物理化学学报 >> 2013, Vol. 29 >> Issue (01): 64-72.doi: 10.3866/PKU.WHXB201211023

电化学和新能源 上一篇    下一篇

一种新型物理交联型凝胶聚合物电解质的制备与表征

左翔, 蔡烽, 刘晓敏, 杨晖, 沈晓冬   

  1. 南京工业大学材料科学与工程学院, 江苏 南京 210009
  • 收稿日期:2012-09-07 修回日期:2012-11-02 发布日期:2012-12-14
  • 通讯作者: 杨晖 E-mail:yanghui@njut.edu.cn
  • 基金资助:

    国家自然科学基金(20803035); 2011年度江苏省省属高校自然科学研究重大项目(11KJA430006)和江苏高校优势学科建设工程项目资助

Synthesis and Characterization of a Novel Physically Cross-Linked Gel Polymer Electrolyte

ZUO Xiang, CAI Feng, LIU Xiao-Min, YANG Hui, SHEN Xiao-Dong   

  1. College of Materials Science and Engineering, Nanjing University of Technology, Nanjing 210009, P. R. China
  • Received:2012-09-07 Revised:2012-11-02 Published:2012-12-14
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (20803035), Key Project (2011) of Educational Commission of Jiangsu Province, China (11KJA430006), and Priority Academic Program Development of Jiangsu Higher Education Institutions, China.

摘要:

以甲氧基聚乙二醇甲基丙烯酸酯(MPEGM)和十六烷基聚乙二醇甲基丙烯酸酯(HPEGM)为单体, 三乙二醇二甲醚(TEGDME)为增塑剂, 与锂盐(高氯酸锂, LiClO4)和光引发剂(安息香二甲醚, DMPA)复合制成光敏体系, 经紫外(UV)固化得到物理交联型凝胶聚合物电解质(GPE)薄膜. 用红外(IR)光谱、差热分析(DSC)、拉伸测试和交流阻抗(AC) 等方法对聚合物基体和电解质的性能进行了研究.结果表明: 当共聚物P(MPEGM-co-HPEGM)中HPEGM含量为50%(w)时, 十六烷基链段(C16)在聚氧化乙烯(PEO)链段静电斥力的作用下发生聚集, 自组装形成了物理交联, 提高了共聚物的空间稳定性; 温度和电解质中各组分的含量对电导率均有较大的影响, 综合性能较好的电解质在30℃时电导率可达0.87×10-3 S·cm-1; 采用循环伏安法测得该电解质的电化学窗口为0~4.5 V (vs. Li/Li+), 可以满足锂离子电池的应用要求; 组装成的LiFePO4/GPE/Li电池, 在30℃下以0.1 C和0.2 C倍率进行充放电测试, 首次放电容量分别为154.7和148.0 mAh·g-1.

关键词: 凝胶聚合物电解质, 物理交联, 增塑剂, 三乙二醇二甲醚

Abstract:

A physically cross-linked gel polymer electrolyte (GPE) was obtained by photo-induced radical polymerization of a mixture of methoxy-poly(ethylene glycol) methacrylate (MPEGM), hexadecal-poly (ethylene glycol) methacrylate (HPEGM), triethylene glycol dimethyl ether (TEGDME), lithium salt (lithium perchlorate, LiClO4) and photo-initiator (2, 2-Dimethoxy-2-phenylacetophenone, DMPA). The resulting polymers and gel polymer electrolytes were characterized by infrared spectroscopy (IR), differential scanning calorimetry (DSC), tensile test, and alternating current (AC) impedance measurements. The results showed that the physically cross-linked polymer matrix was formed by C16 aggregation with the effect of electrostatic repulsion of PEO chains when the HPEGM content was high. The ionic conductivity of the obtained GPE is affected by its composition and the temperature. The GPE prepared with the optimum composition exhibited excellent mechanical properties and a relatively high ionic conductivity (up to 0.87×10?3 S·cm-1 at 30℃). In addition, the GPE was found to present a wide electrochemical window (from 0 V to 4.5 V vs. Li/Li+). In addition, a coin cell based on the gel electrolyte, with LiFePO4/C as the cathode and metallic lithium as the anode, showed a discharge capacity as high as 154.7 mAh·g-1 and 148.0 mAh·g-1 at 30℃ under of 0.1 C and 0.2 C, respectively.

Key words: Gel polymer electrolyte, Physical cross-linking, Plasticizer, Triethylene glycol dimethyl ether

MSC2000: 

  • O646