交联型直接甲醇燃料电池质子交换膜的制备及性能研究
发布时间：2018-12-16 12:10
【摘要】：质子交换膜燃料电池可直接将氢气、甲醇等化学能源不经卡诺循环直接转化为电能,具有工作原理简单,绿色、高效的优点。商业化的质子交换膜(PEM)主要是以Nafion膜为代表的全氟磺酸膜。此类膜具有质子传导率高、化学稳定性好和热性能优异的优点,但是其高成本、高的甲醇透过率阻碍了其在直接甲醇燃料电池中的应用。因此,研究制备新型芳杂环聚合物质子交换膜以替代全氟磺酸膜已成为目前的研究热点。本文以制备交联型芳杂环质子交换膜为出发点,制备了共价交联聚倍半硅氧烷(POSS)/磺化聚酰亚胺质子交换膜以及离子交联磺化聚醚醚酮质子交换膜,以期降低传统芳杂环质子交换膜甲醇透过率。研究交联结构对质子传导、机械性能、阻醇性能等的影响。具体研究工作如下：1.通过控制交联剂八氨基倍半硅氧烷(OAPS)的含量(0.2～1.6 mol%)合成了一系列不同交联度的八氨基倍半硅氧烷(OAPS)共价交联磺化聚酰亚胺(SPIs)质子交换膜。研究发现,POSS交联结构在提高所得材料机械性能和化学稳定性的同时,降低了其甲醇透过率。另外,POSS的存在促进了有机-无机微相分离结构,提高了所得膜的质子传导率。在20-80℃、100%湿度下,所制得的交联型薄膜具有和Nafion 117膜相当的质子传导率。所得的薄膜具有比Nafion膜更低的甲醇透过率。当OAPS的含量为0.4 mol%时,80℃下质子传导率为0.111S cm-1,高于Nafion膜(0.10 S cm-1)。2.将二氮芴结构引入到磺化聚醚醚酮(SPEEK)主链结构,通过磺酸基与二氮芴结构中的吡啶环的酸碱相互作用得到具有离子交联结构的质子交换膜。所制得的薄膜具有良好的机械性能、热稳定性能、氧化稳定性以及尺寸稳定性。此外,和Nafion 117膜相比,该类离子交联型质子交换膜具有更低的甲醇透过率(0.56×10-7～1.8×10-7cm2 s-1)。30 ℃时,相对选择性(2.46～4.82×104 Ss·cm-3)明显高于Nafion膜(1.34×104Ss·cm-3)。80 ℃时,磺化度为80%的磺化聚醚醚酮薄膜的质子传导率为8.1 mS cm-1,达到了应用要求。
[Abstract]:Proton exchange membrane fuel cells can directly convert hydrogen, methanol and other chemical energy into electric energy without Carnot cycle. It has the advantages of simple working principle, green and high efficiency. Commercial proton exchange membrane (PEM) is mainly perfluorinated sulfonic acid membrane represented by Nafion membrane. This kind of membrane has the advantages of high proton conductivity, good chemical stability and excellent thermal performance, but its high cost and high methanol transmittance hinder its application in direct methanol fuel cells. Therefore, the preparation of novel aromatic heterocyclic polymer proton exchange membranes to replace perfluorinated sulfonic acid membranes has become a hot research topic. Based on the preparation of cross-linked aromatic heterocyclic proton exchange membranes, (POSS) / sulfonated polyimide proton exchange membranes and ion crosslinked sulfonated polyether ether ketone proton exchange membranes were prepared. In order to reduce the methanol transmissivity of the conventional aromatic heterocyclic proton exchange membrane. The effects of crosslinking structure on proton conduction, mechanical properties and alcohol resistance were studied. The specific research work is as follows: 1. A series of (OAPS) covalent crosslinked sulfonated polyimide (SPIs) proton exchange membranes with different crosslinking degrees were synthesized by controlling the content of octamine-octa-trisiloxane (OAPS) (0.21.60 mol%). It is found that the crosslinking structure of POSS can improve the mechanical properties and chemical stability of the materials and decrease the methanol transmittance. In addition, the existence of POSS promotes the separation structure of organic-inorganic microphase and increases the proton conductivity of the membrane. At 20-80 鈩，
本文编号：2382312
[Abstract]:Proton exchange membrane fuel cells can directly convert hydrogen, methanol and other chemical energy into electric energy without Carnot cycle. It has the advantages of simple working principle, green and high efficiency. Commercial proton exchange membrane (PEM) is mainly perfluorinated sulfonic acid membrane represented by Nafion membrane. This kind of membrane has the advantages of high proton conductivity, good chemical stability and excellent thermal performance, but its high cost and high methanol transmittance hinder its application in direct methanol fuel cells. Therefore, the preparation of novel aromatic heterocyclic polymer proton exchange membranes to replace perfluorinated sulfonic acid membranes has become a hot research topic. Based on the preparation of cross-linked aromatic heterocyclic proton exchange membranes, (POSS) / sulfonated polyimide proton exchange membranes and ion crosslinked sulfonated polyether ether ketone proton exchange membranes were prepared. In order to reduce the methanol transmissivity of the conventional aromatic heterocyclic proton exchange membrane. The effects of crosslinking structure on proton conduction, mechanical properties and alcohol resistance were studied. The specific research work is as follows: 1. A series of (OAPS) covalent crosslinked sulfonated polyimide (SPIs) proton exchange membranes with different crosslinking degrees were synthesized by controlling the content of octamine-octa-trisiloxane (OAPS) (0.21.60 mol%). It is found that the crosslinking structure of POSS can improve the mechanical properties and chemical stability of the materials and decrease the methanol transmittance. In addition, the existence of POSS promotes the separation structure of organic-inorganic microphase and increases the proton conductivity of the membrane. At 20-80 鈩，
本文编号：2382312
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