本文選題：燃料電池　切入點：質(zhì)子交換膜　出處：《蘭州大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：質(zhì)子交換膜作為質(zhì)子交換膜燃料電池的核心組成部分,直接決定著燃料電池工作性能與使用壽命,目前由杜邦公司生產(chǎn)并制造的商業(yè)化Nafion系列膜具有較高的質(zhì)子傳導(dǎo)率以及良好的綜合性能,但以Nafion膜為代表的全氟磺酸型質(zhì)子交換膜依舊存在諸如甲醇滲透率高、造價昂貴、易溶脹、質(zhì)子傳導(dǎo)率嚴(yán)重依賴膜內(nèi)含水量等缺點。雖然以改性、摻雜、交聯(lián)等方法為基礎(chǔ)的磺化芳香族聚合物使磺酸型質(zhì)子交換膜的性能得到了一定改善,但高磺化度的磺化芳香族聚合物仍然會使膜過度溶脹,降低水和條件下的穩(wěn)定性。酸堿類聚合物質(zhì)子交換膜通過聚合物結(jié)構(gòu)中帶有堿性的官能團(tuán)與摻雜的酸性基團(tuán)進(jìn)行酸堿相互作用,或者以聚合物中同時存在的酸性與堿性基團(tuán)進(jìn)行作用,使聚合物膜吸收一定含量的酸來完成質(zhì)子傳導(dǎo)。這類質(zhì)子交換膜對濕度的依賴較低,具有較為可觀的質(zhì)子傳導(dǎo)能力,而且在熱穩(wěn)定性、吸水溶脹率以及耐水解性等綜合性能方面都能夠滿足質(zhì)子交換膜的要求。本文選取具有較好的機(jī)械性能、優(yōu)異的熱穩(wěn)定性以及耐腐蝕性能的聚芳醚砜為主體材料,以具有堿性基團(tuán)且能以氫鍵作用進(jìn)行結(jié)合的生命體重要組成結(jié)構(gòu)——堿基腺嘌呤為改性結(jié)構(gòu),設(shè)計并制備溶脹率較低、傳導(dǎo)率較高、綜合性能良好的酸堿性質(zhì)子交換膜,主要從以下兩方面進(jìn)行研究。具體包括:1.通過接枝的方法將腺嘌呤接入到聚合物側(cè)鏈,制備側(cè)鏈含有腺嘌呤結(jié)構(gòu)的聚芳醚砜類聚合物,通過聚芳醚砜側(cè)鏈的堿性基團(tuán)與摻雜鹽酸進(jìn)行作用,形成腺嘌呤接枝型酸堿質(zhì)子交換膜PAES-A-x,同時測試了PAES-A-x的質(zhì)子傳導(dǎo)率以及其他綜合性能。結(jié)果表明,腺嘌呤接枝型酸堿質(zhì)子交換膜PAES-A-x具有較為可觀的質(zhì)子傳導(dǎo)率,且在具有較低溶脹率的同時,具有良好的熱穩(wěn)定性和機(jī)械性能以滿足質(zhì)子交換膜材料的要求。2.制備主鏈含有帶吡啶結(jié)構(gòu)的Cardo型聚芳醚砜材料,進(jìn)一步摻雜堿基腺嘌呤與聚合物通過氫鍵作用進(jìn)行結(jié)合,摻雜鹽酸后,形成酸化的PPAES/A-x復(fù)合質(zhì)子交換膜,測試該摻雜型質(zhì)子交換膜PPAES/A-x的各項性能,并闡述腺嘌呤引入下堿性基團(tuán)和鹽酸作用后對于質(zhì)子傳導(dǎo)率以及其他綜合性能的影響。結(jié)果表明,分子間氫鍵作用下的PPAES/A-x膜具有良好的吸水率與傳導(dǎo)率的同時,顯著降低了溶脹率,其熱穩(wěn)定性和氧化穩(wěn)定性等其他綜合性能均表現(xiàn)出較高水平。
[Abstract]:The core of the proton exchange membrane as proton exchange membrane fuel cell component, directly determines the performance of the fuel cell and the service life of the proton conduction at present by commercial film DuPont Co Nafion series production and manufacturing has high efficiency and good overall performance, but the fluorosulfonic proton membrane with Nafion as the representative of the exchange film still problems such as high cost, high methanol permeability, easy to swelling, proton conductivity is heavily dependent on membrane water content and other disadvantages. Although the modification, doping, sulfonated aromatic polymer crosslinking method based sulfonic acid proton exchange membrane performance that has been some improvement, but the sulfonated aromatic polymer with high sulfonation degree will still the film excessive swelling, reduce water and stability. Under the condition of functional groups and polymers doped with acid-base proton exchange membrane by polymer structure with alkaline acid Groups of acid-base interactions, or acidic and basic groups also exist in the polymer, the polymer film absorption of certain content of acid to complete proton transfer. This type of proton exchange membrane depends on the humidity is low, with considerable proton conduction ability, and the thermal stability, swelling rate and hydrolysis and other aspects of the comprehensive performance can meet the requirements of the proton exchange membrane. This paper has good mechanical properties, excellent thermal stability and corrosion resistance of polyarylethersulfone as main material, with alkali group and in hydrogen bonding with the weight of life structure is composed of modified adenine the structure, design and preparation of the swelling rate is low, high conductivity, good comprehensive properties of acid-base proton exchange membrane, mainly from the following two aspects including: 1.. The method will be access to the adenine graft polymer side chain, preparation of side chain containing adenine structure poly aryl ether sulfone polymers, the poly aryl ether sulfone side chain alkaline groups and doping hydrochloric acid, the formation of adenine grafted acid-base proton exchange membrane PAES-A-x, and tested the proton conductivity of PAES-A-x and the other comprehensive performance. The results showed that the graft type acid-base proton exchange membrane adenine PAES-A-x has considerable proton conduction rate, and has low swelling rate and has good thermal stability and mechanical properties to meet the requirements of the.2. proton exchange membrane material prepared with pyridine containing Cardo type main chain structure of polyarylethersulfone materials further, doped with adenine and polymer are combined through hydrogen bonding, doped with hydrochloric acid after the formation of the PPAES/A-x composite proton exchange membrane to test the acidification, doped proton exchange The properties of PPAES/A-x film, and expounds the influence on the proton conductivity and other properties of the adenine introduced basic groups and hydrochloric acid. The results show that the intermolecular hydrogen bonding interactions under the PPAES/A-x membrane has good water absorption rate and the transmission rate at the same time, significantly reduced the swelling ratio, its thermal stability and oxidation stability etc. other properties are exhibited a higher level.

【學(xué)位授予單位】：蘭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TM911.4;TB383.2

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