物理化学学报 >> 2015, Vol. 31 >> Issue (10): 1905-1913.doi: 10.3866/PKU.WHXB201508261

电化学和新能源 上一篇    下一篇

TMAH改性PVDF一步接枝PSBMA质子交换膜的制备与性能

张嘉汉1,郭贵宝1(),安胜利2(),郝燕1,张董1,闫凯波1   

  1. 1 内蒙古科技大学化学与化工学院,包头014010
    2 内蒙古科技大学材料与冶金学院,包头014010
  • 收稿日期:2015-05-22 发布日期:2015-10-10
  • 基金资助:
    国家自然科学基金(51474133);内蒙古自治区自然科学基金(2013MS0210);内蒙古科技大学大学生科技创新基金(2014073)

Synthesis and Properties of Proton Exchange Membranes via Single-Step Grafting PSBMA onto PVDF Modified by TMAH

Jia-Han. ZHANG1,Gui-Bao. GUO1(),Sheng-Li. AN2(),Yan. HAO1,Dong. ZHANG1,Kai-Bo. YAN1   

  1. 1 School of Chemistry and Chemical Engineering, Inner Mongolia University of Science and Technology, Baotou 014010, P. R. China
    2 School of Material and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, P. R. China
  • Received:2015-05-22 Published:2015-10-10
  • Supported by:
    the National Natural Science Foundation of China(51474133);Natural Science Foundation of Inner Mongolia, China(2013MS0210);Students Science and Technology Innovation Foundation of Inner Mongolia University of Science and Technology, China(2014073)

摘要:

使用四甲基氢氧化铵(TMAH)液相改性聚偏氟乙烯(PVDF),以过氧化苯甲酰(BPO)为引发剂,一步将磺酸基甲基丙烯酸甲酯(SBMA)接枝到改性的PVDF上,制备了聚偏氟乙烯接枝聚磺酸基甲基丙烯酸甲酯(PVDFg-PSBMA)质子交换膜.利用傅里叶变换红外(FTIR)光谱和扫描电镜-X射线能谱(SEM-EDX)分析了膜的结构、形貌及硫元素分布情况.同时研究了不同质量分数的TMAH甲醇溶液对PVDF-g-PSBMA膜电导率和甲醇渗透率的影响.结果表明, TMAH使PVDF脱去HF产生碳碳双键且SBMA成功接枝到改性的PVDF骨架上,硫元素在膜内外分布均匀; PVDF-g-PSBMA膜的电导率和甲醇渗透率随TMAH在甲醇中质量分数的增多而增大, TMAH质量分数为20%的膜的质子电导率在20 ℃下达到0.0892 S·cm-1,常温下的甲醇渗透率为4.04 × 10-7cm2·s-1;热重分析(TGA)表明,膜的热稳定性良好,耐热温度高达270 ℃.该膜作为电解质材料的直接甲醇燃料电池(DMFC)的最大功率密度达到17.06 mW·cm-2.

关键词: 质子交换膜, 聚偏氟乙烯, 液相改性, 四甲基氢氧化铵, 磺酸基甲基丙烯酸甲酯

Abstract:

Poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) proton exchange membranes were synthesized via single-step grafting sulfobetaine methacrylate (SBMA) onto PVDF. Benzoyl peroxide (BPO) was the initiator, and the PVDF was initially modified by tetramethylammonium hydroxide (TMAH) in the liquid phase. Microstructure morphologies and sulfur distributions in the membrane were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX), respectively. The PVDF formed C=C double bonds following dehydrofluorination by TMAH. SBMA was grafted onto the modified PVDF backbones, forming a homogeneous sulfur distribution in the interior and exterior of the membrane. Proton conductivities and methanol permeabilities of PVDF-g-PSBMA membranes increased with the increasing of the TMAH mass fraction in methanol. When the mass fraction was 20%, the proton conductivity of the membrane was 0.0892 S·cm-1 at 20 ℃, and the methanol permeability was 4.04 × 10-7 cm2·s-1 at ambient temperature, respectively. The membrane exhibited good thermal stability up to 270 ℃, as verified by thermogravimetric analysis (TGA). With this membrane, the peak power density of a direct methanol fuel cell (DMFC) was 17.06 mW·cm-2.

Key words: Proton exchange membrane, Poly(vinylidene fluoride), Liquid-phase modification, Tetramethylammonium hydroxide, Sulfobetaine methacrylate

MSC2000: 

  • O646