磺化聚醚醚酮及其納米復合質子交換膜的制備與性能研究
發(fā)布時間：2018-11-10 16:57
【摘要】：直接甲醇燃料電池(DMFC)是一種直接以甲醇作燃料的新型質子交換膜燃料電池(PEMFC),具有能量效率高、清潔無污染等優(yōu)點,是現(xiàn)今最有前景的清潔能源之一。質子交換膜(PEM)是DMFC的核心組成部件之一,擔負著傳導質子并分隔陰陽極的雙重作用,對燃料電池的運行狀況起著決定性的作用。但是現(xiàn)在廣泛使用的全氟磺酸膜不僅價格昂貴,還存在著嚴重的甲醇滲透問題,大大降低了燃料電池的性能。因此,需要開發(fā)價格低廉、燃料透過率低的無氟磺化高分子材料�；撬峄勖衙淹�(SPEEK)具有相對高的導質子性、良好的熱穩(wěn)定性和力學性能,且廉價易得,是一種很好的質子交換膜材料。本文成功制備了一系列以乙醇/水混合溶液為溶劑的SPEEK質子交換膜。與以DMAc為溶劑的質子交換膜相比,質子電導率得到提高。成膜溫度對膜的性能有很大的影響。較低的成膜溫度有利于親水相聚集,促進相分離。同時,促進膜表面磺酸基團的聚集排布,從而膜具有更高的質子。首先利用聚多巴胺和十二烷基苯磺酸鈉(SDBS)在石墨相碳化氮(Graphitic Carbon Nitride,g-C_3N_4)的吸附作用,制備了兩種改性g-C_3N_4。將其與SPEEK摻雜制備了SPEEK/改性g-C_3N_4復合質子交換膜。聚多巴胺和SDBS上的親水基團使g-C_3N_4納米片與SPEEK基體的界面相容性提高,復合膜中離子簇相密度增加,親水區(qū)連接性更好,膜中質子流動性增強。摻雜改性g-C_3N_4的復合膜的質子電導率得到提高。g-C_3N_4納米片與SPEEK相互作用,使聚合物鏈的流動性被抑制,甲醇滲透率降低。通過將SDBS和g-C_3N_4均勻分散的混合液直接與SPEEK鑄膜液共混制備了SPEEK/g-C_3N_4/SDBS復合質子交換膜。g-C_3N_4分散均勻,與SPEEK聚合物基質的界面相容性大大改善。SPEEK基體中形成連續(xù)的親水通道,離子簇密度增加,膜中質子流動性增強。此外,SDBS表面的磺酸根與SPEEK聚合物相互作用,形成連續(xù)的離子簇,增加了導電通路。制備的SPEEK/g-C_3N_4/SDBS復合質子交換膜的質子電導率有很大提高,添加2 wt%填料時,導電性比純SPEEK膜提高了60%。
[Abstract]:Direct methanol fuel cell (DMFC) is a new type of proton exchange membrane fuel cell (PEMFC),) with direct methanol as fuel. It has the advantages of high energy efficiency, clean and pollution-free, and is one of the most promising clean energy sources. Proton exchange membrane (PEM) is one of the core components of DMFC, which plays a dual role in conducting protons and separating anode and cathode, and plays a decisive role in the operation of fuel cells. However, the perfluorinated sulfonic acid membrane, which is widely used now, is not only expensive, but also has serious methanol permeation problem, which greatly reduces the performance of fuel cells. Therefore, it is necessary to develop fluorine-free sulfonated polymer materials with low price and low fuel transmittance. Sulfonated polyether ether ketone (SPEEK) is a kind of proton exchange membrane material with relatively high proton conductivity, good thermal stability and mechanical properties. In this paper, a series of SPEEK proton exchange membranes using ethanol / water mixed solution as solvent have been successfully prepared. Compared with the proton exchange membrane using DMAc as solvent, the proton conductivity was improved. The temperature of film formation has a great influence on the performance of the film. Lower film forming temperature is favorable to hydrophilic gathering and promoting phase separation. At the same time, it promotes the aggregation and arrangement of sulfonic groups on the membrane surface, so that the membrane has higher protons. Firstly, two kinds of modified g-C _ 3N _ 4 were prepared by the adsorption of poly (dopamine) and sodium dodecylbenzene sulfonate (SDBS) on graphite-phase carbonized nitrogen (Graphitic Carbon Nitride,g-C_3N_4). SPEEK/ modified g-C_3N_4 composite proton exchange membrane was prepared by doping it with SPEEK. The interfacial compatibility between g-C_3N_4 nanoparticles and SPEEK matrix was improved by the hydrophilic groups on polydopamine and SDBS. The ionic cluster phase density and hydrophilic zone connectivity of the composite membranes were increased, and the proton fluidity in the membranes was enhanced. The proton conductivity of the composite membrane doped with modified g-C_3N_4 was improved. The interaction between g-C_3N_4 nanoparticles and SPEEK inhibited the flowability of polymer chain and decreased the methanol permeability. The SPEEK/g-C_3N_4/SDBS composite proton exchange membrane was prepared by blending the uniformly dispersed mixture of SDBS and g-C_3N_4 with the casting solution of SPEEK directly. The g-C_3N_4 was uniformly dispersed. The interfacial compatibility with SPEEK polymer matrix was greatly improved. A continuous hydrophilic channel was formed in the SPEEK matrix, the ion cluster density increased and the proton fluidity in the membrane increased. In addition, the sulfonic radical on the surface of SDBS interacts with the SPEEK polymer to form a continuous ion cluster, which increases the conduction pathway. The proton conductivity of the SPEEK/g-C_3N_4/SDBS composite proton exchange membrane was greatly improved. The conductivity of the SPEEK/g-C_3N_4/SDBS composite proton exchange membrane was increased by 60% than that of the pure SPEEK membrane when 2 wt% filler was added.
【學位授予單位】：華北電力大學(北京)
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TM911.4;TQ425.23
本文編號：2323030
[Abstract]:Direct methanol fuel cell (DMFC) is a new type of proton exchange membrane fuel cell (PEMFC),) with direct methanol as fuel. It has the advantages of high energy efficiency, clean and pollution-free, and is one of the most promising clean energy sources. Proton exchange membrane (PEM) is one of the core components of DMFC, which plays a dual role in conducting protons and separating anode and cathode, and plays a decisive role in the operation of fuel cells. However, the perfluorinated sulfonic acid membrane, which is widely used now, is not only expensive, but also has serious methanol permeation problem, which greatly reduces the performance of fuel cells. Therefore, it is necessary to develop fluorine-free sulfonated polymer materials with low price and low fuel transmittance. Sulfonated polyether ether ketone (SPEEK) is a kind of proton exchange membrane material with relatively high proton conductivity, good thermal stability and mechanical properties. In this paper, a series of SPEEK proton exchange membranes using ethanol / water mixed solution as solvent have been successfully prepared. Compared with the proton exchange membrane using DMAc as solvent, the proton conductivity was improved. The temperature of film formation has a great influence on the performance of the film. Lower film forming temperature is favorable to hydrophilic gathering and promoting phase separation. At the same time, it promotes the aggregation and arrangement of sulfonic groups on the membrane surface, so that the membrane has higher protons. Firstly, two kinds of modified g-C _ 3N _ 4 were prepared by the adsorption of poly (dopamine) and sodium dodecylbenzene sulfonate (SDBS) on graphite-phase carbonized nitrogen (Graphitic Carbon Nitride,g-C_3N_4). SPEEK/ modified g-C_3N_4 composite proton exchange membrane was prepared by doping it with SPEEK. The interfacial compatibility between g-C_3N_4 nanoparticles and SPEEK matrix was improved by the hydrophilic groups on polydopamine and SDBS. The ionic cluster phase density and hydrophilic zone connectivity of the composite membranes were increased, and the proton fluidity in the membranes was enhanced. The proton conductivity of the composite membrane doped with modified g-C_3N_4 was improved. The interaction between g-C_3N_4 nanoparticles and SPEEK inhibited the flowability of polymer chain and decreased the methanol permeability. The SPEEK/g-C_3N_4/SDBS composite proton exchange membrane was prepared by blending the uniformly dispersed mixture of SDBS and g-C_3N_4 with the casting solution of SPEEK directly. The g-C_3N_4 was uniformly dispersed. The interfacial compatibility with SPEEK polymer matrix was greatly improved. A continuous hydrophilic channel was formed in the SPEEK matrix, the ion cluster density increased and the proton fluidity in the membrane increased. In addition, the sulfonic radical on the surface of SDBS interacts with the SPEEK polymer to form a continuous ion cluster, which increases the conduction pathway. The proton conductivity of the SPEEK/g-C_3N_4/SDBS composite proton exchange membrane was greatly improved. The conductivity of the SPEEK/g-C_3N_4/SDBS composite proton exchange membrane was increased by 60% than that of the pure SPEEK membrane when 2 wt% filler was added.
【學位授予單位】：華北電力大學(北京)
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：TM911.4;TQ425.23
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