噻唑和吡咯烷季铵化氢氧根离子交换膜的制备及性能

发布时间：2018-03-15 05:37

  本文选题：氢氧根离子交换膜　切入点：噻唑　出处：《大连理工大学》2015年硕士论文　论文类型：学位论文

【摘要】：氢氧根离子交换膜燃料电池是一项新兴的燃料电池,相比于质子交换膜燃料电池,它具有电极反应速率快、制备成本低和可用非贵金属作为催化剂等优点,更适合于直接甲醇燃料电池。氢氧根离子交换膜作为其核心部件,起着分隔阴阳极室和传导氢氧根离子的作用,直接决定着氢氧根离子交换膜燃料电池的性能和寿命。氢氧根离子传导率低、离子传导基团稳定性差是氢氧根离子交换膜需要进一步改善的关键问题。本文分别采用噻唑、1-甲基吡咯烷作为季铵化基团,以综合性能优异的工程材料聚醚醚酮(PEEK)和具有高性能的工程塑料聚醚砜(PES)作为基体材料,成功制备了噻唑季铵化PEEK和PES、和1-甲基吡咯烷季铵化PEEK和PES氢氧根离子交换膜。首先选用噻唑作为季铵基团,采用溶液浇铸法成功制备出PEEK-ThOH和PES-ThOH膜,并对系列膜的各项性能进行了测试,结果表明：IEC在0.48 mmol/g-1.13mmol/g范围内的PES-ThOH膜吸水率(≤60%)和溶胀度(≤30%)均适中。IEC为1.26mmol/g的PES-ThOH膜在60℃时的吸水率相对较高,使得膜的氢氧根离子传导率在60℃时达到了最大值(35.7 mScm-1);相比于PES-ThOH膜,PEEK-ThOH膜的吸水率均略有提高,IEC在0.88 mmol/g-1.56mmol/g范围内的PEEK-ThOH膜可以保持良好的吸水率(≤100%)以及适中的溶胀度(≤40%),IEC为1.78mmol/g的PEEK-ThOH膜氢氧根离子传导率在60℃时增势变缓,但也达到了50.3mScm-1。PES-ThOH的TOD(161℃)略高于PEEK-ThOH的TOD(148℃)。PES-ThOH和PEEK-ThOH膜在20℃时的化学稳定性较好,在30-60℃时的化学稳定性较差,PES-ThOH的化学稳定性稍优于PEEK-ThOH。为了进一步提高膜的氢氧根离子传导率,选用碱性更强的1-甲基吡咯烷作为季铵基团,制各出PEEK-PyOH和PES-PyOH膜,也对系列膜的各项性能进行了测试,结果表明：IEC为1.48mmol/g的PES-PyOH膜在温度升至60℃时,因过度吸水而溶解在水中,IEC为1.21 mmol/g的PES-PyOH膜氢氧根离子传导率在60℃时最高可以达到48.6mS/cm;对于PEEK-PyOH膜,常温下,随着IEC从0.96mmol/g增加到2.07mmol/g,对应的吸水率从38.2%增加到152.3%,IEC为2.07mmol/g的PEEK-PyOH膜在常温下的氢氧根离子传导率可以达到36.8 mScm-1,在50℃C时达到最高,为53.5 mScm-1。PES-PyOH的TOD(248℃)高于PEEK-PyOH的TOD(115℃), PES-PyOH和PEEK-PyOH膜的化学稳定性随温度的变化规律与PES-ThOH和PEEK-ThOH膜一致,但PES-ThOH和PEEK-ThOH膜要优于PES-PyOH和PEEK-PyOH膜。
[Abstract]:Hydroxyl ion exchange membrane fuel cell is a new kind of fuel cell. Compared with proton exchange membrane fuel cell, it has the advantages of fast electrode reaction rate, low preparation cost and the use of non-precious metal as catalyst. It is more suitable for direct methanol fuel cells. As the core component of the membrane, the hydroxyl ion exchange membrane acts as the function of separating the cathode and anode chambers from conducting the hydroxide ions. This directly determines the performance and lifetime of the hydrogen-oxygen ion exchange membrane fuel cell. The poor stability of ionic conduction group is the key problem for the further improvement of hydroxyl ion exchange membrane. In this paper, thiazolium 1-methylpyrrolidine is used as quaternary ammonium group, and thiazolium 1-methylpyrrolidine is used as quaternary ammonium group. The engineering materials (polyether ether ketone) (PEEK) and engineering plastics (polyether sulfone) (PES) with excellent comprehensive properties were used as matrix materials. Thiazolium quaternary ammonium PEEK and PESand 1-methylpyrrolidine quaternary ammonium PEEK and PES hydroxide ion exchange membranes were successfully prepared. Firstly, PEEK-ThOH and PES-ThOH films were successfully prepared by solution casting with thiazole as quaternary ammonium group. The results showed that the water absorption rate (鈮，

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