CN113773542A - 一种全氟质子交换膜及其制备方法和应用 - Google Patents
一种全氟质子交换膜及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种全氟质子交换膜及其制备方法和应用,所述制备方法包括以下步骤:(1)将聚氨酯预聚体、环氧树脂和全氟磺酸树脂混合,加入三乙胺,在去离子水中剪切乳化得到乳液;(2)将乳液与乙二胺混合,经干燥及固化处理得到所述全氟质子交换膜。聚氨酯预聚体和环氧树脂聚合得到聚氨酯/环氧树脂互穿聚合物,在全氟磺酸树脂中原位形成三维拓扑状结构的聚合物复合膜,这样全氟磺酸质子膜的机械强度大大提高、渗氢电流密度大大降低。
Description
技术领域
本发明属于功能高分子材料领域,涉及一种全氟质子交换膜及其制备方法和应用。
背景技术
质子交换膜燃料电池PEMFC是一种将化学能通过电化学反应直接转化为电能,高效、环境友好的发电装置。具有启动快,工作温度低,无噪声和无污染等优点,在汽车、家用住宅、中小型发电站和便携式装置中有着广泛的应用前景。
质子交换膜,在其中起到传递质子、阻隔阴极和阳极反应气体、阻隔电池内部电子传递的作用,是质子交换膜燃料电池的关键材料。目前使用的全氟磺酸质子交换膜,在80℃和适当湿度下,虽然具有良好的质子传导性,但其机械强度差、化学稳定性差、渗氢电流密度大。
CN101692487A公开了一种燃料电池用低透气型质子交换膜的制备方法,用超声浸渍-喷涂结合的方法,在膨体聚四氟乙烯微孔薄膜的表面上复合全氟磺酸树脂,其中超声浸渍是将膨体聚四氟乙烯微孔薄膜浸渍在用超声波震荡的全氟磺酸树脂溶液中;喷涂是将超声浸渍后的膨体聚四氟乙烯微孔薄膜的两侧表面反复进行覆盖喷涂上料至质子交换膜的厚度达到预定要求。
CN101667648A公开了一种燃料电池用保水型质子交换膜的制备方法,包括在膨体聚四氟乙烯微孔薄膜的表面涂敷全氟磺酸树脂溶液,其制备方法包括:通过浸渍的方式,使全氟磺酸树脂成份和二氧化硅成份,填充到膨体聚四氟乙烯微孔薄膜的微孔中,通过喷涂全氟磺酸树脂成份和二氧化硅成份的方式,控制复合质子交换的厚度。
上述方案将全氟磺酸树脂溶液涂敷在膨体聚四氟乙烯两侧固化成膜,这是利用了膨体聚四氟乙烯机械强度高的缘故。但是膨体聚四氟乙烯和全氟磺酸树脂相容性差,必须事先做表面处理,工艺比较复杂;而且渗氢电流大的问题,因此,开发一种工艺简单且渗氢电流小的全氟质子交换膜是十分必要的。
发明内容
本发明的目的在于提供一种全氟质子交换膜,本发明通过使用聚氨酯预聚体、环氧树脂和全氟磺酸树脂溶液混合,其中聚氨酯预聚体和环氧树脂聚合得到聚氨酯/环氧树脂互穿聚合物,在全氟磺酸树脂中原位形成三维拓扑状结构的聚合物复合膜,这样全氟磺酸质子膜的机械强度大大提高、渗氢电流密度大大降低。
为达到此发明目的,本发明采用以下技术方案:
第一方面,本发明提供了一种全氟质子交换膜的制备方法,所述制备方法包括以下步骤:
(1)将聚氨酯预聚体、环氧树脂和全氟磺酸树脂混合,加入三乙胺,在去离子水中剪切乳化得到乳液;
(2)将乳液与乙二胺混合,经干燥及固化处理得到所述全氟质子交换膜。
本发明通过将聚氨酯预聚体、环氧树脂和全氟磺酸树脂溶液混合,其中聚氨酯预聚体和环氧树脂聚合得到聚氨酯/环氧树脂互穿聚合物,在全氟磺酸树脂中原位形成三维拓扑状结构的聚合物复合膜,这样全氟磺酸质子膜的机械强度大大提高、渗氢电流密度大大降低。
优选地,步骤(1)所述聚氨酯预聚体通过如下方法制得:
将甲苯二异氰酸酯与聚己二酸丁二醇酯和/或聚四氢呋喃二元醇混合,加热反应后,降温加入二羟甲基丙酸、N,N-二甲基甲酰胺、丙酮和桂酸二丁基锡进行扩链反应,得到聚氨酯预聚体。
优选地,所述加热反应的温度为80~90℃,例如:80℃、82℃、85℃、88℃或90℃等。
优选地,所述加热反应的时间为2~4h,例如:2h、2.5h、3h、3.5h或4h等。
优选地,所述降温的终点为50~60℃,例如:50℃、52℃、55℃、58℃或60℃等。
优选地,所述扩链反应的温度为50~60℃,例如:50℃、52℃、55℃、58℃或60℃等。
优选地,所述扩链反应的时间为3~4h,例如:3h、3.2h、3.5h、3.8h或4h等。
优选地,所述扩链反应后进行二次降温。
优选地,所述二次降温的终点为温度<20℃。
优选地,步骤(1)所述聚氨酯预聚体和环氧树脂的质量比为(4~6):(6~4),例如:4:6、4.5:5.5、5:5、5.5:4.5或6:4等。
优选地,所述聚氨酯预聚体和环氧树脂的总质量与全氟磺酸树脂的质量比为(1~4):(6~9),例如:1:9、1.5:8.5、2:8、3:7或4:6等。
聚氨酯/环氧树脂与全氟磺酸树脂的重量比少于1:9时,质子导电率、拉伸强度、渗氢电流密度变化不大。当高于5:5时,拉伸强度比较高,渗氢电流密度明显减小,但质子导电率下降明显。这说明聚氨酯/环氧树脂互穿聚合物有助于提高全氟磺酸质子交换膜的机械强度和减少渗氢电流密度。由于聚氨酯/环氧树脂互穿聚合物没有质子传导的作用,加入量过多,质子传导率下降。
优选地,步骤(1)所述剪切乳化的时间为1~2h,例如:1h、1.2h、1.5h、1.8h或2h等。
优选地,所述剪切乳化的过程中加入保水粒子和/或质子传导粒子。
优选地,所述保水粒子和/或质子传导粒子的质量浓度为3~15wt%,例如:3wt%、5wt%、8wt%、10wt%、12wt%或15wt%等。
优选地,所述保水粒子包括SiO2、TiO2或ZrO2中的任意一种或至少两种的组合。
优选地,所述质子传导粒子包括Zr(HPO4)2。
优选地,步骤(2)所述固化的温度为80~100℃,例如:80℃、85℃、90℃、95℃或100℃等。
优选地,所述固化的时间为1~4h,例如:1h、2h、3h或4h等。
第二方面,本发明提供了一种全氟质子交换膜,所述全氟质子交换膜通过如第一方面所述方法制得。
第三方面,本发明提供了一种燃料电池,所述燃料电池包含如第二方面所述的全氟质子交换膜。
相对于现有技术,本发明具有以下有益效果:
本发明通过使用聚氨酯预聚体、环氧树脂和全氟磺酸树脂溶液混合,其中聚氨酯预聚体和环氧树脂聚合得到聚氨酯/环氧树脂互穿聚合物,在全氟磺酸树脂中原位形成三维拓扑状结构的聚合物复合膜,这样全氟磺酸质子膜的机械强度大大提高、渗氢电流密度大大降低。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
实施例1
本实施例提供了一种全氟质子交换膜,所述全氟质子交换膜的制备方法如下:
(1)聚氨酯预聚体的制备:将甲苯二异氰酸酯(TDI)与聚己二酸丁二醇酯加入三口烧瓶中,在85℃反应3h,降温至55℃,将二羟甲基丙酸(DMPA)与N,N-二甲基甲酰胺(DMF)加入反应体系中,并加入适量丙酮降黏,滴加桂酸二丁基锡(DBTDL)搅拌均匀,扩链3h,然后降温至20℃以下得到聚氨酯预聚体;
(2)在预聚体中加入等质量的环氧树脂(EP)和20wt%的全氟磺酸树脂溶液,其中聚氨酯/环氧树脂和全氟磺酸树脂的质量比为1:9;搅拌混合均匀。加入三乙胺(TEA)中和,室温下在8wt%Zr(HPO4)2的去离子水中剪切乳化1.5h;
(3)在乳液中加入乙二胺(EDA),自然干燥后于80℃后固化4h,得到所述全氟质子交换膜。
实施例2
本实施例提供了一种全氟质子交换膜,所述全氟质子交换膜的制备方法如下:
(1)聚氨酯预聚体的制备:将甲苯二异氰酸酯(TDI)与聚己二酸丁二醇酯加入三口烧瓶中,在85℃反应3h,降温至55℃,将二羟甲基丙酸(DMPA)与N,N-二甲基甲酰胺(DMF)加入反应体系中,并加入适量丙酮降黏,滴加桂酸二丁基锡(DBTDL)搅拌均匀,扩链3h,然后降温至20℃以下得到聚氨酯预聚体;
(2)在预聚体中加入等质量的环氧树脂(EP)和20wt%的全氟磺酸树脂溶液,其中聚氨酯/环氧树脂和全氟磺酸树脂的质量比为2:8;搅拌混合均匀。加入三乙胺(TEA)中和,室温下在8wt%TiO2的去离子水中剪切乳化1.5h;
(3)在乳液中加入乙二胺(EDA),自然干燥后于80℃后固化4h,得到所述全氟质子交换膜。
实施例3
(1)聚氨酯预聚体的制备:将甲苯二异氰酸酯(TDI)与聚己二酸丁二醇酯加入三口烧瓶中,在85℃反应3h,降温至55℃,将二羟甲基丙酸(DMPA)与N,N-二甲基甲酰胺(DMF)加入反应体系中,并加入适量丙酮降黏,滴加桂酸二丁基锡(DBTDL)搅拌均匀,扩链3h,然后降温至20℃以下得到聚氨酯预聚体;
(2)在预聚体中加入等质量的环氧树脂(EP)和20wt%的全氟磺酸树脂溶液,其中聚氨酯/环氧树脂和全氟磺酸树脂的质量比为3:7;搅拌混合均匀。加入三乙胺(TEA)中和,室温下在8wt%Zr(HPO4)2的去离子水中剪切乳化1.5h;
(3)在乳液中加入乙二胺(EDA),自然干燥后于80℃后固化4h,得到所述全氟质子交换膜。
实施例4
(1)聚氨酯预聚体的制备:将甲苯二异氰酸酯(TDI)与聚己二酸丁二醇酯加入三口烧瓶中,在85℃反应3h,降温至55℃,将二羟甲基丙酸(DMPA)与N,N-二甲基甲酰胺(DMF)加入反应体系中,并加入适量丙酮降黏,桂酸二丁基锡和甲苯二异氰酸酯滴加桂酸二丁基锡(DBTDL)搅拌均匀,扩链3h,然后降温至20℃以下得到聚氨酯预聚体;
(2)在预聚体中加入等质量的环氧树脂(EP)和20wt%的全氟磺酸树脂溶液,其中聚氨酯/环氧树脂和全氟磺酸树脂的质量比为4:6;搅拌混合均匀。加入三乙胺(TEA)中和,室温下在8wt%Zr(HPO4)2的去离子水中剪切乳化1.5h;
(3)在乳液中加入乙二胺(EDA),自然干燥后于80℃后固化4h,得到所述全氟质子交换膜。
实施例5
(1)聚氨酯预聚体的制备:将甲苯二异氰酸酯(TDI)与聚己二酸丁二醇酯加入三口烧瓶中,在85℃反应3h,降温至55℃,将二羟甲基丙酸(DMPA)与N,N-二甲基甲酰胺(DMF)加入反应体系中,并加入适量丙酮降黏,滴加桂酸二丁基锡(DBTDL)搅拌均匀,扩链3h,然后降温至20℃以下得到聚氨酯预聚体;
(2)在预聚体中加入等质量的环氧树脂(EP)和20wt%的全氟磺酸树脂溶液,其中聚氨酯/环氧树脂和全氟磺酸树脂的质量比为1:12;搅拌混合均匀。加入三乙胺(TEA)中和,室温下在8wt%Zr(HPO4)2的去离子水中剪切乳化1.5h;
(3)在乳液中加入乙二胺(EDA),自然干燥后于80℃后固化4h,得到所述全氟质子交换膜。
实施例6
(1)聚氨酯预聚体的制备:将甲苯二异氰酸酯(TDI)与聚己二酸丁二醇酯加入三口烧瓶中,在85℃反应3h,降温至55℃,将二羟甲基丙酸(DMPA)与N,N-二甲基甲酰胺(DMF)加入反应体系中,并加入适量丙酮降黏,滴加桂酸二丁基锡(DBTDL)搅拌均匀,扩链3h,然后降温至20℃以下得到聚氨酯预聚体;
(2)在预聚体中加入等质量的环氧树脂(EP)和20wt%的全氟磺酸树脂溶液,其中聚氨酯/环氧树脂和全氟磺酸树脂的质量比为5:5;搅拌混合均匀。加入三乙胺(TEA)中和,室温下在8wt%Zr(HPO4)2的去离子水中剪切乳化1.5h;
(3)在乳液中加入乙二胺(EDA),自然干燥后于80℃后固化4h,得到所述全氟质子交换膜。
对比例1
本对比例仅将20wt%的全氟磺酸树脂溶液涂敷在PTFE板上,在100℃加热,形成全氟磺酸质子交换膜。
性能测试:
取实施例1-6和对比例1得到的质子交换膜进行电导率测试和拉伸强度测试,按国标《GB/T 20042.3-2009质子交换膜燃料电池第3部分:质子交换膜测试方法》测试,其中电导率测试温度80℃,相对湿度为60%;
将质子交换膜一面喷涂上阳极Pt/C催化剂,载量0.1mg/cm2,另一面喷涂上阴极Pt/C催化剂,载量0.4mg/cm2,各自贴上气体扩散层,做成活性面积为5cm*5cm膜电极,按国标《GB/T 20042.5-2009质子交换膜燃料电池第5部分:膜电极测试方法》测试渗氢电流密度,测试结果如表1所示:
表1
由表1可以看出,由实施例1-6对比可得,所述聚氨酯预聚体和环氧树脂的总质量与全氟磺酸树脂的质量比会影响制得质子交换膜的性能,将聚氨酯预聚体和环氧树脂的总质量与全氟磺酸树脂的质量比控制在(1~4):(6~9),制得质子交换膜的性能较为优异,聚氨酯/环氧树脂与全氟磺酸树脂的重量比少于1:9时,质子导电率、拉伸强度、渗氢电流密度变化不大。当高于4:6时,拉伸强度比较高,渗氢电流密度明显减小,但质子导电率下降明显。这说明聚氨酯/环氧树脂互穿聚合物有助于提高全氟磺酸质子交换膜的机械强度和减少渗氢电流密度。由于聚氨酯/环氧树脂互穿聚合物没有质子传导的作用,加入量过多,质子传导率下降。
由实施例1和对比例1对比可得,本发明通过使用聚氨酯预聚体、环氧树脂和全氟磺酸树脂溶液混合,其中聚氨酯预聚体和环氧树脂聚合得到聚氨酯/环氧树脂互穿聚合物,在全氟磺酸树脂中原位形成三维拓扑状结构的聚合物复合膜,这样全氟磺酸质子膜的机械强度大大提高、渗氢电流密度大大降低。
申请人声明,以上所述仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,所属技术领域的技术人员应该明了,任何属于本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,均落在本发明的保护范围和公开范围之内。
Claims (10)
1.一种全氟质子交换膜的制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将聚氨酯预聚体、环氧树脂和全氟磺酸树脂混合,加入三乙胺,在去离子水中剪切乳化得到乳液;
(2)将乳液与乙二胺混合,经干燥及固化处理得到所述全氟质子交换膜。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)聚氨酯预聚体通过如下方法制得:
将甲苯二异氰酸酯与聚己二酸丁二醇酯和/或聚四氢呋喃二元醇混合,加热反应后,降温加入二羟甲基丙酸、N,N-二甲基甲酰胺、丙酮和桂酸二丁基锡进行扩链反应,得到聚氨酯预聚体。
3.如权利要求2所述的制备方法,其特征在于,所述加热反应的温度为80~90℃;
优选地,所述加热反应的时间为2~4h;
优选地,所述降温的终点为50~60℃。
4.如权利要求1-3任一项所述的制备方法,其特征在于,所述扩链反应的温度为50~60℃;
优选地,所述扩链反应的时间为3~4h。
5.如权利要求1-4任一项所述的制备方法,其特征在于,所述扩链反应后进行二次降温;
优选地,所述二次降温的终点为温度<20℃。
6.如权利要求1-5任一项所述的制备方法,其特征在于,步骤(1)所述聚氨酯预聚体和环氧树脂的质量比为(4~6):(6~4);
优选地,所述聚氨酯预聚体和环氧树脂的总质量与全氟磺酸树脂的质量比为(1~4):(6~9)。
7.如权利要求1-6任一项所述的制备方法,其特征在于,步骤(1)所述剪切乳化的时间为1~2h;
优选地,所述剪切乳化的过程中加入保水粒子和/或质子传导粒子;
优选地,所述保水粒子和/或质子传导粒子的质量浓度为3~15wt%;
优选地,所述保水粒子包括SiO2、TiO2或ZrO2中的任意一种或至少两种的组合;
优选地,所述质子传导粒子包括Zr(HPO4)2。
8.如权利要求1-7任一项所述的制备方法,其特征在于,步骤(2)所述固化的温度为80~100℃;
优选地,所述固化的时间为1~4h。
9.一种全氟质子交换膜,其特征在于,所述全氟质子交换膜通过如权利要求1-8任一项所述方法制得。
10.一种燃料电池,其特征在于,所述燃料电池包含如权利要求9所述的全氟质子交换膜。
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