氧化石墨烯改性复合质子交换膜的制备及性能研究

Preparation and properties of sulfonated poly(ether ether ketone)/graphene oxide proton exchange membranes via electrospinning

  • 摘要: 通过静电纺丝技术成功制备了氧化石墨烯(GO)均匀分散的磺化聚醚醚酮(SPEEK)复合膜(SPEEK-GO-E),研究了GO分散性对复合膜质子电导率与阻醇性能的影响。通过SEM、TEM和AFM等表征手段证实,相较于传统溶液浇注法制备的SPEEK-GO-C膜,静电纺丝法显著改善了GO在基体中的分散性,有效抑制了GO片层的团聚现象。性能测试结果显示,SPEEK-GO-E膜展现出优异的综合性能:30℃时,质子电导率达到1.12 ×10−2 S·cm−1,较纯SPEEK膜提升67%;甲醇渗透率降至5.16 × 10−8 cm2·s−1,比纯SPEEK膜降低了80%。此外,该复合膜表现出各向同性的溶胀特性,吸水率和溶胀率显著降低,尺寸稳定性提升。分析表明,静电纺丝工艺促进了GO在基体中的均匀分散,其表面亲水含氧官能团与SPEEK分子链上的磺酸基团形成强氢键网络,GO的二维片层结构构建了长程有序的质子传输通道,不仅提升了复合膜的质子传导率,同时GO本身形成了有效的物理屏障,阻碍了甲醇分子的渗透,这为开发高性能质子交换膜提供了新思路。

     

    Abstract: The graphene oxide (GO) uniformly dispersed sulfonated poly(ether ether ketone) (SPEEK) composite membrane (SPEEK-GO-E) was successfully prepared by electrospinning. The effect of GO dispersion on proton conductivity and methanol barrier properties was investigated. SEM, TEM, and AFM characterizations confirmed that compared with the solution-cast SPEEK-GO-C membrane, electrospinning significantly improved GO dispersion and effectively suppressed GO agglomeration. Performance tests showed that the SPEEK-GO-E membrane exhibited excellent comprehensive properties: at 30℃, its proton conductivity reached 1.12×10−2 S·cm−1 (67% higher than pure SPEEK), while methanol permeability decreased to 5.16×10−8 cm2·s−1 (80% reduction). Moreover, the membrane demonstrated isotropic swelling behavior with remarkably reduced water uptake and swelling ratio, indicating enhanced dimensional stability. The improved performance is attributed to the uniform GO dispersion enabled by electrospinning, where hydrophilic oxygen-containing groups on GO form strong hydrogen bonds with sulfonic acid groups in SPEEK chains. Simultaneously, the two-dimensional GO sheets construct long-range ordered proton transport channels, which enhance proton conduction while effectively blocking methanol permeation. This study provides a new approach for developing high-performance proton exchange membranes.

     

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