CN101297001A - 离子传导材料、固体聚合物电解质膜和燃料电池 - Google Patents
离子传导材料、固体聚合物电解质膜和燃料电池 Download PDFInfo
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Abstract
本发明提供一种离子传导材料,其特征在于含有一种离子传导主要组分聚合物,以及添加到该主要组分聚合物中的玻璃化转变温度(Tg)比该主要组分聚合物低的聚合物,并提供一种使用该离子传导材料的固体聚合物燃料电池。根据分子运动论以上结构能改进固体聚合物电解质的离子传导性。
Description
技术领域
本发明涉及一种具有改进的离子传导性的离子传导材料,其制造方法,及其固体聚合物电解质膜和使用之的燃料电池。
背景技术
固体聚合物电解质是具有电解质基团的固体聚合物材料,例如在聚合物链上的磺酸基团,其能与特定离子牢固地键合并选择性地允许阳或阴离子渗透。因为固体聚合物电解质具有这种特性,它们形成颗粒、纤维或膜在各种应用中使用,例如电渗析、扩散透析和蓄电池隔膜。
例如,燃料电池通过电池内的诸如氢或甲醇这类燃料的电化学氧化,将燃料的化学能直接转换成电能并将其抽取。近年来,燃料电池作为一种电能的清洁来源而被关注。考虑到其能达到高输出密度并在低温下操作的事实,使用质子交换膜作为电解质的固体聚合物燃料电池尤其被期望作为电动车辆的电源。
用于固体聚合物燃料电池的固体聚合物电解质膜要求具有高的离子传导性。因此,主要使用具有全氟亚烃基骨架且局部具有离子交换基团的氟化膜,例如全氟乙烯醚的侧链端的磺酸基团或羧酸基团。氟电解质膜,以全氟磺酸膜为代表,具有非常高的化学稳定性,由此被称为是能够在苛刻条件下使用的电解质膜。已知的这类氟电解质膜的例子包括Nafion膜(Du Pont)、Dow膜(Dow Chemical)、Aciplex膜(Asahi Kasei Co.,Ltd.)和Flemion膜(Asahi Glass Co.,Ltd.)。
除了以Nafion膜为代表的氟化聚合物电解质膜外,包括以烃作为构成成分的烃电解质膜也是公知的。
尽管常规的离子传导膜拥有一定级别的离子导电性,但是燃料电池需要更高性能的离子传导膜。
因此,当各种新的材料例如氟化材料、烃基材料和烃工程塑性材料已经被建议用作常规的聚合物电解质时,日本专利申请(Kokai)No.2003-349245A研究了其膜形成工艺。
此外,日本专利申请(Kokai)No.2002-008440A描述了为了改进磺化的聚芳撑膜的延展性而不损伤质子传导性,添加高分子量聚乙二醇到磺化的聚芳撑。然而,添加的聚乙二醇仅在于改进磺化的聚芳撑膜的延展性。没有任何改进磺化的聚芳撑的热或电特性的意图的描述。在这些实例中,所用的聚乙二醇也是高分子量化合物,具有2000的高数均分子量。
发明内容
燃料电池电解质膜的功能是传导质子。如果质子传导性提高,由质子传导性产生的电阻下降,从而改进燃料电池性能。尽管多种材料被建议用于改进质子传导性,没有关于质子传导性的实质改进被报道,而是被尝试于改进耐久性等。此外,即使在上述专利文献1所述的膜形成工艺中,也没有关注关于质子传导性的有意义的改进。
这是因为常规技术已经总体而言发展到使得材料和工艺最优化了,并且还没有过基于质子传导性的原理即分子运动论的讨论。
因此,本发明的一个目的在于从分子运动论来改进常规的固体聚合物电解质的离子传导性。
本发明着眼于通过加强聚合物材料的分子运动改善离子传输性能的事实,从而得到了本发明。
具体地,本发明的第一方面是离子传导材料的发明,其特征在于,含有离子传导主要组分聚合物,以及添加在该主要组分聚合物中的、玻璃化转变温度(Tg)比该主要组分聚合物低的聚合物。通过在离子传导电解质(A)中少量添加玻璃化转变温度(Tg)低于(A)的聚合物(B),离子的传输会由于(A)中的(B)的热运动而增强,由此,材料(A)+(B)与(A)本身相较表现出显著高的离子传导性。
尽管就改进离子传导性的观点而言添加的聚合物(B)的Tg优选是尽可能低的,但是Tg要根据与使用相关的附加因素来限定,例如机械强度。因此,添加的聚合物的玻璃化转变温度(Tg)优选为比主要组分聚合物至少低50℃,更优选至少低70℃。此外,为了提高与作为电解质的主要组分聚合物之间的可混性,添加的聚合物优选为水溶性聚合物。
尽管添加的聚合物的添加量可以在宽的范围中选择,但是如果添加量低则几乎没有由于热运动引起的离子传输的改进,如果添加量高则主要组分聚合物的离子传导性以及各种物理特性例如耐热性劣化,而这是不优选的。因此,主要组分聚合物与添加的聚合物之间的重量比优选为99∶1至80∶20,更优选为95∶5至80∶20。
作为上述主要组分聚合物,现有技术已知的各种离子传导聚合物均可以广泛地被采用。此外,至于也添加到主要组分聚合物中的聚合物,广泛种类的均可以采用,只要该聚合具有比主要组分聚合物低的玻璃化转变温度(Tg)。其中优选的例子包括,全氟磺酸聚合物作为主要组分聚合物,并且具有小于3000、优选为2000或更少的数均分子量的聚乙二醇(PEG)作为添加的聚合物的组合。
本发明的第二方面是含有一种或多种上述离子传导材料的固体聚合物电解质膜。根据本发明的固体聚合物电解质膜与使用主要组分聚合物本身时相比较具有显著改进的质子传导性。这里,关于从离子传导材料形成膜的方法没有限制。该膜可以通过将根据本发明的离子传导材料粉末与适合的粘结剂混合来形成。通常能采用的方法包括,在平板上流延(casting)溶液的流延法,通过口模涂布机、comma coater等在平板上涂敷溶液的方法,以及牵拉熔融离子传导材料的方法。
本发明的第三方面是使用一种或多种上述离子传导材料的燃料电池。具体地,提供一种固体聚合物燃料电池,具有这样的膜电极组件(MEA),即其由固体聚合物电解质膜(a)和气体扩散电极(b)构成,其与电解质膜键合且具有作为其主要构成材料的电极催化剂,该催化剂由承载催化金属和质子交换材料的导电载体构成,其中聚合物固体电解质膜和/或质子交换材料由上述离子传导材料或上述固体聚合物电解质膜构成。
本发明的第四方面是用于改进离子传导聚合物的离子传导性的方法发明,其特征在于,在离子传导主要组分聚合物中添加玻璃化转变温度(Tg)比该主要组分聚合物低的聚合物。
如上所述,在根据本发明的用于改进离子传导性的方法中,添加的聚合物的玻璃化转变温度(Tg)优选为比主要组分聚合物至少低50℃,更优选至少低70℃;主要组分聚合物与添加的聚合物之间的重量比优选为99∶1至80∶20,更优选为95∶5至80∶20;并且主要组分聚合物与添加的聚合物的组合优选为,全氟磺酸聚合物与具有小于3000、且优选2000或更少的数均分子量的聚乙二醇(PEG)的组合。
常规的固体电解质膜,例如全氟磺酸膜,仅通过与离子交换基团例如磺酸基团的化学反应来传导离子。相反,在本发明中,通过在离子传导主要组分聚合物中添加玻璃化转变温度(Tg)低于该主要组分聚合物的聚合物,离子的传输会因添加到该离子传导主要组分聚合物中的聚合物的热运动而增强,从而提供显著高的离子传导性。
因此,本发明能够根据分子运动论使常规的固体聚合物电解质膜的离子传导性得到改进。
附图说明
图1表示对于Nafion与添加的聚合物的重量比为95∶5的样品添加的聚合物的Tg与该混合材料的质子传导性;以及
图2表示对于Nafion与添加的聚合物的重量比为80∶20的样品添加的聚合物的Tg与该混合材料的质子传导性。
优选实施方式
现在将通过介绍以下实施例更详细地描述本发明。
具有不同Tg的添加的聚合物混合在NafionTM中。质子传导性在一个大气压下测定。
【质子传导性的测定】
夹在铂电极中间的样品被放置在控制为100℃的恒温炉中。在0.1-1000kHz的频率以及10mV的外加电压下使用频率响应分析仪(由NFElectronic Instruments制造)测定质子传导性。
【玻璃化转变温度(Tg)的测定】
使用市售的由Seiko Instruments Inc.制造的差示扫描量热仪(DSC)测量玻璃化转变温度。
【样品制造】
关于添加的聚合物,市售的聚乙二醇(PEG:380-420的数均分子量,Tg=-9℃,由Merck制造),聚乙二醇(PEG:950-1050的数均分子量,Tg=40℃,由Merck制造),聚乙烯醇(PVA:450-550的数均分子量,Tg=200℃,由Merck制造),聚芳基酰胺(约1500的数均分子量,Tg=150℃,由Aldrich制造)以及聚丙烯酸(Tg=106℃),被溶解在纯水中,然后搅拌所得到的混合物以获得具有20重量%的重量含量的均匀的溶液。这里,聚乙烯醇(PVA)和聚芳基酰胺作为本发明的比较实施例。
这些溶液以以下比例与市售的20重量%的Nafion(EW=1000,由Aldrich制造)混合。将所得到的混合物搅拌2小时以获得均匀的混合溶液。将所获得的溶液涂敷在特氟隆板上,其随后在具盖培养皿内干燥一周以获得膜。用千分尺测量所获得的膜的厚度,并测定质子传导性。
【实施例1】
根据上述工艺制造样品以使得Nafion与添加的聚合物的重量比为95∶5。添加的聚合物的Tg和混合材料的质子传导性如图1所示。在图1中,聚乙二醇(PEG:380-420的数均分子量,Tg=-9℃,由Merck制造)由B1表示,聚乙二醇(PEG:950-1050的数均分子量,Tg=40℃,由Merck制造)由B2表示,聚乙烯醇(PVA:450-550的数均分子量,Tg=200℃,由Merck制造)由B3表示,聚芳基酰胺(约1500的数均分子量,Tg=150℃,由Aldrich制造)由B4表示,聚丙烯酸(Tg=106℃)由B5表示。
【实施例2】
根据上述工艺制造样品以使得Nafion与添加的聚合物的重量比为80∶20。添加的聚合物的Tg和混合材料的质子传导性如图2所示。与图1相同,聚乙二醇(PEG:380-420的数均分子量,Tg=-9℃,由Merck制造)由B1表示,聚乙二醇(PEG:950-1050的数均分子量,Tg=40℃,由Merck制造)由B2表示,聚乙烯醇(PVA:450-550的数均分子量,Tg=200℃,由Merck制造)由B3表示,聚芳基酰胺(约1500的数均分子量,Tg=150℃,由Aldrich制造)由B4表示,聚丙烯酸(Tg=106℃)由B5表示。
从图1和2的结果可以看出,在添加的聚合物的Tg和混合材料的质子传导性之间存在强的相关性。具体地,能够看出,当添加的聚合物具有比 Nafion的Tg高的Tg时,由于较小的分子运动而使质子传导性劣化,而当添加的聚合物具有比Nafion的Tg小的Tg时,由于较大的分子运动而改进了质子传导性。
工业应用
根据分子运动论,通过相对容易的操作将玻璃化转变温度(Tg)比主要组分聚合物低的聚合物添加到离子传导主要组分聚合物中,能改进常规固体聚合物电解质膜的离子传导性。因此,本发明能够广泛的使用在使用各种固体聚合物电解质膜的燃料电池、水电解、氢卤酸电解、盐水电解、氧浓缩器、湿度传感器、气体传感器等中。通过在燃料电池中使用,由此能改进发电性能,由此对燃料电池的实际应用和推广做出贡献。
Claims (12)
1、一种离子传导材料,其特征在于含有离子传导主要组分聚合物,以及添加在该主要组分聚合物中的、玻璃化转变温度(Tg)比该主要组分聚合物低的聚合物。
2、根据权利要求1所述的离子传导材料,其特征在于,所述添加的聚合物具有比主要组分聚合物低至少50℃的玻璃化转变温度(Tg)。
3、根据权利要求1或2所述的离子传导材料,其特征在于,所述添加的聚合物为水溶性聚合物。
4、根据权利要求1~3中任一项所述的离子传导材料,其特征在于,所述主要组分聚合物与添加的聚合物的重量比为99∶1~80∶20。
5、根据权利要求1~4中任一项所述的离子传导材料,其特征在于,所述主要组分聚合物为全氟磺酸聚合物,所述添加的聚合物为数均分子量小于3000的聚乙二醇(PEG)。
6、一种固体聚合物电解质膜,其含有根据权利要求1~5中任一项所述的离子传导材料中的一种或多种。
7、一种燃料电池,其使用一种或多种根据权利要求1~5中任一项所述的离子传导材料。
8、一种改进离子传导性的方法,其特征在于,在离子传导主要组分聚合物中添加玻璃化转变温度(Tg)比该主要组分聚合物低的聚合物。
9、根据权利要求8所述的改进离子传导性的方法,其特征在于,所述添加的聚合物具有比主要组分聚合物低至少50℃的玻璃化转变温度(Tg)。
10、根据权利要求8或9所述的改进离子传导性的方法,其特征在于,所述添加的聚合物为水溶性聚合物。
11、根据权利要求8~10中任一项所述的改进离子传导性的方法,其特征在于,所述主要组分聚合物与添加的聚合物的重量比为99∶1~80∶20。
12、根据权利要求8~11中任一项所述的改进离子传导性的方法,其特征在于,所述主要组分聚合物为全氟磺酸聚合物,所述添加的聚合物为数均分子量小于3000的聚乙二醇(PEG)。
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JP5210078B2 (ja) * | 2008-07-31 | 2013-06-12 | ビッグテクノス株式会社 | 電気剥離性粘着剤組成物、電気剥離性粘着製品及びその剥離方法 |
FR2954766B1 (fr) * | 2009-12-24 | 2015-04-24 | Saint Gobain Ct Recherches | Poudre de granules de ceramique |
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JPH0987510A (ja) * | 1995-09-22 | 1997-03-31 | Japan Synthetic Rubber Co Ltd | プロトン伝導性高分子固体電解質 |
JP2962360B1 (ja) * | 1998-09-03 | 1999-10-12 | 日本電気株式会社 | シングルイオンおよびプロトン伝導性高分子体 |
JP4042285B2 (ja) * | 2000-02-23 | 2008-02-06 | トヨタ自動車株式会社 | 固体高分子電解質膜およびその製造方法 |
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US7396880B2 (en) * | 2005-05-24 | 2008-07-08 | Arkema Inc. | Blend of ionic (co)polymer resins and matrix (co)polymers |
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CN111092250B (zh) * | 2018-10-24 | 2023-04-07 | 丰田自动车株式会社 | 具有桥接结构的质子传导膜和燃料电池 |
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