CN103566780A - 一种氟取代聚芳醚复合阴离子电解质膜的制备方法 - Google Patents

一种氟取代聚芳醚复合阴离子电解质膜的制备方法 Download PDF

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CN103566780A
CN103566780A CN201210265356.9A CN201210265356A CN103566780A CN 103566780 A CN103566780 A CN 103566780A CN 201210265356 A CN201210265356 A CN 201210265356A CN 103566780 A CN103566780 A CN 103566780A
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polyarylether
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fluorine
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CN103566780B (zh
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尚玉明
王要武
王树博
刘永刚
王金海
谢晓峰
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Tsinghua University
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Abstract

本发明属于功能高分子材料制备方法技术领域，特别涉及一种氟取代聚芳醚复合阴离子电解质膜的制备方法。该方法通过将氟取代聚芳醚溶于适当溶剂，加入适量含羟基的交联组分、催化剂及无机组分，得到制膜液，经热处理脱除溶剂，并在制膜过程中完成交联反应，得到交联结构的有机无机复合阴离子电解质膜材料。本发明原料易得、各组分分散均匀、操作简单，所制备的氟取代聚芳醚复合阴离子电解质膜具有良好的尺寸稳定性、机械强度、离子传导能力及低的钒离子渗透性。

Description

一种氟取代聚芳醚复合阴离子电解质膜的制备方法
技术领域
本发明属于功能高分子材料制备方法技术领域，特别涉及一种氟取代聚芳醚复合阴离子电解质膜的制备方法。
背景技术
离子交换膜是一种含离子基团的、对溶液里的离子具有选择透过能力的高分子膜。在聚合物电解质膜燃料电池（PEMFC）、直接甲醇燃料电池（DMFC）和全钒氧化还原液流电池（VRB）等新能源电池中，离子交换膜均是其关键材料，其既要分隔正、负极物质，又要传导离子，形成电流回路，是制约此类电池性能的重要因素。此类电池对膜的要求是高选择性、低膜电阻及足够的化学稳定性。离子交换膜根据其固定基团所带电荷种类的不同可分为阳离子交换膜和阴离子交换膜。
目前，上述几种电池所采用的离子交换膜是全氟磺酸类膜，它具有高的质子电导率、优良的化学稳定，在上述几种电池系统中能够实现基本应用。但因其化学结构本身的限制，也存在诸多缺陷，限制了电池性能的进一步提升。
由于全氟磺酸类膜的固定离子为磺酸根离子，其带有负电荷，因此全氟磺酸类膜是一种酸性的阳离子交换膜。在燃料电池PEMFC或DMFC中，由于全氟磺酸类膜的强酸性所带来的高腐蚀性，导致这两类电池的电极催化剂材料必须是耐腐蚀性良好的贵金属催化剂纳米Pt，而纳米Pt高昂的价格，导致这类电池的成本居高不下，影响了其大规模的商业化进程。而采用碱性的阴离子交换膜，可大大降低膜对催化剂材料的腐蚀，电池中可使用价格更低廉的银、铑、镍和钴等耐腐性较差的材料，这对大幅降低电池成本，促进其大规模商业化具有重要意义。
在全钒氧化还原液流电池（VRB）中，全氟磺酸类膜的固定基团为磺酸根阴离子，有利于电解液中的质子通过，但在质子通过的同时，同为阳离子的钒离子也可以通过，即发生钒渗透，造成了膜两侧电解液的交叉污染，使电池发生自放电，电池性能降低。同时，全氟磺酸类膜的制备工艺复杂，价格昂贵，膜成本在整个全钒液流电池堆成本中占40%以上，造成整个电池堆成本偏高，阻碍了VRB的大规模商业化推广。
发明内容
针对现有技术不足，本发明提供了一种氟取代聚芳醚复合阴离子电解质膜的制备方法。
一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于，该方法的具体步骤如下：
（1）在惰性气氛中，将氟取代聚芳醚结构阴离子聚合物溶于合适溶剂，配置成5 wt%~20 wt%的溶液，其中氟取代聚芳醚结构阴离子聚合物具有如下结构：
Figure BDA0000194183871
，
式中：Ar=
Figure BDA0000194183872
（TMPA）或
Figure BDA0000194183873
（TMBA），R=H 或功能基，功能基的结构为
Figure BDA0000194183874
（Ⅰ）、
Figure BDA0000194183875
（Ⅱ）、
Figure BDA0000194183876
（Ⅲ）、
Figure BDA0000194183877
（Ⅳ）或
Figure BDA0000194183878
（Ⅴ），其中，X为F-、Cl-、Br-、I- 或OH-中的任意一种；所述氟取代聚芳醚结构阴离子聚合物按照文献（刘国舜，多氟聚芳醚阴离子交换膜的合成与表征，[D]. 北京：清华大学，2011.）所述步骤进行合成；然后在缓慢搅拌加入交联组分至其溶解，得到透明溶液；其中交联组分的加入量为氟取代聚芳醚结构阴离子聚合物加入量的1 wt%~40 wt%；
（2）在步骤（1）中所得到的透明溶液中加入无机组分前驱体及水，在0 ℃~80 ℃温度下，搅拌反应1小时~6小时，得到溶胶混合物；其中无机组分前驱体的加入量为氟取代聚芳醚结构阴离子聚合物加入量的3 wt%~30 wt%，加水量为无机组分前驱体加入量的0.1 wt%~10wt%；
（3）将步骤（2）中所得到的溶胶混合物体系温度降至0 ℃~50 ℃后，加入适量交联催化剂，搅拌反应0.5小时~2小时，得到制膜液；其中交联催化剂的加入量为步骤（1）中交联组分加入量的0.5 wt%~10wt%；
（4）将步骤（3）中所得到的制膜液涂覆于基板上，在50 ℃~80 ℃温度下，保持3小时~24小时后，再在100 ℃~150 ℃温度下，保持8小时~24小时后脱膜，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
所述步骤（1）中惰性气氛为氮气或氩气。
所述步骤（1）中氟取代聚芳醚结构阴离子聚合物的功能化程度值（即聚合物结构式中R所代表的H与功能基团的摩尔比）为15%~95%。
所述步骤（1）中氟取代聚芳醚结构阴离子聚合物的数均分子量Mn=5000~200000。
所述步骤（1）中溶剂为二甲基甲酰胺、二甲基乙酰胺、1，2-二氯乙烷、乙腈、二甲基亚砜、二苯砜、环丁砜和N-甲基吡咯烷酮中的一种或多种。
所述步骤（1）中交联组分为聚乙二醇、聚乙烯醇和羟基封端聚二甲基硅氧烷中的一种或多种。
所述步骤（1）中交联组分的数均分子量Mn=500~300000。
所述步骤（2）中无机组分前驱体为硅酸四乙酯、钛酸四丁酯、甲基三乙氧基硅烷、甲基三甲氧基硅烷、丙基三甲氧基硅烷和丙基三乙氧基硅烷中的一种或多种。.
所述步骤（3）中交联催化剂为KOH、NaOH、K2CO3，Na2CO3、三乙胺和四甲基氢氧化胺中的一种或多种。
所述氟取代聚芳醚结构阴离子聚合物的表述可由几种结构因素（Ar-功能基-X-功能化程度）来表述，如（TMPA-Ⅰ-Br--50%）表示聚合物中的Ar为TMPA，并含有功能基I，X为Br-离子，其功能化程度为50%。
本发明的有益效果为：
本发明原料易得、各组分分散均匀、操作简单，所制备的一种具有互穿网络结构的氟取代聚芳醚阴离子电解质膜具有良好的尺寸稳定性、机械强度、离子传导能力及低的钒离子渗透性。
具体实施方式
本发明提供了一种氟取代聚芳醚复合阴离子电解质膜的制备方法，下面结合具体实施方式对本发明做进一步说明。
实施例1
在氮气气氛中，将100 g氟代聚芳醚阴离子聚合物（TMPA-Ⅱ-Cl--15%， Mn=5000）溶于二甲基甲酰胺，配置成浓度为5 wt%的溶液，在搅拌下缓慢加入40 g聚乙二醇（Mn=500）至其溶解，得到透明溶液；
向上述溶液中依次加入3 g钛酸四丁酯和0.03 g水，在80 ℃下搅拌反应1小时，得到溶胶混合物；
将体系温度降至50 ℃后，向溶胶混合物中加入0.2 g交联催化剂KOH，搅拌混合0.5小时，得到制膜液；
将制膜液涂覆于基板上，在80 ℃下保持3小时后，再在150 ℃下保持8小时，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
实施例2
在氮气气氛中，将200 g氟代聚芳醚阴离子聚合物（TMBA-Ⅰ-Br--95%，Mn=200000）溶于二甲基乙酰胺，配置成浓度为15 wt%的溶液，在搅拌下缓慢加入2 g聚乙烯醇（Mn=300000）至其溶解，得到透明溶液；
向上述溶液中依次加入60 g硅酸四乙酯和3 g水，在0 ℃下搅拌反应6小时，得到溶胶混合物；
将体系温度保持在0 ℃，向溶胶混合物中加入0.2 g NaOH，搅拌混合2小时，得到制膜液；
将制膜液涂覆于基板上，在50 ℃下保持24小时后，再在100 ℃下保持24小时，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
实施例3
在氩气气氛中，将100 g氟代聚芳醚阴离子聚合物（TMBA-Ⅳ-OH--50%，Mn=100000）溶于二甲基亚砜，配置成浓度为10 wt%的溶液，在搅拌下缓慢加入20 g羟基封端聚二甲基硅氧烷（Mn=800）至其溶解，得到透明溶液；
向上述溶液中依次加入20 g硅酸四乙酯、10 g丙基三乙氧基硅烷和3 g水，在60 ℃下搅拌反应4小时，得到溶胶混合物；
将体系温度降至10 ℃，向溶胶混合物中加入1 g Na2CO3，搅拌混合1.5小时，得到制膜液；
将制膜液涂覆于基板上，在60 ℃下保持12小时后，再在120 ℃下保持16小时，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
实施例4
在氮气气氛中，将150 g氟代聚芳醚阴离子聚合物（TMPA-Ⅲ-I--80%，Mn=150000）溶于N-甲基吡咯烷酮，配置成浓度为8 wt%的溶液，在搅拌下依次缓慢加入15 g聚乙二醇（Mn=2000）和30 g羟基封端聚二甲基硅氧烷（Mn=500）至其溶解，得到透明溶液；
向上述溶液中依次加入20 g钛酸四丁酯、10 g甲基三甲氧基硅烷和0.03 g水，在20 ℃下搅拌反应3小时，得到溶胶混合物；
将体系温度降至5 ℃，向溶胶混合物中加入0.5 g 四甲基氢氧化胺，搅拌混合1小时，得到制膜液；
将制膜液涂覆于基板上，在70 ℃下保持8小时后，再在150 ℃下保持10小时，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
实施例5
在氩气气氛中，将300 g氟代聚芳醚阴离子聚合物（TMBA-Ⅴ-F--88%，Mn=50000）溶于二甲基亚砜，配置成浓度为20 wt%的溶液，在搅拌下依次缓慢加入24 g聚乙烯醇（Mn=5000）和36 g羟基封端聚二甲基硅氧烷（Mn=100000）至其溶解，得到透明溶液；
向上述溶液中依次加入6 g硅酸四乙酯、18 g丙基三甲氧基硅烷和0.36 g水，在70 ℃下搅拌反应3小时，得到溶胶混合物；
将体系温度降至20 ℃，向溶胶混合物中加入1.8 g三乙胺，搅拌混合1小时，得到制膜液；
将制膜液涂覆于基板上，在50 ℃下保持16小时后，再在100 ℃下保持20小时，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
实施例6
在氮气气氛中，将500 g氟代聚芳醚阴离子聚合物（TMPA-Ⅲ-Br--45%，Mn=150000）溶于环丁砜与二甲基亚砜混合溶剂（体积比1：1），配置成浓度为15 wt%的溶液，在搅拌下依次缓慢加入50 g聚乙二醇（Mn=20000）和25 g聚乙烯醇（Mn=1000）至其溶解，得到透明溶液；
向上述溶液中依次加入25 g 钛酸四丁酯、75 g甲基三乙氧基硅烷和0.25 g水，在0 ℃下搅拌反应5小时，得到溶胶混合物；
将体系温度保持在0 ℃，向溶胶混合物中加入1.5 g K2CO3，搅拌混合2小时，得到制膜液；
将制膜液涂覆于基板上，在60 ℃下保持16小时后，再在110 ℃下保持24小时，脱膜后用去离子水洗涤除去杂离子，得到一种氟取代聚芳醚复合阴离子电解质膜。
表1为实施例1~实施例6所得到的一种氟取代聚芳醚复合阴离子电解质膜的相关性能数据，其性能测试方法参见文献【Feng SG et al.,Journal of Membrane Science, 2009, 335 (1-2): 13-20及Tian B et al.,. Journal of Applied Electrochemistry, 2004, 34 (12):1205-1210】，测试温度为30℃。
表1 互穿网络型氟代聚芳醚类复合阴离子电解质膜的相关性能
Figure BDA0000194183879

Claims (9)

1.一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于，该方法的具体步骤如下：
（1）在惰性气氛中，将氟取代聚芳醚结构阴离子聚合物溶于合适溶剂，配置成5 wt%~20 wt%的溶液，其中氟取代聚芳醚结构阴离子聚合物具有如下结构： ，
式中：Ar=
Figure FDA0000194183862
 或
Figure FDA0000194183863
 ，R=H 或功能基，功能基的结构为
Figure FDA0000194183864
 、
Figure FDA0000194183865
 、 、
Figure FDA0000194183867
 或
Figure FDA0000194183868
 ，其中，X为F-、Cl-、Br-、I- 或OH-中的任意一种；然后在缓慢搅拌加入交联组分至其溶解，得到透明溶液；其中交联组分的加入量为氟取代聚芳醚结构阴离子聚合物加入量的1 wt%~40 wt%； 
（2）在步骤（1）中所得到的透明溶液中加入无机组分前驱体及水，在0 ℃~80 ℃温度下，搅拌反应1小时~6小时，得到溶胶混合物；其中无机组分前驱体的加入量为氟取代聚芳醚结构阴离子聚合物加入量的3 wt%~30 wt%，加水量为无机组分前驱体加入量的0.1 wt%~10 wt%；
（3）将步骤（2）中所得到的溶胶混合物体系温度降至0 ℃~50 ℃后，加入适量交联催化剂，搅拌反应0.5小时~2小时，得到制膜液；其中交联催化剂的 加入量为步骤（1）中交联组分加入量的0.5 wt%~10 wt%；
（4）将步骤（3）中所得到的制膜液涂覆于基板上，在50 ℃~80 ℃温度下，保持3小时~24小时后，再在100 ℃~150 ℃温度下，保持8小时~24小时后脱膜，脱膜后用去离子水洗涤除去杂离子，得到一种具有互穿网络结构的氟取代聚芳醚复合阴离子电解质膜。
2.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（1）中惰性气氛为氮气或氩气。
3.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（1）中氟取代聚芳醚结构阴离子聚合物的功能化程度值为15%~95%。
4.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（1）中氟取代聚芳醚结构阴离子聚合物的数均分子量Mn=5000~200000。 
5.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（1）中溶剂为二甲基甲酰胺、二甲基乙酰胺、1，2-二氯乙烷、乙腈、二甲基亚砜、二苯砜、环丁砜和N-甲基吡咯烷酮中的一种或多种。
6.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（1）中交联组分为聚乙二醇、聚乙烯醇和羟基封端聚二甲基硅氧烷中的一种或多种。
7.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（1）中交联组分的数均分子量Mn=500~300000。 
8.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（2）中无机组分前驱体为硅酸四乙酯、钛酸四丁酯、甲基三乙氧基硅烷、甲基三甲氧基硅烷、丙基三甲氧基硅烷和丙基三乙氧基硅烷中的一种或多种。.
9.根据 权利要求1所述的一种氟取代聚芳醚复合阴离子电解质膜的制备方法，其特征在于：所述步骤（3）中交联催化剂为KOH、NaOH、K2CO3，Na2CO3、三乙胺和四甲基氢氧化胺中的一种或多种。 
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