原位合成法二氧化硅/硅钨酸改性聚乙烯醇质子交换膜的研制
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摘要
以聚乙烯醇(PVA)为基体,利用原位合成法制备了二氧化硅(SiO2)和硅钨酸(SiWA)微粒在PVA基质中均匀分布的二氧化硅/硅钨酸改性聚乙烯醇(SiO2/SiWA-m-PVA)质子交换膜.利用扫描电镜(SEM)和热重分析仪(TG)分别对膜的形貌及热稳定性进行了表征,四氯化硅与钨酸钠摩尔比对SiO2/SiWA-m-PVA质子交换膜的质子导电性能、阻醇性能的影响.结果表明,四氯化硅与钨酸钠摩尔比为1∶1时,原位合成的二氧化硅和硅钨酸在质子交换膜中分散均匀,在温度低于100℃时SiO2/SiWA-m-PVA膜保水性能好;室温质子电导率为1.48×10-2 S/cm,甲醇渗透率为1.37×10-7 cm2/s,比相同条件下Nafion117膜甲醇渗透率低一个数量级,应用于直接甲醇燃料电池单电池能量密度可达11.82mW/cm2.
The silica/silicon tungstate-m-polyvinyl alcohol(SiO2/SiWA-m-PVA)membrane with SiO2 and SiWA pcerticles distributing uniformly in PVP matrix,was prepared by in-situ synthesis.With scanning electron microscopy(SEM)and thermal gravimetric analysis(TG),the morphology and thermal stability of the membrane are characterized.The influence of mole ratio of SiCl4/sodium tungstate on conductivity and methanol permeability is studied by AC impedance spectroscopy and gas chromatography.The results show that the in-situ synthesized silica and silicon tungstate dispersed well in membrane when the molar ratio of silicon tetrachloride to sodium tungstate is 1∶1.SiO2/SiWA-m-PVA membrane has good water retention below 100 ℃.At room temperature,the proton conductivity of 1.48× 10-2 S/cm,methanol permeability of 1.37×10-7 cm2/s lower an order of magnitude than Nafion117 membrane under the same conditions,power density for direct methanol fuel cell is up to 11.82mW/cm2.
The silica/silicon tungstate-m-polyvinyl alcohol(SiO2/SiWA-m-PVA)membrane with SiO2 and SiWA pcerticles distributing uniformly in PVP matrix,was prepared by in-situ synthesis.With scanning electron microscopy(SEM)and thermal gravimetric analysis(TG),the morphology and thermal stability of the membrane are characterized.The influence of mole ratio of SiCl4/sodium tungstate on conductivity and methanol permeability is studied by AC impedance spectroscopy and gas chromatography.The results show that the in-situ synthesized silica and silicon tungstate dispersed well in membrane when the molar ratio of silicon tetrachloride to sodium tungstate is 1∶1.SiO2/SiWA-m-PVA membrane has good water retention below 100 ℃.At room temperature,the proton conductivity of 1.48× 10-2 S/cm,methanol permeability of 1.37×10-7 cm2/s lower an order of magnitude than Nafion117 membrane under the same conditions,power density for direct methanol fuel cell is up to 11.82mW/cm2.
引文
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[2]Bennett B,Koraishy B,Meyers J.Modeling and optimization of the DMFC system:Relating materials properties to system size and performance performance[J].J Power Souces,2012,218(15):268-279.
[3]Sharma S,Pollet B.Support materials for PEMFC and DMFC electrocatalysts-A review[J].J Power Sources,2012,208(15):96-119.
[4]Zhao Wengao,Zhou Xibin,Chen Jing,et al.Controllable electrodeposition of platinum nanoparticles on graphene nanosheet for methanol oxidation reaction[J].J Clust Sci,2013,24(3):739-748.
[5]Yang Chunchen,Lus S J,Shih J Y.A novel organic/inorganic polymer membrane based on poly(vinylalcohol)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid/3-glycidyloxypropyl trimethoxysilane polymer electrolyte membrane for direct methanol fuel cells[J].J Power Sources,2011,196(10):4458-4467.
[6]Madaeni S,Amirinejad S,Amirinejad M.Phosphotungstic acid doped poly(vinyl alcohol)/poly(ether sulfone)blend composite membranes for direct methanol fuel cells[J].J Membr Sci,2011,380(1/2):132-137.
[7]吴翠明,徐铜文,杨伟华,等.无机-有机复合膜应用的研究进展[J].膜科学与技术,2003,23(2):52-57.
[8]张正伟.溶胶-凝胶法制备无机/有机杂化质子交换膜的研究[D]//浙江大学,2006,3.
[9]马宁,蔡芳昌,殷浩,等.交流阻抗法测试质子交换膜电导率的影响因素[J].高分子材料科学与工程,2012,28(11):125-128.
[10]Higa M,Hatemura K,Sugita M.Performance of passive direct methanol fuel cell with poly(vinyl alcohol)-based polymer electrolyte membranes[J].International J Hydrogen Nenergy,2012,37(7):6292-6301.
[11]生瑜,朱德钦,陈建定.聚合物基无机纳米复合材料的制备方法原位生成法[J].高分子通报,2001,8(4):9-23.
[12]浦鸿汀,侯继,杨正龙.杂多酸掺杂聚酰亚胺/二氧化硅复合质子交换膜的制备和性能研究[J].功能材料,2005,36(12):1923-1930.