本文選題：磺化聚芳醚砜 + 側(cè)鏈�。� 參考：《南京理工大學(xué)》2015年碩士論文

【摘要】：作為燃料電池用的電解質(zhì)膜,全氟聚合物膜因?yàn)槠鋬?yōu)異的化學(xué)和物理穩(wěn)定性,高濕低溫下的高質(zhì)子電導(dǎo)率而被廣泛應(yīng)用,例如Nafion和Flemion系列。然而,它們也存在著操作溫度低、成本高、燃料滲透率高等缺點(diǎn)。為了克服這些缺點(diǎn),學(xué)者們開始研究低成本、高效率的芳香族質(zhì)子交換膜。本論文致力于開發(fā)新型的側(cè)鏈型質(zhì)子交換膜材料,通過交聯(lián)、復(fù)合等方法進(jìn)一步進(jìn)行材料改性,并對其性能與結(jié)構(gòu)的關(guān)系進(jìn)行了討論,主要包括質(zhì)子電導(dǎo)率、吸水率、尺寸變化、水解穩(wěn)定性、機(jī)械強(qiáng)度等。以十氟聯(lián)苯、4'4-二羥基二苯砜及2-萘酚-6,8-二磺酸鉀為原料通過親核取代反應(yīng)制備了一系列新型磺化聚醚砜質(zhì)子交換膜SPES-NDSx。所制備的膜(IEC=1.22-2.07 mmol/g)表現(xiàn)出極低的吸水率(27-58%)及優(yōu)異的尺寸穩(wěn)定性。60℃下,SPES-NDS60(1.68 mmol/g)的電導(dǎo)率達(dá)到124 mS/cm,吸水率僅為40%。在合成SPES-NDSx及磺化聚酰亞胺(SPI)兩種聚合物的基礎(chǔ)上,采用不同配比,制備了一系列SPES-NDSx/SPI復(fù)合型質(zhì)子交換膜,并對其性能進(jìn)行了研究。結(jié)果表明,由于SPI的引入,復(fù)合膜的尺寸穩(wěn)定性及機(jī)械性能都有了較大的提高,它們的水解穩(wěn)定性也大大提高,在140℃水中高溫處理24h后,所有復(fù)合膜都仍然具有Ⅳ級以上的穩(wěn)定度,重量損失也都控制在6%以內(nèi)。雖然復(fù)合膜的質(zhì)子電導(dǎo)率隨著SPI含量比例的增加而降低,但SPES-NDS70/SPI系列都顯示出高于Nafion112的質(zhì)子電導(dǎo)率,表現(xiàn)出良好的綜合性能。在合成嵌段型非磺化聚合物主鏈的基礎(chǔ)上,通過引入磺化低聚物作為接枝側(cè)鏈,成功制備了一系列具有不同磺化度及交聯(lián)度的磺化聚醚砜質(zhì)子交換膜bSPAES。因?yàn)榻宦?lián)及側(cè)鏈磺化結(jié)構(gòu)的影響,所有膜都表現(xiàn)出優(yōu)異的尺寸穩(wěn)定性,例如60℃下,所有膜的平面方向尺寸變化都在3%以內(nèi),厚度方向控制在7-16%,尺寸變化的各向異性尤其滿足燃料電池的運(yùn)行需要。同時,bSPAES膜在較低離子交換容量的水平下保持了較高的電導(dǎo)率,其中,bSPAES-5/5膜在整個溫度范圍內(nèi)都表現(xiàn)出與Nafion112相當(dāng)?shù)碾妼?dǎo)率,并具有比Nafion112更優(yōu)異的尺寸性能。
[Abstract]:As electrolyte membranes for fuel cells, perfluoropolymer membranes are widely used because of their excellent chemical and physical stability, high proton conductivity at high humidity and low temperature, such as Nafion and Flemion series. However, they also have the disadvantages of low operating temperature, high cost and high fuel permeability. To overcome these shortcomings, researchers have begun to study low-cost, high-efficiency aromatic proton exchange membranes. This paper is devoted to the development of new side chain proton exchange membrane materials. The properties of the materials are further modified by crosslinking and recombination, and the relationship between the properties and the structure is discussed, including the proton conductivity, water absorption, and so on. Size change, hydrolysis stability, mechanical strength, etc. A series of novel sulfonated polyether sulfone proton exchange membranes SPES-NDSx were prepared by nucleophilic substitution reaction with decafluorinated biphenyl 4- dihydroxy diphenyl sulfone and 2-naphthol -6o 8-disulfonic acid potassium as raw materials. The prepared membranes (IECs 1.22-2.07 mmol/g) showed extremely low water absorption (27-58%) and excellent dimensional stability. The conductivity of SPES-NDS60 (1.68 mmol/g) was 124mS-1 路cmand the water absorption was only 40mS-1 路cm. Based on the synthesis of SPES-NDSx and sulfonated polyimide (SPI), a series of SPES-NDSx / SPI composite proton exchange membranes were prepared and their properties were studied. The results showed that the dimensional stability and mechanical properties of the composite membranes were greatly improved and the hydrolysis stability was greatly improved because of the introduction of SPI. The composite membranes were treated at high temperature at 140 鈩，

本文編號：2092237