纺丝电压为15 kV、PEO/LiClO₄纺丝液质量浓度为6%、[EO]∶[Li⁺]=10∶1（摩尔比）时，静电纺丝方法制备的PEO/LiClO₄SPE纤维膜具有较好的纤维形貌，平均直径为557 nm，分布均一；当[EO]∶[Li⁺]=10∶1时，SPE纤维膜中PEO的熔点仅为53.8℃，结晶度低至18.9%；电解质在30℃时的离子电导率达到5.16×10^-5 S·cm^-1，同时具备良好的电化学稳定性和界面稳定性。

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关键词 ：固态聚合物电解质, 聚氧化乙烯, 静电纺丝, 纤维, 离子电导率

Abstract：

PEO-based solid polymer electrolytes are considered as a promising solid electrolyte in the field of solid-state lithium batteries.PEO/LiClO₄ solid polymer electrolyte(SPE) was prepared through electrostatic spinning technology, in order to meet the demand of industrial production. The effects of spinning voltage, spinning solution concentration and lithium salt content on the morphology and diameter of the fiber were studied.The morphology of SPE fiber was observed by scanning electron microscope and the diameter of SPE fiber was analysed by Image J.Furthermore, the composition, structure and properties of solid polymer electrolyte fiber membranes prepared by electrospinning were studied by DSC, XRD, FTIR-ATR and tensile testing.The results show that the PEO/LiClO₄ solid polymer electrolyte membrane prepared by electrostatic spinning method has good fiber morphology, when the spinning voltage is 15 kV, and the concentration of PEO/LiClO₄ spinning solution is 6%, and the molar ratio ([EO]: [Li⁺]) is 10:1.Meanwhile, the average diameter of the fibers is 557 nm, giving relatively uniform distribution.When[EO]: [Li⁺]=10:1, the melting point of PEO in the SPE fiber membrane is only 53.8℃, with the crystallinity as low as 18.9%. And the ionic conductivity of the prepared SPE exhibits as high as 5.16×10^-5 S·cm^-1 at 30℃.Moreover, the prepared electrospun SPE has good electrochemical stability and interfacial stability.

Key words： solid polymer electrolyte polyethylene oxide electrospinning fiber ionic conductivity

收稿日期: 2021-11-18 出版日期: 2022-10-24

中图分类号:

O632

基金资助:陕西省自然科学基金面上项目(2021JM-427);陕西省自然科学基金-企业-陕煤联合项目(2021JLM-36)

通讯作者: 杨晶晶,陈卫星 E-mail: yangjingjing@xatu.edu.cn;chenwx@xatu.edu.cn

作者简介: 陈卫星(1972—), 男, 教授, 博士, 研究方向为功能高分子材料的合成及应用, 联系地址: 陕西省西安市西安工业大学未央校区材料与化工学院(710021), E-mail: chenwx@xatu.edu.cn
杨晶晶(1985—), 女, 副教授, 博士, 研究方向为固态聚合物电解质的制备与应用, 联系地址: 陕西省西安市西安工业大学未央校区材料与化工学院(710021), E-mail: yangjingjing@xatu.edu.cn

引用本文:

曹倩, 杨晶晶, 陈卫星, 王趁红, 吴新明, 雷亚萍. PEO基固态聚合物电解质膜的静电纺丝制备及性能[J]. 材料工程, 2022, 50(10): 148-156.
Qian CAO, Jingjing YANG, Weixing CHEN, Chenhong WANG, Xinming WU, Yaping LEI. Preparation and properties of solid polymer electrolyte membranes based on PEO by electrospinning. Journal of Materials Engineering, 2022, 50(10): 148-156.

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http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2021.001125 或 http://jme.biam.ac.cn/CN/Y2022/V50/I10/148

Fig.1 SPE纤维膜的制备流程

Fig.2 不同电压下SPE纤维膜的SEM照片
(a)13 kV；(b)15 kV；(c)17 kV；(d)19 kV

Fig.3 不同纺丝液质量浓度时SPE纤维膜的SEM照片
(a)4%；(b)5%；(c)6%；(d)7%

Fig.4 不同锂盐含量时SPE纤维膜的SEM照片
(a)[EO]∶[Li⁺]=20∶1；(b)[EO]∶[Li⁺]=15∶1；(c)[EO]∶[Li⁺]=13∶1；(d)[EO]∶[Li⁺]=10∶1

Fig.5 不同锂盐含量SPE纤维膜的DSC曲线(a)和XRD谱图(b)

Table 1 PEO/LiClO₄ SPE纤维膜的T_m, ΔH_m和Χ_c

Fig.6 不同锂盐含量SPE纤维膜的FTIR-ATR谱图(a)和[EO]∶[Li⁺]=10∶1时SPE浇铸膜和纤维膜的应力-应变曲线(b)

Table 2 不同锂盐含量SPE纤维膜的FTIR-ATR谱图分析结果

Fig.7 30 ℃下不同锂盐含量SPE纤维膜和浇铸膜的阻抗谱(a)和其离子电导率随温度变化曲线(b)

Fig.8 SPE样品的电化学性能(80 ℃)
(a), (b)SPE纤维膜, 浇铸膜的计时电流法分析曲线；(c)SPE纤维膜和浇铸膜的LSV曲线；(d)组装的Li/SPE纤维膜/Li及Li/SPE浇铸膜/Li对称电池的长循环电压曲线

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