碱性季铵化聚醚砜类阴离子交换膜的制备及性能
发布时间：2019-01-06 11:17
【摘要】：阴离子交换膜燃料电池(Anion Exchange Membrane Fuel Cell, AEMFC)结合了质子交换膜燃料电池结构简单,碱性燃料电池氧化速度快以及直接甲醇燃料电池高能量密度等一系列优点,具有很大的发展空间。阴离子交换膜(Anion Exchange Membrane, AEM)作为AEMFC的关键组成部分,起到传递氢氧根离子同时阻隔燃料和氧化剂的作用。本论文制备了几种新型的季铵化聚醚砜阴离子交换膜,并且详细研究了所制备的阴离子膜的基本性能。 首先通过无规共聚的方法制备了两种不同结构的聚醚砜聚合物,然后通过傅-克烷基化反应将氯甲基基团分别引入到聚合物分子主链和侧链上,之后经过季铵化及碱化处理制备了一系列聚醚砜阴离子交换膜。实验结果表明,采用不同结构单体合成的聚醚砜对膜性能影响较大。以双酚芴结构单元合成的聚醚砜阴离子膜因其含有刚性较强的双酚芴单元而具有较好的机械性能及耐碱稳定性,并且由于离子基团主要是连在聚合物侧链上,有利于聚合物形成亲水-疏水微相分离结构,利于OH-的传递。如rQPES(A)-2膜(IEC=1.33mmol/g)在30℃和80℃水中的离子传导率分别为10.6mS/cm和41.4mS/cm,在经4M NaOH溶液浸泡168h后,离子传导率的损失在40%左右。另一方面,以双酚A结构单元合成的聚醚砜阴离子膜rQPES(B)-2膜(IEC=1.26mmol/g)在相同条件下的离子传导率分别为6.7mS/cm和36.1mS/cm,经强碱浸泡后,离子传导率的损失在50%左右。 然后通过改变合成工艺,采用分步加料方式,成功合成了的序列式聚醚砜阴离子交换膜。对所制备的膜进行了性能表征。结果表明：IEC值相似时,序列式阴离子膜在离子传导率、机械性能及耐碱稳定性方面均高于无规型阴离子膜。如sQPES(20/20)-A2膜(IEC=1.72mmol/g)在30℃时的离子传导率为27.8mS/cm,而rQPES(A)-4膜(IEC=1.78mmol/g)在30℃时的离子传导率为23.0mS/cm。经4M NaOH溶液浸泡168h后,序列式阴离子交换膜离子传导率的损失在30%左右,而无规型阴离子交换膜在相同条件下离子传导率的损失在40%以上 最后以合成的季铵化无规型聚醚砜聚合物为原料,采用球磨法制备了一系列TiO2纳米管掺杂型聚醚砜阴离子交换膜。研究表明,适量TiO2纳米管的加入能够在膜离子传导率增大的情况下,有效的抑制膜的溶胀,提高膜的尺寸稳定性和机械性能。例如QPES(A)-TNT-2.0%掺杂膜,在30℃时在平面方向和厚度方向的尺寸变化分别为0.20和0.19,吸水率为98%,离子传导率为25.7mS/cm。相比之下,未掺杂膜在30℃时在平面方向和厚度方向的尺寸变化分别为0.25和0.23,吸水率为92%,离子传导率为23.2mS/cm。这表明纳米材料掺杂改性是制备高性能阴离子交换膜一种非常有效的方式。
[Abstract]:The anion exchange membrane fuel cell (Anion Exchange Membrane Fuel Cell, AEMFC) combines a series of advantages, such as simple structure of proton exchange membrane fuel cell, fast oxidation speed of alkaline fuel cell and high energy density of direct methanol fuel cell. There is a lot of room for development. As a key component of AEMFC, the anion exchange membrane (Anion Exchange Membrane, AEM) acts as a barrier to fuel and oxidant at the same time. In this paper, several new quaternary ammonium polyethersulfone anion exchange membranes were prepared and their basic properties were studied in detail. At first, two kinds of polyethersulfone polymers with different structures were prepared by random copolymerization, and then chloromethyl groups were introduced into the main chain and side chain of polymer by Friedel-gram alkylation reaction. A series of polyethersulfone anion exchange membranes were prepared by quaternization and alkalization. The experimental results show that polyethersulfone (PES) synthesized with different structure monomers has great influence on the performance of the membranes. The polyethersulfone anion membrane synthesized with bisphenol fluorene structure unit has good mechanical properties and alkali-resistant stability because it contains a rigid bisphenol fluorene unit, and the ionic group is mainly attached to the side chain of the polymer. It is advantageous to the formation of hydrophilic-hydrophobic microphase separation structure and the transfer of OH-. For example, the ion conductivities of rQPES (A) 2 membrane (IEC=1.33mmol/g) in water at 30 鈩，
本文编号：2402724
[Abstract]:The anion exchange membrane fuel cell (Anion Exchange Membrane Fuel Cell, AEMFC) combines a series of advantages, such as simple structure of proton exchange membrane fuel cell, fast oxidation speed of alkaline fuel cell and high energy density of direct methanol fuel cell. There is a lot of room for development. As a key component of AEMFC, the anion exchange membrane (Anion Exchange Membrane, AEM) acts as a barrier to fuel and oxidant at the same time. In this paper, several new quaternary ammonium polyethersulfone anion exchange membranes were prepared and their basic properties were studied in detail. At first, two kinds of polyethersulfone polymers with different structures were prepared by random copolymerization, and then chloromethyl groups were introduced into the main chain and side chain of polymer by Friedel-gram alkylation reaction. A series of polyethersulfone anion exchange membranes were prepared by quaternization and alkalization. The experimental results show that polyethersulfone (PES) synthesized with different structure monomers has great influence on the performance of the membranes. The polyethersulfone anion membrane synthesized with bisphenol fluorene structure unit has good mechanical properties and alkali-resistant stability because it contains a rigid bisphenol fluorene unit, and the ionic group is mainly attached to the side chain of the polymer. It is advantageous to the formation of hydrophilic-hydrophobic microphase separation structure and the transfer of OH-. For example, the ion conductivities of rQPES (A) 2 membrane (IEC=1.33mmol/g) in water at 30 鈩，
本文编号：2402724
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