新型聚合物電解質(zhì)基復(fù)合質(zhì)子傳輸膜的制備及其性能研究
發(fā)布時間：2019-07-06 18:16
【摘要】：質(zhì)子交換膜(PEM)作為質(zhì)子交換膜燃料電池(PEMFC)的核心部件在很大程度上決定了PEMFC性能的好壞。現(xiàn)在廣泛應(yīng)用于PEMFC的PEM是杜邦公司生產(chǎn)的Nafion膜。雖然Nafion膜具有高質(zhì)子傳導(dǎo)、化學(xué)穩(wěn)定性好等優(yōu)點，但它的質(zhì)子傳導(dǎo)強烈依賴膜內(nèi)的水含量，高溫時膜性能急劇下降，在作為直接甲醇燃料電池(DMFC)的PEM時燃料滲透嚴重，并且Nafion的生產(chǎn)過程復(fù)雜，造價昂貴。這些問題都是影響Nafion廣泛應(yīng)用的重要原因�；腔姆枷阕寰垭娊赓|(zhì)由于具有良好的機械性能，化學(xué)穩(wěn)定性和熱穩(wěn)定性，尤其是低于Nafion的甲醇滲透和生產(chǎn)成本，，使其在近年的PEM研究中備受科研和能源開發(fā)機構(gòu)的青睞。我們知道，在PEM中質(zhì)子的傳導(dǎo)主要是在膜的親水區(qū)域內(nèi)，親水區(qū)的連續(xù)性越好越有利于質(zhì)子傳導(dǎo)。在磺化的無規(guī)共聚物膜中，磺酸基會聚集形成大的離子簇，親水區(qū)之間的相對間距很大，因此質(zhì)子不能在這種結(jié)構(gòu)中快速的傳導(dǎo)。為了獲得綜合性能好，并且具有連續(xù)質(zhì)子傳輸通道的PEM，很多方法被用于制備改性PEM。 在本論文中，我們以磺化芳香聚電解質(zhì)作為基體，用不同的方法構(gòu)筑了一系列綜合性能好，具有連續(xù)離子簇網(wǎng)絡(luò)和長程質(zhì)子傳輸通道的復(fù)合質(zhì)子交換膜材料。具體工作分為四個部分： 在第一部分工作中，我們利用原位聚合的方法將具有大量酰胺鍵的聚異丙基丙烯酰胺(PNIPAm)引入到無規(guī)共聚合SPI基體中，制備了一系列具有不同PNIPAm含量的SPI-cPNIPAm半互穿網(wǎng)絡(luò)PEM。PNIPAm中的酰胺鍵與SPI中的磺酸基之間形成的氫鍵相作用以及半互穿的三維網(wǎng)絡(luò)結(jié)構(gòu)能夠調(diào)節(jié)復(fù)合膜的微觀結(jié)構(gòu)和性能。當磺酸基和酰胺鍵摩爾比為1:1時，SPI-20%-cPNIPAm膜樣品中離子簇尺寸最小，分布均勻且連續(xù)，形成了利于質(zhì)子傳導(dǎo)的通道。25oC時，該樣品膜的質(zhì)子傳導(dǎo)是純SPI膜的2倍，電池能量密度由純膜的44mW cm2提高到72mW cm2。同時復(fù)合膜也具有良好的機械性能和熱穩(wěn)定性。 在第二部分工作中，我們從不同尺寸石墨出發(fā)，制備了三種具有不同尺寸的氧化石墨烯(GO)。將不同尺寸的GO與SPI復(fù)合，用于考察GO的尺寸效應(yīng)對SPI/GO復(fù)合膜微觀結(jié)構(gòu)和性能的影響。研究發(fā)現(xiàn)，在相同的含量下，尺寸最小的GO對SPI基體的微觀結(jié)構(gòu)和性能影響最大。在最小GO摻雜為0.5wt%的PEM中離子簇從純SPI膜中的25nm縮小到6nm，分布均勻且連續(xù)，形成了有利于質(zhì)子傳導(dǎo)的微觀結(jié)構(gòu)。同時25oC下，這個樣品膜的質(zhì)子傳導(dǎo)高于純SPI膜4倍。復(fù)合膜的機械性能、抗氧化穩(wěn)定性、尺寸穩(wěn)定性和阻醇性能也都有不同程度上的提高。實驗結(jié)果說明，GO的引入能夠調(diào)節(jié)PEM的微觀結(jié)構(gòu)，優(yōu)化PEM的綜合性能。 在第三部分工作中，我們通過8-羥基喹啉-5-磺酸鹽中的羥基與3-異氰酸酯基丙基三乙氧基硅烷中的異氰酸酯的反應(yīng)，得到了含有氮雜環(huán)和磺酸基的有機硅氧烷偶聯(lián)劑(SiSQ)。在表面活性劑(模板劑)的存在下，采用溶膠-凝膠的方法將SiSQ引入到SPI基體中，得到了一系列含有不同介孔有硅氧烷(MsiSQ)摻雜量的SPI-MSiSQ復(fù)合膜。研究發(fā)現(xiàn)MSiSQ相與SPI基體之間有更好的相容性，磺酸基的引入減少了摻雜組分對SPI膜中磺酸基濃度的稀釋作用。復(fù)合膜的質(zhì)子傳導(dǎo)和阻醇性隨著MSiSQ含量的增加而增加。當MSiSQ含量為40wt%時，在25oC下，復(fù)合膜的質(zhì)子傳導(dǎo)為0.23S cm-1，甲醇滲為1.8×10-8cm2/S，選擇性為12.8×106Sscm-3，這與純膜相比分別提高了3、6、23倍。這主要歸因于：一方面是MSiSQ中的喹啉氮原子與SPI中的磺酸基之間的相互作用促使SPI中的大尺寸離子簇分散成尺寸更小的離子簇，在膜中形成了均一連續(xù)的質(zhì)子傳輸通道；另一方面則是磺化有機硅氧烷中的磺酸基與表面活性劑作用，去除表面活性劑后磺酸基聚集在介孔內(nèi)，為質(zhì)子的傳導(dǎo)提供了長程的質(zhì)子傳導(dǎo)通道。此外，復(fù)合膜的電池性能、機械性能、熱穩(wěn)定性和抗氧化性都有很大程度的提高，有望用于DMFC。 在第四部分工作中，我們以聚酯纖維為基底，利用GO與SPES之間的氫鍵相互作用，使兩者通過層層組裝的方式在聚酯纖維的表面形成GO與SPES組裝的多層結(jié)構(gòu)，每一層中磺酸基都沿纖維軸向排列，這為質(zhì)子的傳導(dǎo)提供了長程的質(zhì)子傳導(dǎo)通道，促進質(zhì)子的快速傳導(dǎo)。將SPES與多層組裝聚酯纖維復(fù)合，并對復(fù)合膜的結(jié)構(gòu)和性質(zhì)進行了表征。結(jié)果表明：隨著組裝層的增加復(fù)合膜中的質(zhì)子傳導(dǎo)率逐漸升高。同時復(fù)合膜的機械性能和阻醇性也比純SPES膜有明顯的提高。實驗證明層層結(jié)構(gòu)修飾的纖維能構(gòu)筑更多長程質(zhì)子傳輸通道。
文內(nèi)圖片：
圖片說明：所示，反應(yīng)物H2和O2在擴散層擴散；反應(yīng)氣體到達催化層后被催
[Abstract]:The core components of the proton exchange membrane (PEM) as the proton exchange membrane fuel cell (PEMFC) largely determine the performance of the PEMFC. The PEM, which is now widely used in PEMFC, is a Nafion membrane produced by DuPont. while the nafion membrane has the advantages of high proton conduction and good chemical stability, the proton conduction of the nafion membrane strongly depends on the water content in the membrane, the performance of the membrane drops sharply at the high temperature, the fuel penetration is serious when the pem is a direct methanol fuel cell (dmfc), and the production process of the nafion is complex, And the cost is high. These problems are important factors that affect the wide application of Nafion. Sulfonated aromatic polyelectrolytes have been favored by scientific research and energy development agencies in recent PEM studies due to good mechanical properties, chemical stability and thermal stability, in particular less than Nafion's methanol penetration and production costs. We know that the better the proton conduction in the PEM is in the hydrophilic region of the membrane, the better the continuity of the hydrophilic region is, the better the proton conduction. In the sulfonated random copolymer film, the sulfonic acid resin aggregates to form a large ion cluster, and the relative distance between the hydrophilic regions is large, so that the protons cannot be rapidly conducted in such a structure. In order to obtain a PEM with a good comprehensive performance and a continuous proton transfer channel, many methods are used to prepare the modified PEM. In this paper, we use the sulfonated aromatic polyelectrolytes as the matrix to construct a series of composite proton exchange membrane with continuous ion cluster network and long-range proton transport channel with different methods. Material. The specific work is divided into four parts in that first part of the work, we use the method of in situ polymerization to introduce a polyisopropylamide (PNIPAm) with a large amount of amine bond into the random copolymerization SPI In the matrix, a series of SPI-cPNIPAm semi-interpenetrating network PEM with different PNIPAm content is prepared. The hydrogen bonding phase and the semi-interpenetrating three-dimensional network structure of the amine bond in the PNIPAm and the sulfonic acid groups in the SPI can be used to adjust the microstructure of the composite membrane. And when the molar ratio of the sulfonic acid group and the melamine bond is 1:1, the size of the ion cluster in the SPI-20%-cPNIPAm membrane sample is the smallest, the distribution is uniform and continuous, the channel favorable for proton conduction is formed, the proton conduction of the sample membrane is twice the pure SPI film at the time of 25oC, and the energy density of the battery is increased to 72 mW by the 44 mW cm2 of the pure film. cm2. The composite membrane also has good mechanical properties and heat In that second part of the work, three of the graphite oxide with different size were prepared from different size of graphite. The GO is combined with the SPI to investigate the size effect of GO to the microstructure of the SPI/ GO composite membrane. The effect of GO on the micro-structure and properties of the SPI matrix at the same content was found. Can influence the maximum. In the PEM with the minimum GO doping of 0.5 wt%, the ion cluster is reduced from 25 nm in the pure SPI film to 6 nm, the distribution is uniform and continuous, and the proton conduction is facilitated. At the same time, the proton conductivity of this membrane is higher than that of pure S at 25 oC. The mechanical properties, the anti-oxidation stability, the dimensional stability and the alcohol-resistance of the composite membrane are also different. The results show that the introduction of GO can adjust the micro-structure of the PEM and optimize the PEM. In the work of the third part, the coupling of the organic siloxane containing the nitrogen heterocyclic group and the sulfonic acid group is obtained by the reaction of the hydroxyl groups in the 8-hydroxy-1-5-sulfonate with the isocyanate in the 3-isocyanate-based propyltriethoxysilane. In the presence of a surfactant (templating agent), a sol-gel method is used to introduce the SiSQ into the SPI matrix, and a series of SPI-M containing different mesoporous siloxane (MsiSQ) doping amount is obtained. SiSQ composite membrane has been found to have a better compatibility between the MSiSQ phase and the SPI matrix, and the introduction of the sulfonic acid group reduces the sulfonic acid group in the SPI film by the doping component. The proton conductivity and alcohol resistance of the composite membrane with MSiSQ The amount is increased. When the MSiSQ content is 40% by weight, the proton conductivity of the composite membrane is 0.23 S cm-1 at 25 DEG C, the methanol permeability is 1.8 to 10 to 8 cm2/ S, the selectivity is 12.8 to 106 Sscm-3, which is improved compared with the pure film, respectively. 3,6,23 times. This is due mainly to: on the one hand, the interaction between the diatomic nitrogen atom in MSiSQ and the sulfonic acid group in the SPI causes the large-sized ion cluster in the SPI to be dispersed into smaller ion clusters, and a uniform continuous film is formed in the film. And on the other hand, the sulfonic acid group and the surfactant in the sulfonated organic siloxane are used for removing the surfactant, the sulfonic acid groups are collected in the mesoporous, and the long-range conduction of the protons is provided. in addition, the battery performance, the mechanical property, the thermal stability and the oxidation resistance of the composite membrane are greatly improved, in that work of the fourth part, we use the polyester fiber as the substrate, and use the hydrogen bond interaction between GO and SPES to form the multi-layer structure of GO and SPES assembly on the surface of the polyester fiber by layer-by-layer assembly, and the sulfonic acid in each layer the base is arranged axially along the fiber, which provides a long-range proton conduction path for the conduction of the protons, to promote the rapid conduction of the protons. The SPES is compounded with the multi-layer assembled polyester fiber, and the junction of the composite film The structure and properties of the composite film are characterized. The results show that with the increase of the assembly layer, the composite film The proton conductivity is gradually increased, and the mechanical property and the resistance of the composite membrane are also higher than that of the pure SP. The experimental results show that the layer-by-layer structure-modified fibers can be constructed
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TM911.4;O631.1
本文編號：2511241
文內(nèi)圖片：
圖片說明：所示，反應(yīng)物H2和O2在擴散層擴散；反應(yīng)氣體到達催化層后被催
[Abstract]:The core components of the proton exchange membrane (PEM) as the proton exchange membrane fuel cell (PEMFC) largely determine the performance of the PEMFC. The PEM, which is now widely used in PEMFC, is a Nafion membrane produced by DuPont. while the nafion membrane has the advantages of high proton conduction and good chemical stability, the proton conduction of the nafion membrane strongly depends on the water content in the membrane, the performance of the membrane drops sharply at the high temperature, the fuel penetration is serious when the pem is a direct methanol fuel cell (dmfc), and the production process of the nafion is complex, And the cost is high. These problems are important factors that affect the wide application of Nafion. Sulfonated aromatic polyelectrolytes have been favored by scientific research and energy development agencies in recent PEM studies due to good mechanical properties, chemical stability and thermal stability, in particular less than Nafion's methanol penetration and production costs. We know that the better the proton conduction in the PEM is in the hydrophilic region of the membrane, the better the continuity of the hydrophilic region is, the better the proton conduction. In the sulfonated random copolymer film, the sulfonic acid resin aggregates to form a large ion cluster, and the relative distance between the hydrophilic regions is large, so that the protons cannot be rapidly conducted in such a structure. In order to obtain a PEM with a good comprehensive performance and a continuous proton transfer channel, many methods are used to prepare the modified PEM. In this paper, we use the sulfonated aromatic polyelectrolytes as the matrix to construct a series of composite proton exchange membrane with continuous ion cluster network and long-range proton transport channel with different methods. Material. The specific work is divided into four parts in that first part of the work, we use the method of in situ polymerization to introduce a polyisopropylamide (PNIPAm) with a large amount of amine bond into the random copolymerization SPI In the matrix, a series of SPI-cPNIPAm semi-interpenetrating network PEM with different PNIPAm content is prepared. The hydrogen bonding phase and the semi-interpenetrating three-dimensional network structure of the amine bond in the PNIPAm and the sulfonic acid groups in the SPI can be used to adjust the microstructure of the composite membrane. And when the molar ratio of the sulfonic acid group and the melamine bond is 1:1, the size of the ion cluster in the SPI-20%-cPNIPAm membrane sample is the smallest, the distribution is uniform and continuous, the channel favorable for proton conduction is formed, the proton conduction of the sample membrane is twice the pure SPI film at the time of 25oC, and the energy density of the battery is increased to 72 mW by the 44 mW cm2 of the pure film. cm2. The composite membrane also has good mechanical properties and heat In that second part of the work, three of the graphite oxide with different size were prepared from different size of graphite. The GO is combined with the SPI to investigate the size effect of GO to the microstructure of the SPI/ GO composite membrane. The effect of GO on the micro-structure and properties of the SPI matrix at the same content was found. Can influence the maximum. In the PEM with the minimum GO doping of 0.5 wt%, the ion cluster is reduced from 25 nm in the pure SPI film to 6 nm, the distribution is uniform and continuous, and the proton conduction is facilitated. At the same time, the proton conductivity of this membrane is higher than that of pure S at 25 oC. The mechanical properties, the anti-oxidation stability, the dimensional stability and the alcohol-resistance of the composite membrane are also different. The results show that the introduction of GO can adjust the micro-structure of the PEM and optimize the PEM. In the work of the third part, the coupling of the organic siloxane containing the nitrogen heterocyclic group and the sulfonic acid group is obtained by the reaction of the hydroxyl groups in the 8-hydroxy-1-5-sulfonate with the isocyanate in the 3-isocyanate-based propyltriethoxysilane. In the presence of a surfactant (templating agent), a sol-gel method is used to introduce the SiSQ into the SPI matrix, and a series of SPI-M containing different mesoporous siloxane (MsiSQ) doping amount is obtained. SiSQ composite membrane has been found to have a better compatibility between the MSiSQ phase and the SPI matrix, and the introduction of the sulfonic acid group reduces the sulfonic acid group in the SPI film by the doping component. The proton conductivity and alcohol resistance of the composite membrane with MSiSQ The amount is increased. When the MSiSQ content is 40% by weight, the proton conductivity of the composite membrane is 0.23 S cm-1 at 25 DEG C, the methanol permeability is 1.8 to 10 to 8 cm2/ S, the selectivity is 12.8 to 106 Sscm-3, which is improved compared with the pure film, respectively. 3,6,23 times. This is due mainly to: on the one hand, the interaction between the diatomic nitrogen atom in MSiSQ and the sulfonic acid group in the SPI causes the large-sized ion cluster in the SPI to be dispersed into smaller ion clusters, and a uniform continuous film is formed in the film. And on the other hand, the sulfonic acid group and the surfactant in the sulfonated organic siloxane are used for removing the surfactant, the sulfonic acid groups are collected in the mesoporous, and the long-range conduction of the protons is provided. in addition, the battery performance, the mechanical property, the thermal stability and the oxidation resistance of the composite membrane are greatly improved, in that work of the fourth part, we use the polyester fiber as the substrate, and use the hydrogen bond interaction between GO and SPES to form the multi-layer structure of GO and SPES assembly on the surface of the polyester fiber by layer-by-layer assembly, and the sulfonic acid in each layer the base is arranged axially along the fiber, which provides a long-range proton conduction path for the conduction of the protons, to promote the rapid conduction of the protons. The SPES is compounded with the multi-layer assembled polyester fiber, and the junction of the composite film The structure and properties of the composite film are characterized. The results show that with the increase of the assembly layer, the composite film The proton conductivity is gradually increased, and the mechanical property and the resistance of the composite membrane are also higher than that of the pure SP. The experimental results show that the layer-by-layer structure-modified fibers can be constructed
【學(xué)位授予單位】：東北師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TM911.4;O631.1
【參考文獻】
相關(guān)期刊論文 前4條
1 侯明;衣寶廉;;燃料電池技術(shù)發(fā)展現(xiàn)狀與展望[J];電化學(xué);2012年01期
2 龔光明;吳俊濤;江雷;;靜電紡絲法制備聚酰亞胺新型材料[J];化學(xué)進展;2011年04期
3 師奇松,于建香,顧克壯,馬春寶,劉太奇;靜電紡絲技術(shù)及其應(yīng)用[J];化學(xué)世界;2005年05期
4 王誠;;燃料電池技術(shù)開發(fā)現(xiàn)狀及發(fā)展趨勢[J];新材料產(chǎn)業(yè);2012年02期
本文編號：2511241
本文鏈接：http://sikaile.net/kejilunwen/dianlilw/2511241.html
最近更新
教材專著
