發(fā)布時間：2018-01-24 18:12

  本文關(guān)鍵詞： 燃料電池 孔填充 甲醇滲透 環(huán)氧樹脂 質(zhì)子交換膜 納米纖維 靜電紡絲 復(fù)合膜 直接甲醇燃料電池　出處：《吉林大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：作為一種能夠?qū)⒒瘜W(xué)能轉(zhuǎn)化為電能的電化學(xué)裝置,直接甲醇燃料電池由于其體積小,高燃料利用率,低排放和高能量密度等特性,被認(rèn)為是未來最有希望的清潔能源之一,一直以來得到研究工作者的廣泛關(guān)注。質(zhì)子傳導(dǎo)膜是燃料電池的核心部件,它是一種在燃料電池中傳遞質(zhì)子,分隔電池陽極與陰極的電解質(zhì)材料。常用的質(zhì)子傳導(dǎo)膜材料包括全氟磺酸系列,磺化芳香聚合物(如磺化聚芳醚,磺化聚苯并吡唑,磺化聚酰亞胺)等。質(zhì)子傳導(dǎo)膜的質(zhì)子傳導(dǎo)率,機(jī)械穩(wěn)定性,熱穩(wěn)定性,化學(xué)穩(wěn)定性以及尺寸穩(wěn)定性等性能是質(zhì)子傳導(dǎo)膜的關(guān)鍵數(shù)據(jù)。目前,全氟磺酸聚合物(Nafion~?)由于其高質(zhì)子傳導(dǎo)率和較為突出的綜合性能成為了被最廣泛使用的材料。然而全氟磺酸系列膜也存在著許多眾所周知的缺陷,包括造價較高、陽極反應(yīng)速率低、使用壽命有限、溶脹率高等,尤其是甲醇滲透十分嚴(yán)重,這些問題限制了DMFC的進(jìn)一步應(yīng)用。甲醇從陰極滲透到陽極會導(dǎo)致燃料使用效率下降,陰極催化劑中毒,以致整個電池的性能下降。為了減弱甲醇滲透帶來的影響,實(shí)際應(yīng)用中只能使用低于2M濃度的甲醇溶液作為燃料,大大降低了直接甲醇燃料電池的性能�？紤]到水在質(zhì)子傳導(dǎo)中的作用以及燃料濃度對電池性能的影響,為了得到較高的能量密度,10M甲醇水溶液是直接甲醇燃料電池的理想燃料。因此,這種高濃度甲醇溶液的使用就要求質(zhì)子傳導(dǎo)膜具有極小的甲醇滲透率和較高的尺寸穩(wěn)定性。本論文旨在制備適用于高濃度甲醇溶液中的復(fù)合質(zhì)子交換膜,并分別對其機(jī)械性能,熱學(xué)性能,化學(xué)穩(wěn)定性,傳導(dǎo)率和電池性能進(jìn)行了研究,從而探究傳導(dǎo)膜的不同制備方法和材料對DMFC在高濃度甲醇中的電池性能的影響。具體內(nèi)容分為三部分:孔填充復(fù)合質(zhì)子交換膜,靜電紡絲纖維孔隙填充復(fù)合質(zhì)子交換膜和多維紡絲纖維孔隙填充復(fù)合質(zhì)子交換膜。這三部分內(nèi)容基于同樣的理念,即由機(jī)械強(qiáng)度高,阻醇性好的材料與高質(zhì)子傳導(dǎo)率的材料利用孔隙填充的方法制備復(fù)合質(zhì)子交換膜。第一部分,我們成功制備了基于聚醚砜的孔填充質(zhì)子交換膜,并對其性能進(jìn)行了測試。首先合成了具有低磺化度和一定比例氨基的磺化聚醚砜(ASPES),并利用在鑄膜液中引入離子液體的方法制備了ASPES多孔膜,同時研究了制備過程中離子液體的含量對多孔膜孔形貌的影響。接著我們首次合成了環(huán)氧基封端的磺化聚醚砜低聚物(DSPES)作為復(fù)合膜填充電解質(zhì),并用低聚物DSPES對ASPES多孔膜基體進(jìn)行填充,固化交聯(lián),制備復(fù)合膜。由于ASPES磺酸根含量低,在水中具有良好的尺寸穩(wěn)定性,因而抑制了復(fù)合膜的溶脹效應(yīng),溶脹率的降低使得聚合物分子鏈間作用增強(qiáng),同時抑制了甲醇的滲透作用。在氨基作用下,環(huán)氧聚合物在多孔膜中交聯(lián)形成三維結(jié)構(gòu),大大的提高了復(fù)合膜機(jī)械性能,從而進(jìn)一步抑制了復(fù)合膜的溶脹和甲醇滲透效應(yīng)。得到的復(fù)合膜同時具有優(yōu)異的氧化穩(wěn)定性,熱穩(wěn)定性和機(jī)械強(qiáng)度,雖然其質(zhì)子傳導(dǎo)率略低于Nafion~?,但與同類型的孔填充復(fù)合膜相比,其傳導(dǎo)率仍然相對較高,同時,由于復(fù)合膜具有很低的甲醇滲透率,因此在傳導(dǎo)率和甲醇滲透率之間的選擇性較高,遠(yuǎn)高于Nafion~?膜。在10M甲醇溶液中,復(fù)合膜同樣表現(xiàn)出了高于Nafion~?的單電池性能。第二部分,我們成功制備了兩種PDMS和Nafion~?互為填充相的復(fù)合膜為,從納米尺度抑制復(fù)合膜溶脹及甲醇滲透。一種為Nafion~?填充PDMS靜電紡纖維復(fù)合膜,一種為PDMS填充Nafion~?靜電紡絲纖維復(fù)合膜。我們對兩者及Nafion~?的性能進(jìn)行了測試和比較。實(shí)驗(yàn)中首先分別制備了PDMS和Nafion~?的纖維膜,并分別按照不同的比例使用Nafion~?溶液填充PDMS纖維膜,使用PDMS填充Nafion~?纖維膜。靜電紡絲纖維和填充后的復(fù)合膜表面及截面的形貌同過掃描電鏡度進(jìn)行了表征。由復(fù)合膜和Nafion~?的吸水率溶脹率測試結(jié)果發(fā)現(xiàn),由于疏水性PDMS的引入,復(fù)合膜的吸水溶脹率要遠(yuǎn)低于Nafion~?膜。同時復(fù)合膜的熱穩(wěn)定性氧化穩(wěn)定性在熱失重分析和芬頓試劑測試中均優(yōu)于Nafion~?膜。復(fù)合膜和Nafion~?膜在10M甲醇水溶液中的電池性能同樣與Nafion~?進(jìn)行了比較,證明復(fù)合膜在高濃度甲醇溶液中的電池性能要高于Nafion~?膜,且Nafion~?為填充相時,復(fù)合膜電池性能性能提升幅度較大。第三部分,由上述實(shí)驗(yàn)可知Nafion~?為填充主體時復(fù)合膜電池性能更優(yōu),同時為了提高纖維膜的可填充充性,我們制備了以Nafion~?為填充主體的超薄的聚偏氟乙烯(PVDF)靜電紡絲纖維復(fù)合膜和PVDF/PTFE混合靜電紡絲纖維與Nafion的復(fù)合膜,并將其纖維層用作復(fù)合膜中甲醇的阻醇層。首先我們制備了一系列Nafion~?填充的多層靜電紡絲PVDF纖維復(fù)合膜,并對其與Nafion~?膜的性能進(jìn)行了測試和比較。纖維及復(fù)合膜的形貌和結(jié)構(gòu),熱穩(wěn)定性,機(jī)械穩(wěn)定性,化學(xué)穩(wěn)定性,質(zhì)子傳導(dǎo)率以及單電池性能均得到了表征。與Nafion~?膜相比,PVDF纖維膜的引入顯著的增強(qiáng)了復(fù)合膜的熱穩(wěn)定性和化學(xué)穩(wěn)定性,同時抑制了膜的吸水溶脹作用。復(fù)合膜在10M甲醇溶液中同時表現(xiàn)出了相比于Nafion~?更高的電池性能,然而復(fù)合膜的電池性能相近,并沒有隨著PVDF纖維膜層數(shù)的增加而升高�；谝陨蠈�(shí)驗(yàn)結(jié)果,我們又設(shè)計制備了單側(cè)(陽極側(cè)和陰極側(cè))具有單層PTFE/PVDF纖維阻醇層的Nafion~?115復(fù)合膜,并對其在5 M和10 M甲醇溶液中的電池性能進(jìn)行了測試。測試結(jié)果表明相比于商業(yè)化的Nafion~?115膜,復(fù)合膜的電池性的得到了較大的提高,同時電池的能量密度隨著PTFE在纖維中的質(zhì)量分?jǐn)?shù)的升高而升高,此外,PTFE/PVDF纖維膜在電池陽極側(cè)時,電池性能要高于其在電極陰極側(cè)時。在以上三部分實(shí)驗(yàn)中,分別制備了一系列的多種孔填充復(fù)合膜,包括多孔填充膜和靜電紡絲纖維填充膜等。這些膜的性能在實(shí)驗(yàn)中得到了多方面的測試,尤其是膜在高濃度甲醇溶液中的單電池性能,測試結(jié)果表明了復(fù)合膜孔填充制備方法以及使用材料的有效性,復(fù)合膜的性能均優(yōu)于Nafion~?膜,并通過不斷的改進(jìn),制備的陽極單側(cè)9%PTFE/PVDF與Nafion~?115的性能要遠(yuǎn)好于商用Nafion~?115且方法制備簡單易行,不破壞商品膜的內(nèi)部結(jié)構(gòu),具有重要的參考意義。
[Abstract]:As a way to convert chemical energy into electrical energy electrochemical devices, direct methanol fuel cell because of its small volume, high fuel utilization, low emission characteristics and high energy density, is considered one of the most promising future clean energy, has been widely concerned. The research work is a proton conducting membrane the core components of the fuel cell, it is a kind of proton transfer in the fuel cell, electrolyte battery anode and cathode materials separation. Proton conducting membrane materials used include perfluorinated sulfonic acid series, sulfonated aromatic polymer (such as sulfonated poly aryl ether, sulfonated polyphenylene and pyrazole, sulfonated polyimide). Proton conducting proton conducting membrane the rate of mechanical stability, thermal stability, chemical stability and dimensional stability performance is the key data of proton conducting membrane. At present, perfluorosulfonic acid polymer (Nafion~?) because of its high proton conductivity The comprehensive performance of the more prominent and become the most widely used materials. However Nafion film series also has many defects including high cost as everyone knows, the anode, the reaction rate is low, the service life is limited, the swelling rate higher, especially the methanol permeability is very serious, these problems limit the further application of DMFC from methanol. The cathode to anode penetration will lead to a decline in fuel efficiency, cathode catalyst poisoning, so the battery performance decline. In order to reduce methanol permeability caused by the practical application can be used in the lower concentration of 2M methanol as fuel, greatly reduces the performance of a direct methanol fuel cell. Considering the effect of water on proton conduction in and the fuel concentration on the performance of the battery, in order to obtain a higher energy density, 10M methanol water solution is an ideal fuel for direct methanol fuel cell. So Using this, the dimensional stability of high concentration methanol solution requires a proton conducting membrane with minimal methanol permeability and high proton. This thesis is suitable for preparation of high concentration methanol solution exchange membrane, and the mechanical properties, thermal properties, chemical stability, conductivity and cell performance were studied. Effects of different preparation methods and materials to explore the conductive film on the battery performance of DMFC in high concentration of methanol. The specific content is divided into three parts: the hole filling composite proton exchange membrane, electrospun fibers, complex pore filling alloy PEM and multidimensional spinning fiber pore filling composite proton exchange membrane. These three parts based on the same concept, namely, high mechanical strength, method of pore filling materials prepared by methanol well with high proton conductivity of composite proton exchange membrane. The first part, I We successfully prepared PES hole filling based on proton exchange membrane, and its performance was tested. The first synthesis of sulfonated polyethersulfone with low sulfonation degree and a certain proportion of amino group (ASPES), ASPES and preparation of porous membrane by means of introducing ionic liquids in casting solution were also studied. The influence of content of ionic liquid in the preparation process on the pore morphology. Then we synthesized sulfonated polyether sulfone epoxy terminated oligomer (DSPES) as the composite membrane filled with electrolyte, and the porous ASPES matrix are filled with DSPES polymer crosslinking, preparation of composite film. Because the ASPES sulfonic acid content low, has good dimensional stability in water, thus inhibiting the swelling effect of the composite membrane, reduce the swelling rate of the polymer molecular chain enhanced, while inhibiting the penetration of methanol in ammonia medium under the action of the ring Oxygen crosslinked polymer in porous film formed in the three-dimensional structure, greatly improve the mechanical properties of composite membrane, which further inhibit composite membrane swelling and methanol permeability effect. The resulting composite membrane also has excellent oxidation stability, thermal stability and mechanical strength, while the proton conductivity is slightly lower than Nafion~, but with the same type? The hole is filled with a composite film, its transmission rate is high, is still relatively at the same time, because the methanol permeability of composite membrane has very low, so in between the conductivity and methanol permeability of high selectivity, far higher than Nafion~? Membrane. In methanol solution of 10M, composite membrane also showed higher than that of Nafion~? The single cell performance. The second part, we successfully prepared two kinds of PDMS and Nafion~? Are filled composite film phase, from nano scale inhibition of composite membrane swelling and methanol permeability. A Nafion~ filled PDMS electrospun fiber? Dimensional composite film, a PDMS filled Nafion~? Electrospun fiber composite membrane. We both and Nafion~? Performance were tested and compared. In this experiment, PDMS and Nafion~ respectively were prepared? The fiber membrane, and respectively according to the ratio of Nafion~? PDMS solution filling fiber membrane, filling Nafion~ PDMS? Fiber membrane. Membrane surface and cross-section morphology of the composite fibers by electrospinning and after filling were characterized with scanning electron microscopy. The composite membrane and Nafion~? Water absorption swelling rate test results showed that due to the introduction of hydrophobic PDMS, the swelling rate of composite membrane is much lower than that of Nafion~ membrane. At the same time? The thermal stability of the oxidation stability of composite membrane in thermogravimetric analysis and Fenton reagent test was superior to Nafion~ membrane and Nafion~ membrane.?? The same with the performance of Nafion~ battery membrane in 10M methanol in aqueous solution were compared to prove that? The battery performance of membrane in high concentration methanol solution was higher than that of Nafion~ film, and Nafion~?? as the filling phase, the battery performance of composite membrane to improve greatly. The third part, the experiment shows that Nafion~ is the main performance? Filled composite membrane cell better, at the same time in order to improve can be filled with fiber membrane and we were prepared using Nafion~ as the main filling? Thin polyvinylidene fluoride (PVDF) composite membrane electrospun fiber composite membrane and PVDF/PTFE mixed electrospun fibers and Nafion, and the fiber layer is used as the methanol methanol layer in the composite film. First, we prepared a series of Nafion~ multilayer prepared? The electrospun PVDF fiber composite membrane filled, and the Nafion~? Membrane properties were tested and compared. The morphology and structure of fiber and composite membrane, thermal stability, mechanical stability, chemical stability, proton conductivity and single cell. Could have been characterized with Nafion~? Film compared to the introduction of PVDF fiber membrane significantly enhances the thermal stability of composite membranes and chemical stability, and restrain the swelling effect of membrane. The composite film in 10M methanol solution at the same time show compared to the Nafion~ battery? Higher performance, but the performance of the composite battery the film is similar, and not increased with the increasing of PVDF fiber layers. Based on the above experimental results, we designed the unilateral preparation (anode side and cathode side) with single PTFE/PVDF fiber methanol layer Nafion~? 115 composite film, and the 5 M and 10 M methanol solution in battery performance tested. Test results show that compared to the commercial Nafion~? 115 membrane, composite membrane of the cell was improved, and the energy density of the battery is increased with the increase of mass fraction of PTFE in the fiber and PTFE/PV DF fiber membrane in the anode side, the battery performance is higher than that of the cathode side. In the above three parts were prepared in the experiment, a series of multiple hole filling composite membrane comprises a porous membrane and filled electrospun fibers filled membrane. The performance of these membranes was tested in many aspects in the experiment, especially the single cell performance of membrane in high concentration methanol solution, the test results show that the composite membrane pore filling preparation method and the effectiveness of the use of materials, the performance of composite membranes were better than those of Nafion~? Film, and through continuous improvement, preparation of anode unilateral 9%PTFE/PVDF with Nafion~? 115 performance be far better than the commercial Nafion~? 115 and the preparation method is simple and easy, does not destroy the internal structure of commercial membranes, which has important reference significance.

【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ425.236;TM911.4

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