QAPEI及其复合膜的制备与性能研究
摘要
氢氧根离子交换膜燃料电池工作在碱性环境中,具有电极反应速率快、催化剂选择范围宽以及甲醇渗透率低等优点,但是其电池性能仍有待提高。通常氢氧根离子交换膜是通过氯甲基化聚合物与三甲胺水溶液的非均相季铵化反应制备的,这种方法转化率低,膜的离子传导率低,所以电池性能不高。本文旨在选择以氯甲基化后可以与三甲胺水溶液完全季铵化的聚合物,制备具有较好离子传导率并且适合燃料电池应用的氢氧根离子交换膜。
聚醚酰亚胺(PEI)被发现是满足要求的聚合物,首先采用无毒高活性的氯甲基辛基醚(CMOE)作为氯甲基化试剂制备了一系列不同氯甲基化程度(DC)的氯甲基化PEI (CMPEI)。实验表明溶剂用量、催化剂用量、反应温度等对反应结果有很大的影响,并确定最佳反应条件为：PEI: CMOE:C2H4Cl2:ZnCl2=2.0g:4ml:50ml:1.0g,反应温度60℃。
CMPEI可以溶解到三甲胺水溶液中通过均相反应得到季铵化PEI (QAPEI),核磁谱图表明CMPEI反应完全。为提高膜的机械性能,将QAPEI与亲水粘性的聚乙烯醇(PVA)复合制备QAPEI/PVA复合膜。考察了PVA含量对复合膜机械性能的影响,确定最适宜质量比为QAPEI:PVA=l:0.25.复合膜的离子交换容量、吸水率、溶胀度和离子传导率都随着DC以及温度的升高而升高。在20℃时,复合膜的离子传导率可以达到0.167S/cm,并在60℃时升高到0.289S/cm。复合膜具有非常高的吸水率和比较大的溶胀度,其最大吸水率为344%,最大溶胀度可以达到89%,但是可以保持膜的形貌完整。
为降低膜的溶胀度,将QAPEI与疏水性的聚四氟乙烯(PTFE)膜进行复合制备QAPEI/PTFE复合膜。扫描电镜和红外谱图测试都表明QAPEI与PTFE具有良好的相容性。与QAPEI/PVA复合膜相比,QAPEI/PTFE复合膜的吸水率和溶胀度都有明显的降低,具有更好的机械稳定性。QAPEI/PTFE复合膜的离子交换容量、吸水率、溶胀度和离子传导率与QAPEI/PVA复合膜遵循相同的规律,也随着温度和DC的升高而升高。在20℃时QAPEI/PTFE复合膜的离子传导率可以达到0.119S/cm,并在60℃时升高到0.352S/cm。
Hydroxide exchange membrane fuel cells work in alkaline environment and have many merits, such as high electrochemical reaction rate, wide catalyst options and low methanol permeability. Unfortunately, its performance is poor because of the lower ionic conductivity of the hydroxide exchange membrane. Generally, the hydroxide exchange membrane is prepared by aminating chloromethylated polymers with trimethylamine aqueous solution through heterogeneous reaction which is insufficient and result in the low conductivity. In the present work, polyetherimide (PEI) which could achieve sufficient homogeneous reaction with trimethylamine aqueous solution were chosen to make hydroxide exchange membrane with high conductivity and suitable for use in hydroxide exchange membrane fuel cells.
Chloromethylated polyetherimide (CMPEI) was primarily synthesized by non-toxic and high-efficient chloromethyl octyl ether (CMOE) as chloromethylation reagent. The amount of solvent and catalyst, and the reaction temperature affect the chloromethylation of PEI significantly. The optimized condition is:PEI:CMOE:C2H4Cl2:ZnCl2=2.0g:4ml:50ml:l.0g at60oC. Under optimum condition, a series of CMPEI with different degrees of chloromethylation (DC) were prepared successfully by controlling the reaction time.
Quaternized PEI (QAPEI) was then obtained by dissolving CMPEI in trimethylamine aqueous solution to complete quaternization. The nuclear magnetic resonance (NMR) spectroscopy confirmed the completely conversion of CMPEI. In order to strengthen the mechanical stability of the membrane, hydrophilic polyvinyl alcohol (PVA) was added to prepare QAPEI/PVA composite membranes. The content of PVA was investigated and determined the best mass ratio of QAPEI to PVA was1:0.25. The ion exchange capacity (IEC), water uptake, swelling ratio and hydroxide conductivity of the membranes all increased with the increasing of DC and temperature. The hydroxide conductivity could reach0.167S/cm at20oC and rose to0.289S/cm at60°C. The membrane exhibited water uptake as high as344%and swelling ratio as high as89%accordingly. But the membranes were able to keep their integrated morphology even at60°C.
In order to decrease the water uptake and swelling ratio of the membrane, hydrophobic Polytetrafluoroethylene (PTFE) was used to composite with QAPEI. The results of scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) showed that the QAPEI was well composited with PTFE. As expected, the water uptake and swelling ratio of QAPEI/PTFE was significantly reduced compared with QAPEI/PVA, and the membrane owned good dimensional stability. The ion exchange capacity (IEC), water uptake, swelling ratio and hydroxide conductivity of QAPEI/PTFE composite membranes also increased with the increasing of DC and temperature. The hydroxide conductivity could reach0.119S/cm at20°C and rose to0.352S/cm at60°C.
聚醚酰亚胺(PEI)被发现是满足要求的聚合物,首先采用无毒高活性的氯甲基辛基醚(CMOE)作为氯甲基化试剂制备了一系列不同氯甲基化程度(DC)的氯甲基化PEI (CMPEI)。实验表明溶剂用量、催化剂用量、反应温度等对反应结果有很大的影响,并确定最佳反应条件为：PEI: CMOE:C2H4Cl2:ZnCl2=2.0g:4ml:50ml:1.0g,反应温度60℃。
CMPEI可以溶解到三甲胺水溶液中通过均相反应得到季铵化PEI (QAPEI),核磁谱图表明CMPEI反应完全。为提高膜的机械性能,将QAPEI与亲水粘性的聚乙烯醇(PVA)复合制备QAPEI/PVA复合膜。考察了PVA含量对复合膜机械性能的影响,确定最适宜质量比为QAPEI:PVA=l:0.25.复合膜的离子交换容量、吸水率、溶胀度和离子传导率都随着DC以及温度的升高而升高。在20℃时,复合膜的离子传导率可以达到0.167S/cm,并在60℃时升高到0.289S/cm。复合膜具有非常高的吸水率和比较大的溶胀度,其最大吸水率为344%,最大溶胀度可以达到89%,但是可以保持膜的形貌完整。
为降低膜的溶胀度,将QAPEI与疏水性的聚四氟乙烯(PTFE)膜进行复合制备QAPEI/PTFE复合膜。扫描电镜和红外谱图测试都表明QAPEI与PTFE具有良好的相容性。与QAPEI/PVA复合膜相比,QAPEI/PTFE复合膜的吸水率和溶胀度都有明显的降低,具有更好的机械稳定性。QAPEI/PTFE复合膜的离子交换容量、吸水率、溶胀度和离子传导率与QAPEI/PVA复合膜遵循相同的规律,也随着温度和DC的升高而升高。在20℃时QAPEI/PTFE复合膜的离子传导率可以达到0.119S/cm,并在60℃时升高到0.352S/cm。
Hydroxide exchange membrane fuel cells work in alkaline environment and have many merits, such as high electrochemical reaction rate, wide catalyst options and low methanol permeability. Unfortunately, its performance is poor because of the lower ionic conductivity of the hydroxide exchange membrane. Generally, the hydroxide exchange membrane is prepared by aminating chloromethylated polymers with trimethylamine aqueous solution through heterogeneous reaction which is insufficient and result in the low conductivity. In the present work, polyetherimide (PEI) which could achieve sufficient homogeneous reaction with trimethylamine aqueous solution were chosen to make hydroxide exchange membrane with high conductivity and suitable for use in hydroxide exchange membrane fuel cells.
Chloromethylated polyetherimide (CMPEI) was primarily synthesized by non-toxic and high-efficient chloromethyl octyl ether (CMOE) as chloromethylation reagent. The amount of solvent and catalyst, and the reaction temperature affect the chloromethylation of PEI significantly. The optimized condition is:PEI:CMOE:C2H4Cl2:ZnCl2=2.0g:4ml:50ml:l.0g at60oC. Under optimum condition, a series of CMPEI with different degrees of chloromethylation (DC) were prepared successfully by controlling the reaction time.
Quaternized PEI (QAPEI) was then obtained by dissolving CMPEI in trimethylamine aqueous solution to complete quaternization. The nuclear magnetic resonance (NMR) spectroscopy confirmed the completely conversion of CMPEI. In order to strengthen the mechanical stability of the membrane, hydrophilic polyvinyl alcohol (PVA) was added to prepare QAPEI/PVA composite membranes. The content of PVA was investigated and determined the best mass ratio of QAPEI to PVA was1:0.25. The ion exchange capacity (IEC), water uptake, swelling ratio and hydroxide conductivity of the membranes all increased with the increasing of DC and temperature. The hydroxide conductivity could reach0.167S/cm at20oC and rose to0.289S/cm at60°C. The membrane exhibited water uptake as high as344%and swelling ratio as high as89%accordingly. But the membranes were able to keep their integrated morphology even at60°C.
In order to decrease the water uptake and swelling ratio of the membrane, hydrophobic Polytetrafluoroethylene (PTFE) was used to composite with QAPEI. The results of scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) showed that the QAPEI was well composited with PTFE. As expected, the water uptake and swelling ratio of QAPEI/PTFE was significantly reduced compared with QAPEI/PVA, and the membrane owned good dimensional stability. The ion exchange capacity (IEC), water uptake, swelling ratio and hydroxide conductivity of QAPEI/PTFE composite membranes also increased with the increasing of DC and temperature. The hydroxide conductivity could reach0.119S/cm at20°C and rose to0.352S/cm at60°C.
引文
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