物理化学学报 >> 2011, Vol. 27 >> Issue (11): 2665-2670.doi: 10.3866/PKU.WHXB20111106

催化和表面科学 上一篇    下一篇

化学交联聚乙烯醇改性纤维素碱性阴离子交换复合膜的制备与性能

刘玲玲1, 丁蕾1, 徐莉1, 乔锦丽1, 盛嘉伟2   

  1. 1. 东华大学环境科学与工程学院, 上海 201620;
    2. 浙江工业大学化学工程与材料学院, 杭州 310032
  • 收稿日期:2011-06-13 修回日期:2011-08-23 发布日期:2011-10-27
  • 通讯作者: 乔锦丽 E-mail:qiaojl@dhu.edu.cn
  • 基金资助:

    国家自然科学基金(21173039), 上海市浦江人才基金(08PJ14096), 上海市自然科学基金(09ZR1433300), 浙江省重中之重学科开放基金(20110927), 教育部归国留学人员基金(2009(1001))和上海市重点学科项目(B604)资助项目

Synthesis and Properties of Chemically Cross-Linked Poly(vinyl alcohol) Modified Quaterized Hydroxyethylcellulose Ethoxylate as Novel Alkaline Anion-Exchange Membrane

LIU Ling-Ling1, DING Lei1, XU Li1, QIAO Jin-Li1, SHENG Jia-Wei2   

  1. 1. College of Environmental Science and Engineering, Donghua University, Shanghai 201620, P. R. China;
    2. College of Chemical Engineering and Materials, Zhejiang Industrial University, Hangzhou 310032, P. R. China
  • Received:2011-06-13 Revised:2011-08-23 Published:2011-10-27
  • Contact: QIAO Jin-Li E-mail:qiaojl@dhu.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21173039), Pujiang Foundation of Shanghai, China (08PJ14096), Natural Science Foundation of Shanghai Science and Technology Committee, China (09ZR1433300), Opening Foundation of Zhejing Provincial Top Key Discipline, China (20110927), Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education of China (2009(1001)), and Fund of Shanghai Leading Academic Discipline Project, China (B604).

摘要: 高稳定性碱性阴离子交换膜的制备已成为碱性固体电解质膜研究领域的一大热点. 本文通过聚乙烯醇化学交联改性制备出了季铵化羟乙基乙氧基纤维素碱性阴离子交换膜(PVA/QHECE). 采用傅里叶变换红外(FTIR)光谱、热重(TG)分析、交流(AC)阻抗等方法考察了复合膜的分子结构、热稳定性、耐碱稳定性及离子电导率等性能. 详尽考察了交联时间、交联剂含量、聚合物组成对成膜力学强度、含水率以及OH-电导率的影响. 实验结果表明: 随着交联时间的增加, 膜的溶胀率降低, 力学强度随之增强, 而离子电导率随膜含水率的降低没有发生明显变化, 室温下OH-的电导率在3.26×10-4-4.44×10-4 S·cm-1范围内变化. 热重分析结果显示: 掺入42.9%的QHECE时, 膜的热分解温度达260°C. 此外, 将PVA/QHECE膜在6 mol·L-1 KOH浓碱溶液中80°C浸渍处理168 h, 膜的电导率从4.90×10-4 S·cm-1提高到9.68×10-4 S·cm-1, 而膜的外观和力学强度以及含水率未发生明显变化, 这一结果表明该膜具有很好的耐碱化学稳定性, 有望作为一种新型的碱性燃料电池用离子交换膜.

关键词: 碱性阴离子交换膜, 聚乙烯醇, 季铵化羟乙基乙氧基纤维素, 共混化学交联, OH-电导率, 耐碱稳定性

Abstract: Much attention has been paid to alkaline ion-exchange membranes with high alkaline stability. In this work, chemically cross-linked poly(vinyl alcohol) modified quaterized hydroxyethylcellulose ethoxylate (PVA/QHECE) membranes were prepared and evaluated as OH--conducting polymer electrolytes. The membranes were characterized using Fourier transform infrared (FTIR) spectra, thermogravimetric (TG) analysis, and the alternating current (AC) impedance technique as for their inner structure, thermal stability, alkaline resistance stability, and OH- conductivity (σ). The OH- conductivity of the membranes was investigated as a function of cross-linking time, the content of cross-linking agent, polymer composition, and water uptake. It was found that membrane swelling decreased with cross-linking time accompanied by an improvement in mechanical properties but no obvious decrease in OH- conductivity resulted from the reduced water uptake. The OH- conductivities in the range of 3.26×10-4-4.44×10-4 S·cm-1 were obtained at room temperature ((19 ± 2)°C), depending on the different PVA/QHECE compositions. TG analysis showed that the PVA/QHECE membrane exhibited high thermal stability at up to 260°C when the QHECE content was 42.9%. In addition, the membranes had a high alkaline stability without a loss of integrity and OH- conductivity after immersion in 6 mol·L-1 KOH at 80°C for 168 h.

Key words: Alkaline anion-exchange membrane, PVA, QHECE, Blending and chemical crosslinking, OH- conductivity, Alkaline resistance stability

MSC2000: 

  • O646