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材料导报  2020, Vol. 34 Issue (12): 12152-12157    https://doi.org/10.11896/cldb.19050045
  高分子与聚合物基复合材料 |
1-乙基-3-甲基咪唑硫酸乙酯盐离子液体中采用电化学法合成聚苯胺薄膜及其耐蚀性
周婉秋, 赵玉明, 刘晓安, 杨佳宇, 姜文印, 辛士刚, 康艳红
沈阳师范大学化学化工学院,沈阳 110034
Electrosynthesis of Polyaniline Film in a 1-ethyl-3-methylimidazole Sulfate Ionic Liquid and Its Corrosion Resistance
ZHOU Wanqiu, ZHAO Yuming, LIU Xiao'an, YANG Jiayu, JIANG Wenyin, XIN Shigang, KANG Yanhong
College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
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摘要 为了进一步扩大质子交换膜燃料电池(PEMFC)的实际应用,提高其双极板的耐腐蚀性能至关重要。在不锈钢基体上电化学沉积导电聚苯胺(PANI)薄膜,有可能满足PEMFC对导电性和耐蚀性的要求。前人关于电化学合成PANI主要集中在硫酸、高氯酸等水溶液体系,鲜见离子液体中采用电化学法合成聚苯胺薄膜及其耐蚀性的研究。
   本工作以1-乙基-3-甲基咪唑硫酸乙酯盐(EMIES)离子液体作为聚合反应电解质,采用循环伏安法在316L不锈钢(SS)表面电化学合成PANI薄膜,制备了PANI/316L SS复合材料双极板。用红外光谱、拉曼光谱、紫外可见光谱、X射线光电子能谱和扫描电子显微镜对PANI膜进行结构表征,用开路电位、极化曲线和电化学阻抗谱研究PANI/316L SS腐蚀性能。结果表明:PANI具有中间氧化态结构,EMIES离子液体的阴离子(CH3CH2SO4-)和乙二酸的阴离子(HOOC-COO-)作为“对阴离子”在PANI共轭分子链中发生了共掺杂。
   本工作在316L SS表面获得了平整致密的PANI薄膜。与316L SS裸金属相比,PANI/316L SS的腐蚀电位E0提高0.2~0.4 V,腐蚀电流密度I0降低一个数量级, PANI薄膜使316L SS耐腐蚀性能显著增强。
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周婉秋
赵玉明
刘晓安
杨佳宇
姜文印
辛士刚
康艳红
关键词:  双极板  聚苯胺薄膜  离子液体  掺杂  耐蚀性    
Abstract: To expand the practical application of proton exchange membrane fuel cell (PEMFC), it is important to improve the corrosion resistance of its bipolar plate. Electrochemical deposition of conductive polyaniline (PANI) films on stainless steel (SS) substrate may meet the requirements of PEMFC for conductivity and corrosion resistance. Previous studies on electrochemical synthesis of PANI mainly focused on aqueous systems such as sulfuric acid and perchloric acid, and few studies involved in electrosynthesis of PANI films in ionic liquids and their corrosion resistance.
In this work, PANI films were synthesized by cyclic voltammetry on the surface of 316L SS using 1-ethyl-3-methylimidazole ethyl sulfate (EMIES) ionic liquid as the polymerization electrolyte, and the PANI/316L SS composite materials bipolar plates were prepared. The structure of PANI was characterized by infrared spectrum, Raman spectroscopy, ultraviolet-visible spectrum, X-ray photoelectron spectrum and scanning electron microscope. The corrosion performance of PANI/316L SS was studied by open circuit potential, polarization curve and electrochemical impedance spectroscopy. The results show that PANI has an intermediate oxidation state structure, the anion of the ionic liquid EMIES (CH3CH2SO4-) and the anion of oxalic acid (HOOC-COO-) as “counter anion” are co-doped in PANI conjugated molecular chains.
A flat and compact PANI film is obtained on the surface of 316L SS. Compared with 316L SS bare metal, the corrosion potential E0 of PANI/316L SS increases by 0.2—0.4 V, and the corrosion current density I0 decreases by an order of magnitude. PANI film improves the corrosion resistance of 316L stainless steel obviously.
Key words:  bipolar plate    polyaniline film    ionic liquid    doping    corrosion resistance
                    发布日期:  2020-05-29
ZTFLH:  TG174.4  
基金资助: 辽宁省教育厅重点实验室基础研究项目(LZ2015066)
通讯作者:  wqzhou@imr.ac.cn   
作者简介:  周婉秋,沈阳师范大学教授,2004年于中国科学院金属研究所获得材料学博士学位。主要研究方向为金属材料的腐蚀机理与防护技术。早期的研究集中在镁合金表面化学转化膜的制备及其腐蚀防护机制的研究,近期主要开展导电聚合物的电化学合成及其腐蚀行为研究。主持国家自然科学基金项目2项,辽宁省教育厅重点实验室基础研究项目1项,参加国家863计划3项,发表论文50余篇。
引用本文:    
周婉秋, 赵玉明, 刘晓安, 杨佳宇, 姜文印, 辛士刚, 康艳红. 1-乙基-3-甲基咪唑硫酸乙酯盐离子液体中采用电化学法合成聚苯胺薄膜及其耐蚀性[J]. 材料导报, 2020, 34(12): 12152-12157.
ZHOU Wanqiu, ZHAO Yuming, LIU Xiao'an, YANG Jiayu, JIANG Wenyin, XIN Shigang, KANG Yanhong. Electrosynthesis of Polyaniline Film in a 1-ethyl-3-methylimidazole Sulfate Ionic Liquid and Its Corrosion Resistance. Materials Reports, 2020, 34(12): 12152-12157.
链接本文:  
http://www.mater-rep.com/CN/10.11896/cldb.19050045  或          http://www.mater-rep.com/CN/Y2020/V34/I12/12152
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