本文關(guān)鍵詞：半超支化半交聯(lián)磺化聚酰亞胺復(fù)合質(zhì)子交換膜制備及性能研究　出處：《大連理工大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 有機-無機復(fù)合質(zhì)子交換膜 磺化聚酰亞胺 半交聯(lián) 半超支化 胺化二氧化硅

【摘要】：質(zhì)子交換膜燃料電池(Proton Exchange Membrane Fuel Cell, PEMFC)是一種將燃料的化學(xué)能通過電化學(xué)反應(yīng)直接轉(zhuǎn)化為電能的裝置。其具有環(huán)境污染小,噪音低,壽命長,工作溫度低,比能量大等優(yōu)點,在便攜式電源、可移動動力電源等方面具有廣闊的應(yīng)用前景。而質(zhì)子交換膜(PEM)是質(zhì)子交換膜燃料電池的核心組件,在PEMFC中具有雙重作用； (1)作為電解質(zhì)提供氫離子的傳輸通道； (2)阻隔陰陽兩極,防止兩極反應(yīng)氣體接觸而發(fā)生化學(xué)反應(yīng)。目前,使用最廣泛的質(zhì)子交換膜是由美國杜邦公司開發(fā)的全氟磺酸膜,即Nafion(?)膜。它具有優(yōu)異的熱穩(wěn)定性和化學(xué)穩(wěn)定性,在高濕度的條件下有較高的質(zhì)子傳導(dǎo)率。但是價格昂貴,并且在高溫或低濕度條件下質(zhì)子傳導(dǎo)率低,嚴重限制了其在PEMFC中的廣泛應(yīng)用。因此,研發(fā)一種高性能、低成本的質(zhì)子交換膜非常重要。通過大量的研究發(fā)現(xiàn),磺化聚酰亞胺是一種具有較廣應(yīng)用前景的質(zhì)子交換膜材料,其主要優(yōu)勢在于：較好的質(zhì)子傳導(dǎo)能力、機械性能和熱穩(wěn)定性以及相對低廉的制備成本。但是,磺化聚酰亞胺膜也存在一些需要解決的問題,包括在水中氧化穩(wěn)定性差,嚴重影響燃料電池的使用壽命。為了改善磺化聚酰亞胺膜的氧化穩(wěn)性能,人們嘗試多種改性方法,其中有機-無機雜化是一種常用的方法,其主要優(yōu)點在于復(fù)合膜不僅具有有機物的柔韌性同時具有無機組分的穩(wěn)定性,因此得到越來越多研究者的關(guān)注。本論文選用磺化聚酰亞胺作為質(zhì)子交換膜主鏈,聚砜作為支撐材料,通過酸酐封端磺化聚酰亞胺與胺化二氧化硅進一步縮聚制備得到具有半超支化半交聯(lián)結(jié)構(gòu)的磺化聚酰亞胺復(fù)合質(zhì)子交換膜。其主要內(nèi)容為：首先合成以酸酐封端的磺化聚酰亞胺鏈,其次以表面胺化的二氧化硅作為“Bx型胺類單體”,直接與酸酐封端聚酰亞胺進行縮聚,最后加入支撐材料聚砜制備得到復(fù)合膜。復(fù)合膜中半超支化結(jié)構(gòu)形成的自由體積和胺化二氧化硅可以有效保持復(fù)合膜中的水含量,進一步提高復(fù)合膜的質(zhì)子傳導(dǎo)率,同時半交聯(lián)結(jié)構(gòu)和支撐材料聚砜的存在增強了膜的氧化穩(wěn)定性,延長膜的使用壽命。研究結(jié)果表明,30℃下,SPI/SiO2-10-PSf(SiO2含量為10%)復(fù)合膜在芬頓試劑中開始溶解和完全溶解的時間比SPI/PSf膜分別增加了14和37小時。SPI/SiO2-10-PSf復(fù)合膜在60℃條件下的質(zhì)子傳導(dǎo)率為0.162S·cm-1,高于Nafion115膜(0.124S·cm1-1)。整體上SPI/SiO2-10-PSf復(fù)合膜具有較好的綜合性能,有望替代Nafion膜,應(yīng)用于質(zhì)子交換膜燃料電池中。
[Abstract]:Proton Exchange Membrane Fuel Cell. PEMFC is a device that converts the chemical energy of fuel directly into electric energy by electrochemical reaction, which has the advantages of low environmental pollution, low noise, long life, low working temperature and high specific energy. The proton exchange membrane (PEM) is the core component of the proton exchange membrane fuel cell (PEM), which plays a dual role in PEMFC. 1) providing hydrogen ion transport channel as electrolyte; At present, the most widely used proton exchange membrane is the perfluorinated sulfonic acid membrane developed by DuPont Company of the United States. Membrane. It has excellent thermal and chemical stability, high proton conductivity under high humidity, but high price, and low proton conductivity at high temperature or low humidity. Therefore, it is very important to develop a proton exchange membrane with high performance and low cost. Sulfonated polyimide is a kind of proton exchange membrane material with wide application prospect. Its main advantages lie in better proton conductivity, mechanical properties and thermal stability, and relatively low preparation cost. Sulfonated polyimide membrane also has some problems to be solved, including poor oxidation stability in water, which seriously affects the service life of fuel cell. In order to improve the oxidation stability of sulfonated polyimide membrane. A variety of modification methods have been tried, of which organic-inorganic hybrid is a common method. Its main advantage is that the composite membrane not only has the flexibility of organic matter, but also has the stability of inorganic components. In this thesis, sulfonated polyimide was chosen as the main chain of proton exchange membrane and polysulfone as the supporting material. Sulfonated polyimide composite proton exchange membranes with semi-hyperbranched semi-crosslinked structure were prepared by further condensation of acid anhydride capped sulfonated polyimide and aminated silica. First, sulfonated polyimide chains sealed by anhydride were synthesized. Secondly, the surface aminated silica was used as the "Bx amine monomer", and the polyimide was directly condensed with the acid anhydride terminated polyimide. Finally, the composite membrane was prepared by adding the support material polysulfone. The free volume of semi-hyperbranched structure and the content of water in the composite membrane could be effectively maintained by adding silica amines. The proton conductivity of the composite membrane was further improved, and the existence of semi-crosslinked structure and support material polysulfone enhanced the oxidation stability of the membrane and prolonged the service life of the membrane. The results showed that the membrane was stable at 30 鈩，

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