物理化学学报 >> 2012, Vol. 28 >> Issue (09): 2057-2064.doi: 10.3866/PKU.WHXB201205251

电化学和新能源 上一篇    下一篇

原位交联杂化型聚合物电解质膜的形成机理、结构模型及其电化学性能

梁桂杰1,2, 钟志成1, 许杰3, 徐卫林3, 陈美华1, 张增常1, 李文联1   

  1. 1. 湖北文理学院材料科学与工程研究中心, 湖北襄阳 441053;
    2. 西安交通大学, 金属材料强度国家重点实验室, 西安 710049;
    3. 武汉纺织大学, 新型纺织材料绿色加工及其功能化教育部重点实验室, 武汉 430073
  • 收稿日期:2012-03-30 修回日期:2012-05-24 发布日期:2012-08-02
  • 通讯作者: 梁桂杰 E-mail:lgj511011@163.com
  • 基金资助:

    国家自然科学基金 (51003082),教育部科学技术研究重点项目(208089)和湖北省自然科学基金 (2011CDC062) 资助项目

Formation Mechanism, Structure Model and Electrochemical Performance of an In situ Cross Linking Hybrid Polymer Electrolyte Membrane

LIANG Gui-Jie1,2, ZHONG Zhi-Cheng1, XU Jie3, XU Wei-Lin3, CHEN Mei-Hua1, ZHANG Zeng-Chang1, LI Wen-Lian1   

  1. 1. Research Center for Materials Science & Engineering, Hubei University of Arts and Science, Xiangyang 441053, Hubei Province, P. R. China;
    2. State Key Laboratory for Mechanical Behavior of Materials, Xi'an JiaoTong University, Xi'an 710049, P. R. China;
    3. Key Laboratory of Green Processing and Functional Textiles of New Textile Materials, Ministry of Education, Wuhan Textile University, Wuhan 430073, P. R. China
  • Received:2012-03-30 Revised:2012-05-24 Published:2012-08-02
  • Contact: LIANG Gui-Jie E-mail:lgj511011@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (51003082), Key Project of Science and Technology Research of Ministry of Education (208089) and Natural Science Foundation of Hubei Province,China (2011CDC062).

摘要:

合成含有Ti(Ⅵ)杂化中心的交联(柠檬酸钛络合体-聚乙二醇)聚酯网络作为基体,水解生成的Nano-TiO2粒子为填料,LiI/I2为导电离子,通过原位聚合复合法制备了Nano-TiO2/(柠檬酸钛络合体-聚乙二醇)/LiI/I2交联杂化型聚合物电解质膜。采用局域密度近似(LDA)法、Raman光谱、傅里叶变换红外光谱(FTIR)、透射电子显微镜(TEM)和能量散射X射线分析(EDXA)探讨了交联杂化聚合物基体的形成机理,并建立了其相应的结构模型。在此基础之上,研究了四异丙氧基钛(Ti(iOPr)4)的含量对Nano-TiO2/(柠檬酸钛络合体-聚乙二醇)/LiI/I2电解质膜的结构及电化学性能的影响。研究表明:当Ti(iOPr)4含量高于12 % (w)时,Nano-TiO2粒子和Ti(Ⅵ)杂化中心的共同作用不仅有效提高了电解质膜的离子电导率(σ),而且显著改善了电解质膜与电极间的界面稳定性;Ti(iOPr)4含量为48 % (w)时,电解质膜的室温离子电导率达到最大值9.72×10-5 S·cm-1,电解质膜的界面电阻于6d后趋于稳定。

关键词: 聚合物电解质, 染料敏化太阳能电池, 四异丙氧基钛, 离子电导率, 界面稳定性

Abstract:

A Nano-TiO2/poly(citric acid titanium complex-polyethylene glycol)/LiI/I2 crosslinked hybrid polymer electrolyte membrane has been prepared via in-situ polymerization and compositing. Specifically, the method used the synthesized crosslinked network of poly(citric acid titanium complex-polyethylene glycol) containing the Ti(VI) hybrid center as a substrate, the hydrolyzed Nano-TiO2 as fillers and LiI/I2 as conductive ionics. The formation mechanism of the crosslinked hybrid polymer matrix is discussed. A structural model was established with a local density approximation (LDA) method. The influence of Ti(iOPr)4 content on the structure and electrochemical performance of the electrolyte membrane were investigated with Raman spectra, Fourier transform infrared spectra (FTIR), transmission electron microscopy (TEM), and an energy dispersive X-ray analysis (EDXA) technique. It was found that when the Ti(iOPr)4 content was higher than 12% (w), the combined action of Nano-TiO2 particles and the Ti(VI) hybrid center improved not only the room-temperature ionic conductivity (σ), but also the interfacial stability. At 48% (w) Ti(iOPr)4 content, the value of σ reached a maximum of 9.72×10-5 S·cm-1 and the interface resistance became stable after 6 d.

Key words: Polymer electrolyte, Dye-sensitized solar cells, Titanium tetraisopropoxide, Ionic conductivity, Interface stability

MSC2000: 

  • O646