發(fā)布時(shí)間：2018-01-03 06:31

  本文關(guān)鍵詞：含唑環(huán)的磺化聚芳醚酮砜類質(zhì)子交換膜的制備與性能研究　出處：《長(zhǎng)春工業(yè)大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 三唑 硅烷偶聯(lián)劑 交聯(lián) 質(zhì)子交換膜 燃料電池

【摘要】：隨著能源危機(jī)和環(huán)境污染日益加重,開發(fā)清潔高效無污染的新能源成為了世界各國(guó)科學(xué)研究的熱點(diǎn)。質(zhì)子交換膜燃料電池(Proton Exchange Membrane Fuel Cell,PEMFC),近年來被世界各國(guó)爭(zhēng)相研究,是因其擁有啟動(dòng)迅速、操作便利、能量轉(zhuǎn)換效率高和清潔無污染等優(yōu)點(diǎn)。質(zhì)子交換膜(PEM)作為PEMFC的關(guān)鍵部分,其性能的優(yōu)劣關(guān)乎PEMFC的應(yīng)用前景。如今,商業(yè)應(yīng)用最為普及的PEM是美國(guó)杜邦獨(dú)立研發(fā)的Nafion膜,其具有杰出的化學(xué)穩(wěn)定性和質(zhì)子傳遞性能,但同時(shí)由于其制備成本高、阻醇性能差且高溫質(zhì)子傳導(dǎo)率下降明顯等缺點(diǎn)限制了其進(jìn)一步的推廣應(yīng)用。因此,開發(fā)一種可替代Nafion膜且綜合性能優(yōu)異的新型膜材料成為科研學(xué)者的主要攻克方向。其中,磺化聚芳醚酮砜類(SPAEKS)被認(rèn)為是最有應(yīng)用前景的新型膜材料之一,其本身?yè)碛型怀龅臋C(jī)械性能和熱穩(wěn)定性,且價(jià)格相對(duì)低廉。但是與Nafion膜一樣,該類膜的質(zhì)子傳導(dǎo)主要依賴磺酸基團(tuán),而當(dāng)磺化度較高時(shí)易導(dǎo)致膜發(fā)生過度溶脹,尺寸穩(wěn)定性、氧化穩(wěn)定性、阻醇性能和機(jī)械性能大幅度下降,從而使其使用性能大打折扣。因此,對(duì)磺化聚芳醚酮砜類膜材料進(jìn)行合理的改性和修飾,使其綜合性能提高顯得十分重要。本文首先制備了含三唑側(cè)基的磺化聚芳醚酮砜膜(SPT),以接枝的方式引入了三唑基團(tuán),利用三唑基團(tuán)同時(shí)作為質(zhì)子給體與受體的特性,以及三唑基團(tuán)與磺酸基團(tuán)之間的相互作用,提供了新的質(zhì)子跳躍點(diǎn),使質(zhì)子以跳躍機(jī)理進(jìn)行傳輸,極大的改善了質(zhì)子膜在高溫和低相對(duì)濕度條件下的質(zhì)子傳導(dǎo)率。120oC時(shí),SPT-4膜的質(zhì)子傳導(dǎo)率高達(dá)0.166 S cm~(-1),遠(yuǎn)比相同測(cè)試標(biāo)準(zhǔn)Nafion膜的質(zhì)子傳導(dǎo)率要高。為進(jìn)一步增強(qiáng)膜的阻醇能力,我們向體系內(nèi)引入有機(jī)硅氧烷材料,以三唑改性的γ-縮水甘油醚氧丙基三甲氧基硅烷(GT)為交聯(lián)劑,通過溶膠-凝膠法成功制得三唑改性KH560/磺化聚芳醚酮砜交聯(lián)膜(AMSP/GT)。實(shí)驗(yàn)結(jié)果表明,交聯(lián)結(jié)構(gòu)改善了膜的尺寸穩(wěn)定性,同時(shí)抑制了甲醇的透過,60oC時(shí),AMSP/GT-30的甲醇滲透系數(shù)僅為9.95×10~(-7) cm~2 s~(-1),這要比相同測(cè)試標(biāo)準(zhǔn)下Nafion膜的甲醇透過率小一個(gè)數(shù)量級(jí)。同時(shí),三唑基團(tuán)的存在,提高了膜在高溫時(shí)的質(zhì)子傳輸性能,120oC時(shí),AMSP/GT-30的質(zhì)子傳導(dǎo)率可達(dá)0.106 S cm~(-1)。通過引入三唑基團(tuán)和構(gòu)建交聯(lián)結(jié)構(gòu),本文成功制備了阻醇性能良好且高溫質(zhì)子傳導(dǎo)率優(yōu)異的新型質(zhì)子交換膜材料。
[Abstract]:With the increasing energy crisis and environmental pollution. The development of clean, efficient and pollution-free new energy has become a hot spot of scientific research all over the world. Proton Exchange membrane fuel Cell (. Proton Exchange Membrane Fuel Cell. In recent years, PEMFC has been studied by many countries all over the world because of its rapid start-up and convenient operation. Proton exchange membrane (PEM) is a key part of PEMFC, and its performance is related to the application prospect of PEMFC. PEM, which is the most popular commercial application, is an independent Nafion membrane developed by DuPont, USA. It has excellent chemical stability and proton transfer performance, but at the same time because of its high cost of preparation. The poor performance of alcohol and the obvious decrease of proton conductivity at high temperature limit its further application. The development of a new membrane material which can replace Nafion membrane and has excellent comprehensive properties has become the main research direction of researchers. Sulfonated poly (aryl ether ketone sulfone) (SPAEKS) is considered as one of the most promising novel membrane materials with outstanding mechanical properties and thermal stability. And the price is relatively low, but like Nafion membrane, the proton conduction of this kind of membrane mainly depends on the sulfonic group, but when the sulfonation degree is high, the membrane is prone to excessive swelling, dimensional stability, oxidation stability. The properties of alcohol resistance and mechanical properties were greatly reduced, so the performance of sulfonated poly (aryl ether ketone sulfone) membrane was modified and modified reasonably. It is very important to improve its comprehensive properties. Firstly, the sulfonated poly (aryl ether ketone sulfone) membrane SPT was prepared, and the triazole group was introduced by grafting. Using the properties of triazole group as a proton donor and acceptor, and the interaction between triazole group and sulfonic group, a new proton hopping point is provided, which makes the proton transport by jumping mechanism. The proton conductivities of SPT-4 membrane at high temperature and low relative humidity were greatly improved. The proton conductivity of SPT-4 membrane was as high as 0.166s / cm ~ (-1) under high temperature and low relative humidity. The proton conductivity of the Nafion membrane is much higher than that of the same test standard. In order to further enhance the alcohol resistance of the membrane, we introduced the organic siloxane material into the system. Triazole modified 緯 -glycidyl ether oxypropyl trimethoxysilane (GTZ) was used as crosslinking agent. Triazole modified KH560 / sulfonated poly (aryl ether ketone sulfone) crosslinked membrane was successfully prepared by sol-gel method. The experimental results showed that the crosslinking structure improved the dimensional stability of the membrane. At 60oC, the methanol permeability coefficient of AMSP / GT-30 was only 9.95 脳 10 ~ (-7) cm~2 ~ (-1). This is an order of magnitude less than the methanol transmittance of Nafion membrane under the same test standard. At the same time, the existence of triazole groups improves the proton transport performance of the membrane at 120oC at high temperature. The proton conductivity of AMSP/GT-30 can reach 0.106s / cm ~ (-1). The triazole group was introduced and the cross-linking structure was constructed. In this paper, a novel proton exchange membrane material with good alcohol resistance and high temperature proton conductivity was successfully prepared.
【學(xué)位授予單位】：長(zhǎng)春工業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB383.2;TM911.4

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本文編號(hào)：1372797