CN109121441A - 离子传导性高分子电解质膜铸造过程中根据提高极性溶剂的相分离的效果使离子通道的大小得到调节的离子传导性高分子电解质膜及其制备方法 - Google Patents
离子传导性高分子电解质膜铸造过程中根据提高极性溶剂的相分离的效果使离子通道的大小得到调节的离子传导性高分子电解质膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及离子传导性高分子电解质膜铸造过程中通过提高极性溶剂的相分离的效果来调节离子通道的大小及离子传导率的离子传导性高分子电解质膜及其制备方法。
Description
技术领域
本发明涉及通过将极性有机溶剂与亲水性溶剂以特定比率混合来调节或扩张离子传导性高分子电解质膜的离子通道的大小的方法。
背景技术
已广泛作为现有代表性阳离子传导性高分子电解质膜使用的代表性物质为由杜邦公司开发的Nafion。Nafion为氟类聚四氟乙烯(PTFE)主链与磺酸基末端的亲水性支链相结合的结构,由于亲水性、疏水性之间的相分离清晰,其离子通道形成得大且清晰。因此,具有在加湿条件下基于磺酸基的解离的高阳离子传导率(0.1S/cm)高的优点。
与氟类高分子电解质膜(例如,Nafion)相比,非氟类高分子电解质膜(例如,磺化聚醚醚酮(sPEEK)、磺化聚芳醚砜(sPAES))的主链(芳香族、疏水性)与支链(磺酸基、亲水性)之间的相分离小,因此具有较小的通道结合性及大小。然而,由于离子传导率通过离子通道,因而存在如下的问题,即,与氟类高分子电解质膜相比,具有更小的离子通道的非氟类高分子电解质膜的离子传导率更低。
除了阳离子传导性高分子电解质膜以外,在碱性环境中传导阴离子的电解质膜像上述高分子电解质膜一样,也按照主链的种类分为氟类、非氟类,支链具有胺类阳离子组(例如,季铵、苄基三甲基铵(benzyl trimethyl ammonium)、甲基咪唑鎓(methylimidazolium)、烷基铵(alkyl ammonium)、共振稳定胍盐(resonance stabilizedguanidinium)等)。
离子传导性高分子电解质膜的离子传导率是由离子交换能力及离子通道的大小决定。离子交换能力越高,离子传导率越高,但是由于高离子交换容量(IEC,ion exchangecapacity),因而存在因吸水膨胀(water swelling)急剧增加而导致溶解在水中的缺点。因此,若可以在不调节离子交换容量的情况下调节离子通道的大小,则可以容易地调节离子传导性高分子电解质膜的离子传导率,而没有吸水膨胀的问题。
发明内容
技术问题
本发明提供离子传导性高分子膜,上述离子传导性高分子膜可在无需调节离子传导性高分子电解质自身的离子交换容量或无需添加亲水性无机粒子的情况下,调节离子传导性高分子电解质的离子通道的大小,从而可调节离子传导率,而不降低物理性质。
解决问题的手段
本发明的一实施方式涉及通过将包含离子传导性非氟类或氟类高分子电解质和有机溶剂的溶液与亲水性溶剂以规定比率混合来调节高分子电解质膜的离子通道的大小的方法。
本发明的再一实施方式涉及通过在离子传导性非氟类或氟类高分子电解质和第一亲水性溶剂的混合溶液中以规定比率添加与上述非氟类或氟类高分子电解质的亲水性官能团兼容性突出的第二亲水性溶剂来调节高分子电解质膜的离子通道的大小的方法。
在本发明的另一实施方式中,本发明涉及由上述的方法制备而成的离子传导性高分子电解质膜,与不包含亲水性溶剂的高分子电解质膜相比,离子传导性高分子电解质膜的离子通道的大小得以扩张。
发明的效果
本发明可通过在由上述有机溶剂和上述高分子电解质形成的溶液内添加亲水性溶剂或者在上述高分子与亲水性溶剂以特定比率混合的溶剂内添加与亲水性官能团兼容性突出的极性亲水性溶剂来调节或扩张离子传导性高分子电解质膜的离子通道的大小。
附图说明
图1示出干燥步骤中的时间与加热温度的例。
图2为示出通过混合亲水性溶剂来调节高分子电解质膜的离子通道的大小的结构的概念图。
图3示出本发明的离子传导性高分子电解质膜相比于不具有极性溶剂效果的高分子电解质膜具有增加的离子传导率。
图4示出在实验2中获取的小角散射曲线。
具体实施方式
以下,对本发明进行详细说明。
本发明涉及调节离子传导性高分子电解质膜的离子通道的大小的方法。
本发明的调节离子传导性高分子电解质膜的离子通道的大小的方法包括在由有机溶剂和高分子电解质形成的溶液内以特定比率混合极性溶剂的步骤。更具体地,调节离子传导性高分子电解质膜的离子通道的大小的方法包括将包含离子传导性非氟类或氟类高分子电解质和有机溶剂的溶液与亲水性溶剂以规定比率混合的步骤。
并且,本发明的调节离子传导性高分子电解质膜的离子通道的大小的方法包括在上述高分子与亲水性溶剂以特定比率混合的溶剂内添加与亲水性官能团兼容性突出的极性亲水性溶剂并进行混合的步骤。更具体地,调节离子传导性高分子电解质膜的离子通道的大小的方法包括在离子传导性非氟类或氟类高分子电解质和第一亲水性溶剂的混合溶液中以规定比率添加与上述非氟类或氟类高分子电解质的亲水性官能团兼容性突出的第二亲水性溶剂的步骤。上述第一亲水性溶剂与第二亲水性溶剂可以是相同或互不相同的溶剂。
上述混合步骤为将由有机溶剂和非氟类高分子电解质或氟类高分子电解质形成的离子传导性高分子电解质溶液与极性溶剂混合的步骤。
上述离子传导性高分子电解质膜可以无限制地用作燃料电池用离子传导性膜。
上述非氟类高分子电解质或氟类高分子电解质为与作为磺酸基(SO3H)、胺基(NH3)或磷酸基(-PO3H2)中的至少一种基团的亲水性阳离子交换官能团相结合而成的结构或具有胺类亲水性阴离子交换官能团(例如,季铵、苄基三甲基铵、甲基咪唑鎓、烷基铵、共振稳定胍盐等)的结构。
根据制备方法,可将上述非氟类高分子电解质膜分为交联烃(cross-linkedhydrocarbons)、接枝聚合物(grafted polymer)、聚合物共混物(polymer blends),根据结合有亲水性官能团的结构可分为官能团直接与主链(main chain)相结合的结构、接枝有包含官能团的支链(side chain)的结构、由疏水性嵌段和亲水性嵌段组成的嵌段共聚物。
上述非氟类高分子电解质膜的主链由疏水性芳香族烃组成,官能团包含阳离子源和阴离子源,并呈现亲水性。
上述非氟类高分子电解质可以是聚芳撑类、聚醚酮及聚醚醚酮中的一种非氟类高分子或者可以是上述非氟类高分子与如下的亲水性离子交换官能团相结合而成的结构:上述亲水性离子交换官能团为磺酸基(SO3H)、胺基(NH3)、磷酸基(-PO3H2)的亲水性阳离子交换官能团及胺类亲水性阴离子交换官能团中的至少一种。
上述非氟类高分子电解质可以是磺化聚醚醚酮(sulfonatedpolyetheretherketone(sPEEK))、磺化聚醚酮(sulfonated polyetherketone(sPEK))、磺化聚醚砜(sulfonated polyethersulfone(sPES))、磺化聚芳醚砜(sulfonatedpolyarylethersulfone(sPAES))的阳离子传导性高分子膜或Neosepta、AR204SZRA、IPA、Selemion AMV或FAS的阴离子传导性高分子膜。
上述氟类高分子电解质为由疏水性的氟类主链(backbone)和亲水性支链(sidechain)形成的高分子电解质,根据主链的结构分为全氟类、半氟类,根据支链的官能团种类分为磺酸基、磷酸基、胺基等,根据支链的长度分为长支链(long side chain)或短支链(short sidechain)。
上述氟类高分子电解质可以为如下的氟类高分子与亲水性离子交换官能团相结合而成的结构(例如,季铵、苄基三甲基铵、甲基咪唑鎓、烷基铵、共振稳定胍盐等):上述氟类高分子为聚四氟乙烯(Polytetrafluoroethrylene,PTFE)、聚氟乙烯(Polyvinylfluoride,PVF)、聚偏氟乙烯(Polyvinylidine fluoride,PVDF)、聚四氟乙烯(Polyethylenetetrafluoroethylene,ETFE)的氟类基团中的至少一种,上述亲水性离子交换官能团为具有磺酸基(SO3H)、胺基(NH3)、磷酸基(-PO3H2)的亲水性阳离子交换官能团及胺类亲水性阴离子交换官能团的结构中的至少一种。
上述氟类高分子电解质可以为Nafion、Aquivion、Flemion、Gore、Aciplex、R-1030、Aciplex A-192或Morgane ADP。
上述有机溶剂为用作高分子溶解溶剂的极性非质子性溶剂,上述亲水性溶剂可以是与上述有机溶剂相比极性高的极性质子性溶剂。
用作高分子溶解溶剂的代表性的极性非质子性溶剂可以是选自由N,N-二甲基乙酰胺(N,N-dimethylacetamide,DMAc)、N-甲基吡咯烷酮(N-methyl pyrrolidone,NMP)、二甲亚砜(imethyl sulfoxide,DMSO)以及N,N-二甲基甲酰胺(N,N-dimethylformamide,DMF)组成的组中的至少一种。
优选的,上述亲水性溶剂使用具有高偶极矩并且能够与通道形成氢键的极性质子性溶剂。代表性的上述亲水性溶剂可以为选自由叔丁醇(t-butanol)、正丙醇(n-propanol)、乙醇(ethanol)、甲醇(methanol)、氨(ammonia)、乙酸(acetic acid)、水组成的组中的至少一种。
在上述方法中,相对于有机溶剂,可混合1~100重量百分比的亲水性溶剂。上述有机溶剂中可以以1~30重量百分比,优选地,以1~20重量百分比,更优选地,以1~10重量百分比溶解非氟类或氟类高分子电解质。
上述方法可通过调节高分子电解质膜的离子通道的大小来提高燃料电池用高分子电解质膜的离子传导率。
本发明涉及离子传导率得到提高的高分子电解质膜的制备方法。
上述高分子电解质膜的制备方法包括:将包含离子传导性非氟类或氟类高分子电解质和有机溶剂的溶液与亲水性溶剂以规定比率混合的步骤;以及将混合的上述溶液涂敷在基材上并进行干燥的步骤。
并且,上述高分子电解质膜的制备方法包括:在离子传导性非氟类或氟类高分子电解质和第一亲水性溶剂的混合溶液中以规定比率添加与上述非氟类或氟类高分子电解质的亲水性官能团兼容性突出的第二亲水性溶剂的步骤;以及将混合的上述溶液涂敷在基材上并进行干燥的步骤。
上述第一亲水性溶剂与第二亲水性溶剂可以为相同或互不相同的溶剂。
可通过上述方法调节或扩张离子通道的大小。更具体地,与不包含亲水性溶剂的高分子电解质膜相比,本申请的离子传导性高分子电解质膜的离子通道的大小得以扩张。与不包含亲水性溶剂的高分子电解质膜(即,不具有极性溶剂效果的高分子电解质膜)相比,离子传导性高分子电解质膜的离子通道的大小可增加至150%。
上述混合步骤可参照上文。
上述涂敷步骤可使用任何公知的膜形成方法。
上述干燥步骤为蒸发亲水性溶剂和有机溶剂的步骤。上述干燥步骤可使用任何公知的方法。
图1示出干燥步骤中的时间与加热温度的例。参照图1,在亲水性溶剂为水的情况下,上述干燥步骤在80℃的温度下将水蒸发规定时间,接着将温度提升到100℃来完全去除水,再可将温度提升到120℃来去除有机溶剂。
图2为示出通过混合亲水性溶剂(蓝色粒子)来调节高分子电解质膜的离子通道的大小的结构的概念图。磺化高分子电解质由疏水性主链和亲水性支链的相分离形成离子通道,非氟类烃类高分子电解质膜的相分离程度小于氟类高分子电解质膜,因此形成大小更小的离子通道,并且由于端点(dead-end)数量多,降低通道的连接性。
在另一实施方式中,本发明涉及由上述方法制备而成的燃料电池用高分子电解质膜。
与不具有亲水性溶剂效果的高分子电解质膜相比,本发明的高分子电解质膜由于极性亲水性溶剂而可调节离子通道的大小。
本发明的实施方式
以下,参照实施例进一步对本发明进行详细说明,但本发明并不局限于此。
实施例1
将包含二甲基乙酰胺(DMAc)的磺化聚醚醚酮(sulfonated polyetheretherketone,sPEEK)溶液(5重量百分比的磺化聚醚醚酮)与水混合并搅拌一天。相对于二甲基乙酰胺的重量,分别添加1~100%的水。
将完成搅拌的混合溶液在80℃的烤箱中铸造过夜。完成铸造后,将蒸馏水倒入玻璃器皿,并小心地从玻璃器皿剥开膜。接着,为了去除残留在电解质膜中的有机溶剂,在1M的硫酸溶液中并在80℃的条件下煮沸1小时,接着在100℃的水中煮沸1小时。
比较例1
除了不添加水以外,以与实施例1相同的方法执行。
实验1:测量离子传导率
测量在实施例1和比较例1制备的高分子电解质膜的厚度后,将Bekktech公司的四探针电导率电池(4probe conductivity cell)与交流阻抗(AC impedance)相连接后,在80℃/100%的相对湿度(RH)条件下,测量离子传导率。
实验2:小角散射法
利用浦项粒子加速器中心的4C SAXS2光束示出小角散射曲线。
图3和表1示出在80℃/100%的加湿条件下,在实验1中测量的离子传导率。
表1
水/二甲基乙酰胺(%) | 离子传导率增加率(%) |
0~100 | 100~150 |
参照图3和表1,当在80℃的条件下,相对于有机溶剂,添加0~100重量百分比的水时,与比较例1相比,实施例1增加了100~150%的离子传导率。
图4示出在实验2中获取的小角散射曲线。表2示出利用图4的数据导出的离子通道的上升率。
表2
水/二甲基乙酰胺(%) | 离子通道大小的上升率(%) |
0~100 | 100~150 |
参照表2可确认,与比较例1相比,实施例1(当相对于有机溶剂,添加0~100重量百分比的水时)的离子通道的大小增加至100~150%。
以上,说明了本发明的具体实施例。本发明所属领域普通技术人员可以理解,在不脱离本质上的特性的范围内,本发明可以以变形的形态体现。本发明的范围由发明要求保护范围示出,而非上述说明,并且在其等同范围内的所有差异点应被解释为包括在本发明中。
产业上的可利用性
本发明可用作离子传导性高分子电解质膜。
Claims (16)
1.一种调节高分子电解质膜的离子通道的大小的方法,其特征在于,将包含离子传导性非氟类或氟类高分子电解质和有机溶剂的溶液与亲水性溶剂以规定比率混合。
2.一种调节高分子电解质膜的离子通道的大小的方法,其特征在于,在离子传导性非氟类或氟类高分子电解质和第一亲水性溶剂的混合溶液中以规定比率添加与上述非氟类或氟类高分子电解质的亲水性官能团兼容性突出的第二亲水性溶剂。
3.根据权利要求2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,上述第一亲水性溶剂与第二亲水性溶剂为相同或互不相同的溶剂。
4.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,上述有机溶剂为用作用于溶解高分子的溶剂的极性非质子性溶剂,上述亲水性溶剂为极性高于上述有机溶剂的极性的极性质子性溶剂。
5.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,极性有机溶剂为选自由N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜以及N,N-二甲基甲酰胺组成的组中的一种,上述亲水性溶剂为选自由叔丁醇、正丙醇、乙醇、甲醇、氨、乙酸、水组成的组中的至少一种。
6.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,上述氟类高分子电解质为如下的氟类高分子与亲水性离子交换官能团相结合而成的结构:上述氟类高分子为聚四氟乙烯、聚氟乙烯、聚偏氟乙烯、聚四氟乙烯的氟类基团中的至少一种,上述亲水性离子交换官能团为具有磺酸基、胺基、磷酸基的亲水性阳离子交换官能团及胺类亲水性阴离子交换官能团的结构中的至少一种。
7.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,上述氟类高分子电解质为Nafion、Aquivio n、Flemion、Gore、Aciplex、R-1030、AciplexA-192或Morgane AD P。
8.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,上述非氟类高分子电解质为聚芳撑类、聚醚酮及聚醚醚酮中的一种非氟类高分子或者为上述非氟类高分子与如下的亲水性离子交换官能团相结合而成的结构:上述亲水性离子交换官能团为磺酸基、胺基、磷酸基的亲水性阳离子交换官能团及胺类亲水性阴离子交换官能团中的至少一种。
9.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,上述非氟类高分子电解质为磺化聚醚醚酮、磺化聚醚酮、磺化聚醚砜、磺化聚芳醚砜的阳离子传导性高分子膜或阴离子传导性高分子膜。
10.根据权利要求1或2所述的调节高分子电解质膜的离子通道的大小的方法,其特征在于,在上述调节高分子电解质膜的离子通道的大小的方法中,相对于上述有机溶剂,混合1~100重量百分比的亲水性溶剂。
11.一种通过调节权利要求1或2所述的高分子电解质膜的离子通道的大小来提高燃料电池用高分子电解质膜的离子传导率的方法。
12.一种离子传导性高分子电解质膜的制备方法,其特征在于,包括:
将包含离子传导性非氟类或氟类高分子电解质和有机溶剂的溶液与亲水性溶剂以规定比率混合的步骤;以及
将混合的上述溶液涂敷在基材上并进行干燥的步骤。
13.一种离子传导性高分子电解质膜的制备方法,其特征在于,包括:
在离子传导性非氟类或氟类高分子电解质和第一亲水性溶剂的混合溶液中以规定比率添加与上述非氟类或氟类高分子电解质的亲水性官能团兼容性突出的第二亲水性溶剂的步骤;以及
将混合的上述溶液涂敷在基材上并进行干燥的步骤,
上述第一亲水性溶剂与第二亲水性溶剂为相同或互不相同的溶剂。
14.一种离子传导性高分子电解质膜,其特征在于,由权利要求12或13所述的离子传导性高分子电解质膜的制备方法制备而成,与不包含亲水性溶剂的高分子电解质膜相比,离子传导性高分子电解质膜的离子通道的大小得以扩张。
15.根据权利要求14所述的离子传导性高分子电解质膜,其特征在于,与不具有极性溶剂效果的高分子电解质膜相比,离子传导性高分子电解质膜的离子通道的大小增加至150%。
16.一种高分子燃料电池,其特征在于,包括权利要求14所述的离子传导性高分子电解质膜。
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US20190123373A1 (en) | 2019-04-25 |
WO2017175959A1 (ko) | 2017-10-12 |
KR101931411B1 (ko) | 2018-12-20 |
KR20170115354A (ko) | 2017-10-17 |
US10797334B2 (en) | 2020-10-06 |
CN109121441B (zh) | 2022-02-22 |
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