CN115109236A - 一种含sp3碳基骨架结构的哌啶叔胺基团聚合物及其应用 - Google Patents
一种含sp3碳基骨架结构的哌啶叔胺基团聚合物及其应用 Download PDFInfo
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- CN115109236A CN115109236A CN202210925091.4A CN202210925091A CN115109236A CN 115109236 A CN115109236 A CN 115109236A CN 202210925091 A CN202210925091 A CN 202210925091A CN 115109236 A CN115109236 A CN 115109236A
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Abstract
本发明提供一种含sp3碳基骨架结构的哌啶叔胺基团聚合物及其应用,至少包括四苯基甲烷以及哌啶叔胺类结构单元,在主链化学结构上包含四苯基甲烷基团,所制备的聚合物具有轻度交联,使得所制备材料具有优异的机械强度,且由于主链上sp3碳基骨架结构的支撑作用,一方面减少了聚合物的折叠链段的形成,另一方面降低了聚合物的成膜后的芳香烃结构的ππ作用,从而减少结晶区域的形成,更利于亲水相的构建,因此显著提高了该类膜的离子电导率。
Description
技术领域
本发明涉及新能源电化学器件领域,特别涉及一种含有sp3碳基骨架结构的哌啶叔胺基团聚合物、以及利用含有sp3碳基骨架结构的哌啶叔胺基团聚合物制备的阴离子交换膜、阴离子交换聚合物粘合剂的应用。
背景技术
近年来,随着世界范围内对可替代能源需求的不断增长,阴离子交换膜和阴离子交换聚合物粘合剂在新能源电化学器件中的应用也受到越来越多研究人员的关注,其可以应用于碱性燃料电池、电解水、二氧化碳还原、液流电池等领域,具有良好的发展前景,也在氯碱工业、重金属回收、水处理、湿法冶金等传统工业中起到了举足轻重的作用,并受到了十分广泛的关注。阴离子交换膜和阴离子交换聚合物粘合剂是一类含有阳离子功能基团,对阴离子具有选择透过性的高分子聚合物,然而目前的应用场景需求要求阴离子交换膜具有更高的电导率、更好的力学、热学和化学稳定性。
专利CN107910576A公开了一类高化学稳定性的阴离子聚合物膜的制备方法,采用芳基类单体与N-烷基-4-哌啶酮共聚后得到主链不含醚键的聚合产物,而后使用卤代烷烃进行季铵化反应制得阴离子交换聚合物,该阴离子交换聚合物的主链不含极性基团,且以高化学稳定性的哌啶环作为季铵阳离子,具有良好的化学稳定性。专利CN109070022A公开了用作氢氧化物交换膜和离聚物的聚(芳基哌啶)聚合物,在芳基类单体和N-烷基-4-哌啶酮的基础上,加入三氟苯乙酮类单体共聚得到主链不含醚键的聚合产物,而后使用卤代烷烃进行季铵化反应制得化学稳定性良好的阴离子交换聚合物。专利CN111269401A公开了一种包含哌啶季铵类结构单元和芴类基团以及芳香类单体的阴离子交换聚合物聚合物。该发明使得材料具有优异的机械强度,且主链上苯环的扭曲性和转动性弱,聚合物成膜后的微观结构规整度较高,从而具有良好的化学稳定性。虽然利用上述专利可获得化学稳定性良好的阴离子交换聚合物,但是阴离子交换聚合物的机械强度和离子电导率有待进一步提升。
综上所述,目前市面上的阴离子交换聚合物或阴离子交换膜虽然化学稳定性良好,但是机械强度和离子电导率依旧无法满足特殊应用场景的需求,尤其是在大尺寸大规模应用中,强的机械强度和高的离子电导率直接决定了碱性燃料电池、电解水、二氧化碳还原、液流电池等器件的耐用度和效率。因此需要开发一种兼具优异的机械强度、高离子电导率和高化学稳定性的阴离子交换聚合物,从而提升相关电化学装置的性能。
发明内容
本发明的目的在于提供一种含有sp3碳基骨架结构的哌啶叔胺基团聚合物及其应用,含有sp3碳基骨架结构的哌啶叔胺基团聚合物可被应用于制作阴离子交换膜和阴离子交换聚合膜,同时兼备优异的机械强度、高离子电导率和高化学稳定性。
为实现以上目的,第一方面,本技术方案提供一种含sp3碳基骨架结构的哌啶叔胺基团聚合物,包括:式(1)所示的四苯基甲烷类结构单元,以及式(2)所示的哌啶叔胺类结构单元;
本发明所述的含sp3碳基骨架结构的哌啶叔胺基团聚合物,还包括:式(3)所示的三氟甲基单元结构、式(4)和式(5)所示的芳基类结构单元、式(6)所示的芴类结构单元以及式(7)所示的二苯基烷烃类结构单元中的一种或至少两种组合;其中式(4)中的n为0~10的整数;其中式(7)中的n为1~20的整数:
在一些实施例中,所述四苯基甲烷结构单元(1)与哌啶叔胺类结构单元(2)的摩尔比为(0.005~1):1。
优选地,所述(3)所示的三氟甲基单元结构、式(4)和式(5)所示的芳基类结构单元、式(6)所示的芴类结构单元以及式(7)所示的二苯基烷烃类结构单元中的一种或至少两种组合与哌啶叔胺类结构单元(2)的摩尔比为(0.005~2):1。
优选地,所述含哌啶叔胺基团的聚合物的数均分子量为0.1万~100万。
优选地,所述R1选自氢、甲基、乙基、丙基、丁基、戊基、己基或苯基中的任意一种。
优选地,所述R2选自甲基、乙基、丙基、丁基、戊基、己基、环丙基、环丁基、环戊基、环己基和苯基、甲醇、1-乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、1-庚醇、1-辛醇、1-溴甲烷、1-溴乙烷、1-溴丙烷、1-溴丁烷、1-溴戊烷、1-溴己烷、1-溴庚烷、1-溴辛烷、1-乙烯、1-丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯中的任意一种或至少两种组合。
所述R3和R4各自独立地选自氢、C1-C10链状烷基或C3-C10环烷基中的任意一种,优选地,所述R3和R4各自独立地选自氢、甲基、乙基、丙基、丁基、戊基、己基中的任意一种。
另外,第二方面,本方案还提供了一种含SP3碳基骨架结构的哌啶叔胺基团聚合物的制备方法,包括以下步骤:
使单体发生聚合反应,所述单体包括式(8)四苯基甲烷单体,式(9)所示的哌啶酮单体:
优选地,所述R1和R2各自独立地选自氢、C1-C10链状烷基或C3-C10环烷基中或苯环等芳香类的任意一种。
优选地,所述式(9)所示的哌啶酮单体包括N-甲基-4-哌聢酮、N-乙基-4-哌聢酮、N-丙基-4-哌聢酮、4-哌啶酮或N-异丙基-4-哌啶酮中的任意一种或至少两种组合。
在一些实施例中,所述单体还包括式(10)所示的三氟甲基酮单体、式(11)和式(12)所示的芳基类单体、式(13)所示的芴类单体以及式(14)所示的二苯甲基烷烃类单体中的一种或至少两种组合;其中式(11)中n为0~10的整数;其中式(14)中n为1~20的整数:
优选地,所述式(10)所示的三氟甲基酮单体中R2包括甲基、乙基、丙基、丁基、戊基、己基、环丙基、环丁基、环戊基、环己基和苯基、甲醇、1-乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、1-庚醇、1-辛醇、1-溴甲烷、1-溴乙烷、1-溴丙烷、1-溴丁烷、1-溴戊烷、1-溴己烷、1-溴庚烷、1-溴辛烷、1-乙烯、1-丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯中的任意一种或至少两种组合。
优选地,所述式(11)和式(12)所示的芳香类单体包括联苯、对三联苯、间三联苯或对四联苯中的任意一种或至少两种组合.
优选地,所述式(13)所示的芴类结构单体中R3和R4各自独立地选自氢、C1-C10链状烷基或C3-C10环烷基中的任意一种,优选地,所述R3和R4各自独立地选自氢、甲基、乙基、丙基、丁基、戊基、己基中的任意一种。
优选地,所述式(14)所示的二苯基烷烃类单体包含二苯甲烷、1,2-二苯基乙烷、1,3-二苯基丙烷、1,4-二苯基丁烷、1,5-二苯基戊烷、1,6-二苯基己烷、1,7-二苯基庚烷、1,8-二苯基辛烷中的任意一种或至少两种组合。
优选地,所述聚合反应的溶剂包括二氯甲烷、氯仿、四氯乙烷、甲苯、三氟乙酸或三氟甲磺酸中的任意一种或至少两种组合。
优选地,所述聚合反应在催化剂存在下进行,所述催化剂包括三氟乙酸、甲基磺酸、三氟甲磺酸、五氟丙酸或七氟丁酸中的任意一种或至少两种组合;优选地,所述聚合反应的温度为-20~80℃;。
优选地,所述聚合反应的时间为0.1~120h。
第三方面,以上制备的sp3碳基骨架结构的哌啶叔胺基团聚合物的应用可被应用于水处理器、气体分离器或制备阴离子交换聚合物。
第四方面,当其sp3碳基骨架结构的哌啶叔胺基团聚合物应用于制备阴离子交换聚合物时,含sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物的结构包括:
式(15)所示的四苯基甲烷类结构单元,以及(16)和/或(17)所示的哌啶季胺类结构单元:
优选地,所述R1和R2各自独立地选自氢、C1-C10链状烷基或C3-C10环烷基中的任意一种。
优选地,所述R1选自氢、甲基、乙基、丙基、丁基、戊基、苯基或己基中的任意一种。
优选地,所述R2选自氢、甲基、乙基、丙基、丁基、戊基、己基、苯基、甲醇、1-乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、1-庚醇、1-辛醇中的任意一种。
优选地,所述式(16)中所述X-为阴离子。
优选地,式(16)中所述X-选自OH-、Cl-、Br-、I-、BF4 -、HCO3 -的任意一种,进一步优选为OH-。
优选地,式(16)中所述X-为OH-,所述阴离子交换聚合物的离子交换容量为0.1~10mmol/g。
优选地,式(17)中所述X-为阴离子。
优选地,式(17)中所述n为0~10的整数。
优选地,式(17)中所述X-选自OH-、Cl-、Br-、I-、BF4 -、HCO3 -的任意一种,进一步优选为OH-。
优选地,式(17)中所述X-为OH-,所述阴离子交换聚合物的离子交换容量为0.1~10mmol/g。
优选地,所述阴离子交换聚合物还包括式(18)所示的三氟甲基单元结构、式(19)和式(20)所示的芳基类结构单元、式(21)所示的芴类结构单元以及式(22)所示的二苯基烷烃类结构单元中的一种或多种组合;
优选地,所述式(18)中所述R3选自甲基、乙基、丙基、丁基、戊基、己基、环丙基、环丁基、环戊基、环己基和苯基、甲醇、1-乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、1-庚醇、1-辛醇、1-溴甲烷、1-溴乙烷、1-溴丙烷、1-溴丁烷、1-溴戊烷、1-溴己烷、1-溴庚烷、1-溴辛烷、1-乙烯、1-丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯中的任意一种或至少两种组合。
优选地,所述式(19)中的n为0~10的整数。
优选地,所述式(21)中R4和R5各自独立地选自氢、C1-C10链状烷基或C3-C10环烷基中的任意一种,式(21)所述芴类结构中R4和R5各自独立地选自氢、甲基、乙基、丙基、丁基、戊基、己基中的任意一种。
优选地,所述四苯基甲烷结构单元(15)与哌啶季胺类结构单元(16)和/或(17)的摩尔比为(0.005~1):1。
优选地,所式(18)所示的三氟甲基单元结构、式(19)和式(20)所示的芳基类结构单元、式(21)所示的芴类结构单元以及式(22)所示的二苯甲基烷烃类结构单元中的一种或至少两种组合与哌啶叔胺类结构单元(14)和/或(15)的摩尔比为(0.005~2):1。
优选地,所述式(22)所示的二苯基烷烃类结构单元中n为1~20的整数。
优选地,所述式(22)所示的二苯基烷烃类结构单元包含二苯甲烷、1,2-二苯基乙烷、1,3-二苯基丙烷、1,4-二苯基丁烷、1,5-二苯基戊烷、1,6-二苯基己烷、1,7-二苯基庚烷、1,8-二苯基辛烷中的任意一种或至少两种组合。
优选地,所述含哌啶叔胺基团的聚合物的数均分子量为0.1万~100万;
第五方面,本方案提供一种含sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物的制备方法,包括以下步骤:
1)使单体发生聚合反应,所述单体包括式(8)四苯基甲烷单体,式(9)所示的哌啶酮单体。
优选地,1)中所述R1选自氢、C1-C10链状烷基或C3-C10环烷基中或苯环等芳香类的任意一种;
优选地,1)中所述式(9)哌啶酮单体包括N-甲基-4-哌聢酮、N-乙基-4-哌聢酮、N-丙基-4-哌聢酮、4-哌啶酮或N-异丙基-4-哌啶酮中的任意一种或至少两种组合;
使单体聚合发生反应,所述单体还包括式(10)所示的三氟甲基酮单体、式(11)和式(12)所示的芳基类单体、式(13)所示的芴类单体和式(14)所示的二苯基烷烃类单体中的一种或至少两种组合;其中(11)所述n为0~10的整数;其中(14)所述n为1~20的整数:
优选地,1)中所述式(10)中所述R2选自甲基、乙基、丙基、丁基、戊基、己基、环丙基、环丁基、环戊基、环己基和苯基、甲醇、1-乙醇、1-丙醇、1-丁醇、1-戊醇、1-己醇、1-庚醇、1-辛醇、1-溴甲烷、1-溴乙烷、1-溴丙烷、1-溴丁烷、1-溴戊烷、1-溴己烷、1-溴庚烷、1-溴辛烷、1-乙烯、1-丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯中的任意一种或至少两种组合;
优选地,1)中所述式(11)和式(12)所示的芳香类单体包括联苯、对三联苯、间三联苯或对四联苯中的任意一种或至少两种组合;
优选地,1)中所述式(13)所示的芴类结构单体中R3和R4各自独立地选自氢、C1-C10链状烷基或C3-C10环烷基中的任意一种,优选地,所述R3和R4各自独立地选自氢、甲基、乙基、丙基、丁基、戊基、己基中的任意一种;。
优选地,1)中所述式(14)所示的二苯基烷烃类单体包含二苯甲烷、1,2-二苯基乙烷、1,3-二苯基丙烷、1,4-二苯基丁烷、1,5-二苯基戊烷、1,6-二苯基己烷、1,7-二苯基庚烷、1,8-二苯基辛烷中的任意一种或至少两种组合。
优选地,1)中所述聚合反应的溶剂包括二氯甲烷、氯仿、四氯乙烷、甲苯、三氟乙酸或三氟甲磺酸中的任意一种或至少两种组合;
优选地,1)中所述聚合反应在催化剂存在下进行,所述催化剂包括三氟乙酸、甲基磺酸、三氟甲磺酸、五氟丙酸或七氟丁酸中的任意一种或至少两种组合;优选地,所述聚合反应的温度为-20~80℃;
优选地,1)中所述聚合反应的时间为0.1~120h。
2)用1)中所述sp3碳基骨架结构的哌啶叔胺基团聚合物和烷基化试剂反应,从而得到sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物。
优选地,所述烷基化试剂包括碘甲烷、碘乙烷、碘丙烷、碘丁烷、碘戊烷、碘己烷、溴乙烷、溴丙烷、溴丁烷、溴戊烷、溴己烷、溴代环丙烷、溴代环丁烷、溴代环戊烷、溴代环己烷、1,2-二溴乙烷、1,3-二溴丙烷、1,4-二溴丁烷、1-5-二溴戊烷、1-6-二溴己烷、1,2-二碘乙烷、1,3-二碘丙烷、1,4-二碘丁烷、1-5-二碘戊烷、1-6-二碘己烷中的任意一种或至少两种组合;
优选地,2)中所述反应溶剂包括二甲基亚砜、1-甲基-2-吡咯烷酮、二甲基甲酰胺、二甲基乙酰胺、甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙三醇或水中的任意一种或至少两种组合;
优选地,2)中所述反应时间为0.1~120h。
优选地,2)中所述反应稳定为0~180℃。
第六方面,本方案提供一种阴离子交换膜,所述阴离子交换膜是通过sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物溶于溶液固化或流延膜机加工制备得到的,或者通过sp3碳基框架结构的哌啶叔胺基团阴离子交换聚合物与其他高分子材料,例如聚苯醚、聚四氟乙烯、聚乙烯醇、聚砜等,(包括且不限于其他阴离子交换聚合物,例如聚咪唑盐类阴离子交换聚合物、聚哌啶叔胺类阴离子聚合物等)共混后溶于溶液固化或流延膜机加工制备得到的。
优选地,所述溶解阴离子交换膜的溶液包括包括二甲基亚砜、1-甲基-2-吡咯烷酮、二甲基甲酰胺、二甲基乙酰胺、甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、乙二醇、丙三醇或水中的任意一种或至少两种组合。
优选地,将上述的阴离子交换聚合物溶液浇铸或流延于基底上,并进行干燥处理。
优选地,所述基底包括玻璃板、聚四氟乙烯板、陶瓷板、钢带、聚对苯二甲酸乙二醇酯基膜、聚酰胺基膜、聚四氟乙烯多孔膜、聚乙烯多孔膜、聚丙烯多孔膜、玻璃纤维或碳纤维中的任意一种或至少两种组合。
优选地,干燥温度为80~280℃中的一种温度或者多种温度阶段式干燥;
优选地,干燥时间为0.1~120h。
优选地,将上述的阴离子交换聚合物置于流延膜机中,制备出平整的膜。在一些实施例中,膜具体厚度为1~500μm。
第七方面,本发明提供了一类制备含sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物粘合剂的方法,所述阴离子交换聚合物粘合剂是通过上文所述的阴离子交换聚合物溶液,喷涂或滴涂在某一金属基底催化剂上或与粉末催化剂共混后喷涂或滴涂在某一金属基底或碳基导电基底上。
优选地,所述基底包括镍网、镍纤维毡、泡沫镍、不锈钢网、不锈钢毡、泡沫不锈钢、钛网、钛纤维毡、泡沫钛、铜网、PTFE基磁控溅射铜、铜片、碳纸、碳布等。
本方案提供的阴离子交换膜和阴离子交换聚合物粘合剂的应用,可被用于碱性电解水、碱性燃料电池、二氧化碳还原和液流电池。
相较现有技术,本技术方案提供了一种含有sp3碳基骨架结构的哌啶叔胺基团聚合物,该聚合物在主链化学结构上包含四苯基甲烷基团,所制备的聚合物具有轻度交联,使得所制备的材料具有更优异的机械强度。且由于主链上sp3碳基骨架结构的支撑作用,降低聚合物的成膜后的芳香烃结构的π-π作用,从而减少结晶区域的形成,从而增加聚合物结构中哌啶季胺盐的氢氧根交换的实际使用率,更利于亲水相的构建,因此显著提高了该类膜的离子电导率。
附图说明
图1是本发明实施例1所得阴离子交换聚合物的核磁H谱图。
图2是本发明实施例2所得阴离子交换聚合物的核磁H谱图。
图3是对比例1所得阴离子交换聚合物的核磁H谱图。
图4是本发明实施例1~3与对比例1~3的阴离子交换聚合物80℃下的OH-离子电导率对比图。
图5是本发明实施例1~3与对比例1~3的室温下抗拉强度对比图。
图6是本发明实施例1~3与对比例1~3在80℃1M(mol/L)NaOH溶液中浸泡2000h阳离子剩余率的对比图。
图7是二氧化碳电化学还原flow cell示意图。
图8是电解水膜电极电解池示意图。
图9是膜电极燃料电池示意图。
图10是液流池示意图。
图11是实施例1应用于二氧化碳电化学还原flow cell实例图。
图12是实施例1和对比例2以及对比例3应用于碱性电解水MEA电解槽的实例槽压-电流密度图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员所获得的所有其他实施例,都属于本发明保护的范围。
可以理解的是,术语“一”应理解为“至少一”或“一个或多个”,即在一个实施例中,一个元件的数量可以为一个,而在另外的实施例中,该元件的数量可以为多个,术语“一”不能理解为对数量的限制。
实施例一:
提供一种阴离子交换聚合物,结构如下所示:
该阴离子交换聚合物的制备方法如下:
(1)称取2.0g(8.68mmo1)的三联苯于100mL烧瓶中,加入1.02g(mmol)的N-甲基-4-哌啶酮,加入四苯基甲烷54.53mg(0.17mmol),随后加入8.8mL二氯甲烷溶解分散反应物。在0℃条件下加入1.5mL三氟乙酸和8.8mL三氟甲磺酸,反应6小时。将粘稠紫色产物倒入1M(mol/L)K2CO3溶液中,室温浸泡24小时,过滤得到白色固体产物,用去离子水充分洗涤后烘干,得到目标产物。
(2)季铵化反应。称取1.0g上述中间聚合物,加入20mL的二甲基亚砜,随后加入1.0mL碘甲烷,室温下反应12小时,随后升高温度至60℃下反应12小时。将反应产物倒入含有乙醇的乙醚(乙醚与乙醇的体积比为6:1)溶剂中,沉淀得到黄色沉淀,随后用乙酸乙酯洗涤三次后用水洗涤并烘干,得到阴离子为I-的阴离子交换聚合物。
(3)成膜及离子交换。称取120mg上述阴离子交换聚合物,加入5mL二甲亚砜,充分溶解后倒入直径为6cm的玻璃培养皿中,120℃下烘干成膜,将膜从玻璃上剥离。将该阴离子交换膜浸泡于1M KOH溶液中,80℃离子交换12小时,得到阴离子为OH-的碱性膜。
利用型号为Bruker AVANCE NEO(500MHz)的核磁共振波谱仪,对所得阴离子交换聚合物进行表征分析,氢谱核磁图如图1所示,在测试中使用氘代二甲基亚砜(d6-DMS0)溶解样品。
实施例二:
提供一种阴离子交换聚合膜,结构如下:
该阴离子交换膜的制备方法如下:
1)称取2.0g(8.68mmo1)的三联苯于100mL烧瓶中,加入0.92g(8.12mmol)的N-甲基-4-哌啶酮,加入四苯基甲烷54.53mg(0.17mmol),加入2,2,2-三氟苯乙酮156.70mg(0.90mmol),随后加入8.8mL二氯甲烷溶解分散反应物。在0°C条件下加入1.5mL三氟乙酸和8.8mL三氟甲磺酸,反应6小时。将粘稠紫色产物倒入1M(mol/L)K2CO3溶液中,室温浸泡24小时,过滤得到白色固体产物,用去离子水充分洗涤后烘干,得到目标产物。
2)季铵化反应。称取1.0g上述中间聚合物,加入20mL的二甲基亚砜,随后加入1.0mL碘甲烷,室温下反应12小时,随后升高温度至60℃下反应12小时。将反应产物倒入含有乙醇的乙醚(乙醚与乙醇的体积比为6:1)溶剂中,沉淀得到黄色沉淀,随后用乙酸乙酯洗涤三次后用水洗涤并烘干,得到阴离子为I-的阴离子交换聚合物。
3)成膜及离子交换。称取120mg上述阴离子交换聚合物,加入5mL二甲亚砜,充分溶解后倒入直径为6cm的玻璃培养皿中,120℃下烘干成膜,将膜从玻璃上剥离。将该阴离子交换膜浸泡于1M KOH溶液中,80℃离子交换12小时,得到阴离子为OH-的碱性膜。
利用型号为Bruker AVANCE NEO(500MHz)的核磁共振波谱仪,对所得阴离子交换聚合物进行表征分析,氢谱核磁图如图2所示。
实施例三:
阴离子交换聚合物的混合物,由以下两种结构的聚合物混合制备。
分别称取60mg上述两种阴离子交换聚合物,加入5mL二甲亚砜,充分溶解后倒入直径为6cm的玻璃培养皿中,120℃下烘干成膜,将膜从玻璃上剥离。将该阴离子交换膜浸泡于1M KOH溶液中,80℃离子交换12小时,得到阴离子为OH-的碱性膜。
对比实施例一
阴离子交换聚合物,其结构如下:
制备路线如下所示:
1)称取2.0g(8.68mmo1)的三联苯于100mL烧瓶中,加入0.98g(8.68mmol)的N-甲基-4-哌啶酮,随后加入8.8mL二氯甲烷溶解分散反应物。在0℃条件下加入1.5mL三氟乙酸和8.8mL三氟甲磺酸,反应6小时。将粘稠紫色产物倒入1M(mol/L)K2CO3溶液中,室温浸泡24小时,过滤得到白色固体产物,用去离子水充分洗涤后烘干,得到目标产物。
2)季铵化反应。称取1.0g上述中间聚合物,加入20mL的二甲基亚砜,随后加入1.0mL碘甲烷,室温下反应12小时,随后升高温度至60℃下反应12小时。将反应产物倒入含有乙醇的乙醚(乙醚与乙醇的体积比为6:1)溶剂中,沉淀得到黄色沉淀,随后用乙酸乙酯洗涤三次后用水洗涤并烘干,得到阴离子I-的阴离子交换聚合物。
3)成膜及离子交换。称取120mg上述阴离子交换聚合物,加入5mL二甲亚砜,充分溶解后倒入直径为6cm的玻璃培养皿中,120℃下烘干成膜,将膜从玻璃上剥离。将该阴离子交换膜浸泡于1M KOH溶液中,80℃离子交换12小时,得到阴离子为OH-的碱性膜。
利用型号为Bruker AVANCE NEO(500MHz)的核磁共振波谱仪,对所得阴离子交换聚合物进行表征分析,氢谱核磁图如图3所示。
对比实施例二
提供一种阴离子交换聚合物,结构如下;
本方案提供一种阴离子交换聚合物PiperION A40-HCO3,由Versogen公司生产。
对比实施例三
性能测试:
1)离子交换容量测试
利用核磁测试中的H谱测量阴离子交换膜的离子交换容量,具体如下:使用型号为Bruker AVANCE NEO(500MHz)的核磁共振波谱仪,对所得阴离子交换聚合物进行表征分析,对季铵氮所连甲基上氢峰和主链苯环上氢峰分别进行面积积分,通过二者峰面积比,计算离子交换容量。
2)离子电导率测试
利用四电极交流阻抗法测量全湿态阴离子交换膜在纯水中的OH-离子电导率,具体的测试参数如下:取面积2X2cm2,厚度25μm的膜材料,使用Autolab302N电化学工作站,在频率0.1Hz~1000KHz内进行交流阻抗测试,对曲线进行拟合计算离子电导率。对比例1、对比例2、对比例3、实施例1、实施例2以及实施例3在80℃下的离子电导率如图4所示。
3)抗拉强度测试
利用拉力试验机(生产厂家:岛津公司,型号:AGS-X10KN)测量阴离子交换膜在室温下的拉伸强度。对比例1、对比例2、对比例3、实施例1、实施例2以及实施例3在的拉伸强度如图5所示。
4)稳定性测试
通过将阴离子交换膜浸泡于80℃的1M NaOH溶液,观察2000h后的氢谱核磁谱图变化,测量阴离子交换膜中阳离子剩余率。对比例1、对比例2、对比例3、实施例1、实施例2以及实施例3在80℃下1M(mol/L)NaOH溶液中浸泡2000h后的阳离子剩余率如图6所示。
从图4-6中可以看到:实施例1-3的离子电导率均是高于对比实施例1-3的例子电导率,实施例1-3的拉伸强度也远高于对比实施例1-3的拉伸强度,表示本方案提供的阴离子交换膜的离子电导率和机械强度都有所提高,且实施例1-3的稳定性也未受到明显的影响。
实施例1所示的阴离子交换膜在二氧化碳电化学还原中的应用。
基于实施例1,将该案例中制备的阴离子交换膜用于CO2RR,也就是CO2还原:
使用Flow cell电解池设备。Flow cell电解池的具体结构如附图8所示:组件①CO2气体流动室;组件②硅胶垫片;组件③阴极(CO2RR)催化剂;组件④阴极电解液流动室;组件⑤离子传输膜;组件⑥阳极催化剂;组件⑦阳极电解液流动室;组件⑧垫板。
即:利用三腔室流动电解池,三腔室流动电解池依次为CO2气体流动室、阴极液流室及阳极液流室,CO2气体流动室与阴极液流室之间设置气体扩散电极,利用气体扩散电极将CO2气体流动室与阴极液流室隔开,阴极液流室与阳极液流室之间设置西瓜基生物离子传输膜,利用阴离子交换膜将阴极液流室与阳极液流室隔开,然后密封,阳极对电极设置于阳极液流室内,且阴极液流瓶通过导管与阴极液流室相连通,阳极液流瓶通过导管与阳极液流室相连通,CO2气体流动室为聚四氟乙烯材质,最后将电源的正极、负极分别与阳极对电极和CO2气体流动室的外表面相连接。
1)使用实施例1中所示的阴离子交换膜;
2)以KOH溶液为电解液;
3)水氧化和CO2还原的阳极和阴极催化剂分别为S(Ni,Fe)OOH和钴肽菁(CoPc);
4)CO2流量为20sccm;
5)阳极电解液和阴极电解液的流速分别为35ml/min和10ml/min。
6)在一定电压范围内对通入电解池的CO2进行还原。这个电压按照实际操作设定。
最终测得结果如图11所示,将实施例1作为阴离子交换膜使用的实验结果和对比例2、对比例3作为阴离子传输膜使用的实验结果进行对比,可见,在不同电流密度下还原CO2所对应的槽压(Cell Voltage),实施例1所用槽压最小。性能优于对比例2和对比例3。
实施例1所示的阴离子交换膜在碱性电解水中的应用。
MEA电解池的具体结构如附图8所示:组件①不锈钢垫板;组件②铜电极;组件③石墨材质阴极电解液流动室;组件④阴极催化剂;组件⑤离子传输膜;组件⑥阳极催化剂;组件⑦石墨材质阳极电解液流动室。
本测试使用Fe-Ni3S2为阳极气体扩散电极(1.0cm2,厚度0.75mm),以Ni4Mo/MoO2/NF为阴极气体扩散电极(1.0cm2,厚度1mm),以实施例1制备的阴离子交换膜为膜材料,将上述的膜电极组件(MEA)组装到器件中。阳极阴极持续通入50mLmin-1的1M KOH,电解池运行温度80℃,并使用装配10A电流放大器的Autolab302N测试性能.极化曲线测试前用循环伏安法(CV)活化1h,电压范围为1.0~2.6V,扫速:200mV s-1.极化曲线测试使用的电压范围为1.0~2.6V,扫速:10mV s-1.电化学阻抗谱在恒电压1.8V进行测试,施加10mV波动电压,扰动频率:1Hz~100KHz.
催化剂制备过程如下:
首先,对泡沫镍(NF,2.0×3.0cm2)进行前处理.具体操作为:先将泡沫镍置于3MHCl中超声20min后取出,分别用去离子水和无水乙醇冲洗数次,烘干备用.
Fe-Ni3S2催化剂制备:催化剂是通过一步水热法合成的.催化剂典型的合成方法如下:将硫脲(2.0mmol)、FeSO4·7H2O(0.5mmol)和柠檬酸钠(25mg)溶解于甲醇(15mL)和去离子水(20mL)的混合溶剂中。充分溶解后,溶液转移至不锈钢高压釜(规格:50mL)中,并将清洗后的NF浸入溶液中.反应釜密封后,将其转移至烘箱,在160℃下反应8小时,然后自然冷却至室温.将反应后的NF用去离子水和无水乙醇冲洗数次,烘干备用.
Ni4Mo/MoO2/NF催化剂制备:将Ni(NO3)2·6H2O(40mM)和(NH4)6Mo7O24(25mg)溶解于去离子水(15mL)中.充分溶解后,溶液转移至不锈钢高压釜(规格:50mL)中,并将清洗后的NF(2.0×2.0cm2)浸入溶液中.反应釜密封后,将其转移至烘箱,在150℃下反应6小时,然后自然冷却至室温.将反应后的NF用去离子水和无水乙醇冲洗数次,烘干备用.随后,将反应后的NF放到石英舟中,置入到管式炉中,在H2/Ar(v/v,5/95)氛围中500℃条件下煅烧2h.煅烧结束后,降温至室温后取出,放到干燥器备用.
碱性电解水MEA测试结果如图12所示。结果显示,分别在2.0V和2.6V的槽压下,实施例1所示的阴离子交换膜为基础的MEA器件显示出高于对比例2和对比例3SustainionX37-50 Grade T中所示的阴离子交换膜为基础的MEA器件的电流密度。证明了实施例1所示阴离子交换膜的优越性能。
本发明不局限于上述最佳实施方式,任何人在本发明的启示下都可得出其他各种形式的产品,但不论在其形状或结构上作任何变化,凡是具有与本申请相同或相近似的技术方案,均落在本发明的保护范围之内。
Claims (13)
9.一种阴离子交换膜,其特征在于,所述阴离子交换膜是通过权利要求5-6任一所述sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物溶于溶剂固化或流延膜机加工制备得到的,或者通过权利要求5-6任一所述的sp3碳基框架结构的哌啶叔胺基团阴离子交换聚合物与其他高分子材料共混后溶于溶液固化或流延膜机加工制备得到的。
10.一种阴离子交换聚合物粘合剂,其特征在于,所述阴离子交换聚合物粘合剂是通过权力要求5-6任一所述sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物溶于溶剂,制备得到阴离子交换聚合物粘合剂溶液。
11.一种根据权利要求5-6任一所述的sp3碳基骨架结构的哌啶叔胺基团阴离子交换聚合物的应用,其特征在于,用于碱性电解水、碱性燃料电池、二氧化碳还原和液流电池。
12.一种根据权利要求9所述的阴离子交换膜的应用,其特征在于,用于碱性电解水、碱性燃料电池、二氧化碳还原和液流电池。
13.一种根据权利要求10所述的阴离子交换聚合物粘合剂的应用,其特征在于,用于碱性电解水、碱性燃料电池、二氧化碳还原和液流电池。
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CN115651240A (zh) * | 2022-10-26 | 2023-01-31 | 西湖大学 | 基于MOFs框架的阴离子交换膜及其制备方法和应用 |
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CN115651240B (zh) * | 2022-10-26 | 2023-09-08 | 西湖大学 | 基于MOFs框架的阴离子交换膜及其制备方法和应用 |
CN115612069A (zh) * | 2022-11-08 | 2023-01-17 | 惠州亿纬燃料电池有限公司 | 一种芳基哌啶叔胺基聚合物及其制备方法和应用 |
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