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

引用本文: 梁桂杰, 钟志成, 许杰, 徐卫林, 陈美华, 张增常, 李文联. 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[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201205251 shu

Citation: LIANG Gui-Jie, ZHONG Zhi-Cheng, XU Jie, XU Wei-Lin, CHEN Mei-Hua, ZHANG Zeng-Chang, LI Wen-Lian. Formation Mechanism, Structure Model and Electrochemical Performance of an In situ Cross Linking Hybrid Polymer Electrolyte Membrane[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201205251 shu

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

基金项目:
国家自然科学基金 (51003082) (51003082)

教育部科学技术研究重点项目(208089) (208089)

湖北省自然科学基金 (2011CDC062) 资助项目 (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:

English

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

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 Date: 30 March 2012
Available Online: 02 August 2012
Fund Project:
国家自然科学基金 (51003082)

教育部科学技术研究重点项目(208089)

湖北省自然科学基金 (2011CDC062) 资助项目

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:

1. [1]
  
  (1) Fenton, D. E.; Parker, J. M.;Wright, P. V. Polymer 1973, 14,589.
  (1) Fenton, D. E.; Parker, J. M.;Wright, P. V. Polymer 1973, 14,589.
2. [2]
  (2) Li, X. L.; Guo, J.;Wu, Q.; Cheng, Y.; Long, Y. C.; Jiang, Z. Y.Acta Phys. -Chim. Sin. 2005, 21, 397. [李雪莉, 郭娟, 吴强, 程岩, 龙英才, 江志裕. 物理化学学报, 2005, 21, 397.]doi: 10.3866/PKU.WHXB20050411(2) Li, X. L.; Guo, J.;Wu, Q.; Cheng, Y.; Long, Y. C.; Jiang, Z. Y.Acta Phys. -Chim. Sin. 2005, 21, 397. [李雪莉, 郭娟, 吴强, 程岩, 龙英才, 江志裕. 物理化学学报, 2005, 21, 397.]doi: 10.3866/PKU.WHXB20050411
3. [3]
  (3) Li, Y. J.; Zhan, H.; Liu, S. Q.; Huang, K. L.; Zhou, Y. H. Acta Phys. -Chim. Sin. 2010, 26, 2387. [李亚娟, 詹晖, 刘素琴,黄可龙, 周运鸿. 物理化学学报, 2010, 26, 2387.] doi: 10.3866/PKU.WHXB20100818(3) Li, Y. J.; Zhan, H.; Liu, S. Q.; Huang, K. L.; Zhou, Y. H. Acta Phys. -Chim. Sin. 2010, 26, 2387. [李亚娟, 詹晖, 刘素琴,黄可龙, 周运鸿. 物理化学学报, 2010, 26, 2387.] doi: 10.3866/PKU.WHXB20100818
4. [4]
  (4) Quartarone, E.; Mustarelli, P.; Magistris, A. Solid State Ion1998, 110, 1. doi: 10.1016/S0167-2738(98)00114-3(4) Quartarone, E.; Mustarelli, P.; Magistris, A. Solid State Ion1998, 110, 1. doi: 10.1016/S0167-2738(98)00114-3
5. [5]
  (5) Robitaille, C. D.; Fauteux, D. J. Electrochem. Soc. 1986, 133,315. doi: 10.1149/1.2108569(5) Robitaille, C. D.; Fauteux, D. J. Electrochem. Soc. 1986, 133,315. doi: 10.1149/1.2108569
6. [6]
  (6) Wieczorek,W.; Raducha, D.; Zalewska, A.; Stevens, J. R.J. Phys. Chem. B 1998, 102, 8725. doi: 10.1021/jp982403f(6) Wieczorek,W.; Raducha, D.; Zalewska, A.; Stevens, J. R.J. Phys. Chem. B 1998, 102, 8725. doi: 10.1021/jp982403f
7. [7]
  (7) Yang, H.; Liu, J.; Lin, Y.; Zhang, J.; Zhou, X. Electrochim. Acta2011, 56, 6271.(7) Yang, H.; Liu, J.; Lin, Y.; Zhang, J.; Zhou, X. Electrochim. Acta2011, 56, 6271.
8. [8]
  (8) Stephan, A. M. Eur. Polym. J. 2006, 42, 21. doi: 10.1016/j.eurpolymj.2005.09.017(8) Stephan, A. M. Eur. Polym. J. 2006, 42, 21. doi: 10.1016/j.eurpolymj.2005.09.017
9. [9]
  (9) Kumar, M.; Sekhon, S. S. Eur. Polym. J. 2002, 38, 1297. doi: 10.1016/S0014-3057(01)00310-X(9) Kumar, M.; Sekhon, S. S. Eur. Polym. J. 2002, 38, 1297. doi: 10.1016/S0014-3057(01)00310-X
10. [10]
  (10) Wu, X. L.; Xin, S.; Seo, H. H.; Kim, J.; Guo, Y. G.; Lee, J. S.Solid State Ion. 2011, 186, 1.(10) Wu, X. L.; Xin, S.; Seo, H. H.; Kim, J.; Guo, Y. G.; Lee, J. S.Solid State Ion. 2011, 186, 1.
11. [11]
  (11) Chu, P. P.; Reddy, M. J. J. Power Sources 2003, 115, 288. doi: 10.1016/S0378-7753(02)00717-6(11) Chu, P. P.; Reddy, M. J. J. Power Sources 2003, 115, 288. doi: 10.1016/S0378-7753(02)00717-6
12. [12]
  (12) Johan, M. R.; Fen, L. B. Ionics 2010, 16, 335.(12) Johan, M. R.; Fen, L. B. Ionics 2010, 16, 335.
13. [13]
  (13) Zhang, J.; Han, H.W.;Wu, S. J.; Xu, S.; Yang, Y.; Zhou, C. H.;Zhao, X. Z. Solid State Ion. 2007, 178, 1595. doi: 10.1016/j.ssi.2007.10.009(13) Zhang, J.; Han, H.W.;Wu, S. J.; Xu, S.; Yang, Y.; Zhou, C. H.;Zhao, X. Z. Solid State Ion. 2007, 178, 1595. doi: 10.1016/j.ssi.2007.10.009
14. [14]
  (14) Geng, Y.; Shi, Y. T.;Wang, L. D.; Ma, B. B.; Gao, R.; Zhu, Y. F.;Dong, H. P.; Qiu, Y. Phys. Chem. Chem. Phys. 2011, 13, 2417.(14) Geng, Y.; Shi, Y. T.;Wang, L. D.; Ma, B. B.; Gao, R.; Zhu, Y. F.;Dong, H. P.; Qiu, Y. Phys. Chem. Chem. Phys. 2011, 13, 2417.
15. [15]
  (15) Lee, R. H.; Cheng, T. F.; Chang, J.W.; Ho, J. H. Colloid Polym. Sci. 2011, 289, 817.(15) Lee, R. H.; Cheng, T. F.; Chang, J.W.; Ho, J. H. Colloid Polym. Sci. 2011, 289, 817.
16. [16]
  (16) Zhang, D.W.; Li, X. D.; Huang, S. M.;Wang, Z. A.; Shi, J. H.;Sun, Z.; Yin, X. J. International Journal of Nanoscience 2010,9, 257.(16) Zhang, D.W.; Li, X. D.; Huang, S. M.;Wang, Z. A.; Shi, J. H.;Sun, Z.; Yin, X. J. International Journal of Nanoscience 2010,9, 257.
17. [17]
  (17) Basak, P.; Manorama, S. V. Eur. Polym. J. 2004, 40, 1155. doi: 10.1016/j.eurpolymj.2004.01.013(17) Basak, P.; Manorama, S. V. Eur. Polym. J. 2004, 40, 1155. doi: 10.1016/j.eurpolymj.2004.01.013
18. [18]
  (18) Kuo, P. L.; Hou, S. S.; Lin, C. Y.; Chen, C. C.;Wen, T. C. J. Polym. Sci. Pol. Chem. 2004, 42, 2051. doi: 10.1002/pola.20056(18) Kuo, P. L.; Hou, S. S.; Lin, C. Y.; Chen, C. C.;Wen, T. C. J. Polym. Sci. Pol. Chem. 2004, 42, 2051. doi: 10.1002/pola.20056
19. [19]
  (19) Liang, G. J.; Xu, J.; Xu,W. L.; Shen, X. L.; Zhang, H.; Yao, M.Polym. Compos. 2011, 32, 511.(19) Liang, G. J.; Xu, J.; Xu,W. L.; Shen, X. L.; Zhang, H.; Yao, M.Polym. Compos. 2011, 32, 511.
20. [20]
  (20) Liang, G.; Xu, J.; Xu,W. L.; Shen, X. L.; Bai, Z. K.; Yao, M.Polym. Eng. Sci. 2011, 51, 2526.(20) Liang, G.; Xu, J.; Xu,W. L.; Shen, X. L.; Bai, Z. K.; Yao, M.Polym. Eng. Sci. 2011, 51, 2526.
21. [21]
  (21) Liang, G.; Xu,W. L.; Xu, J.; Shen, X. L.; Yao, M. Influence ofWeight Ratio of Citric Acid Cross Linker on the Structure andConductivity of the Crosslinked Polymer Electrolytes. InAdvanced Materials Research, International Symposium onChemical Engineering and Material Properties, Shenyang,China, Nov 4-6, 2011; Zhang, H. M.,Wu, B., Eds.; Trans TechPublications Ltd: Switzerland, 2011; pp 391-392.(21) Liang, G.; Xu,W. L.; Xu, J.; Shen, X. L.; Yao, M. Influence ofWeight Ratio of Citric Acid Cross Linker on the Structure andConductivity of the Crosslinked Polymer Electrolytes. InAdvanced Materials Research, International Symposium onChemical Engineering and Material Properties, Shenyang,China, Nov 4-6, 2011; Zhang, H. M.,Wu, B., Eds.; Trans TechPublications Ltd: Switzerland, 2011; pp 391-392.
22. [22]
  (22) Kefalas, E. T.; Panagiotidis, P.; Raptopoulou, C. P.; Terzis, A.;Mavromoustakos, T.; Salifoglou, A. Inorg. Chem. 2005, 44,2596. doi: 10.1021/ic049276o(22) Kefalas, E. T.; Panagiotidis, P.; Raptopoulou, C. P.; Terzis, A.;Mavromoustakos, T.; Salifoglou, A. Inorg. Chem. 2005, 44,2596. doi: 10.1021/ic049276o
23. [23]
  (23) Deng, Y. F.; Zhou, Z. H.;Wan, H. L. Inorg. Chem. 2004, 43,6266. doi: 10.1021/ic0496018(23) Deng, Y. F.; Zhou, Z. H.;Wan, H. L. Inorg. Chem. 2004, 43,6266. doi: 10.1021/ic0496018
24. [24]
  (24) Collins, J. M.; Uppal, R.; Incarvito, C. D.; Valentine, A. M.Inorg. Chem. 2005, 44, 3431. doi: 10.1021/ic048158y(24) Collins, J. M.; Uppal, R.; Incarvito, C. D.; Valentine, A. M.Inorg. Chem. 2005, 44, 3431. doi: 10.1021/ic048158y
25. [25]
  (25) Feng, M.;Wang, Y. F.;Wang, H.; Cao, X.W.; Lan, G. X.; Fan,X. J. Chinese Journal of Light Scattering 2008, 20, 265. [冯敏, 王玉芳, 王翚, 曹学伟, 蓝国祥, 范秀菊. 光散射学报,2008, 20, 265.](25) Feng, M.;Wang, Y. F.;Wang, H.; Cao, X.W.; Lan, G. X.; Fan,X. J. Chinese Journal of Light Scattering 2008, 20, 265. [冯敏, 王玉芳, 王翚, 曹学伟, 蓝国祥, 范秀菊. 光散射学报,2008, 20, 265.]
26. [26]
  (26) Zampieri, M.; Lazaro, S. R.; Paskocimas, C. A.; Ferreira, A. G.;Lon , E.; Varela, J. A. J. Sol-Gel Sci. Technol. 2006, 37, 9. doi: 10.1007/s10971-005-4892-2
  (26) Zampieri, M.; Lazaro, S. R.; Paskocimas, C. A.; Ferreira, A. G.;Lon , E.; Varela, J. A. J. Sol-Gel Sci. Technol. 2006, 37, 9. doi: 10.1007/s10971-005-4892-2

扫一扫看文章

计量

PDF下载量: 766
文章访问数: 2994
HTML全文浏览量: 68

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs