CN1624013A - 包含端磺酸基的聚合物、聚合物电解液及采用它的燃料电池 - Google Patents

包含端磺酸基的聚合物、聚合物电解液及采用它的燃料电池 Download PDF

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CN1624013A
CN1624013A CNA2004100859030A CN200410085903A CN1624013A CN 1624013 A CN1624013 A CN 1624013A CN A2004100859030 A CNA2004100859030 A CN A2004100859030A CN 200410085903 A CN200410085903 A CN 200410085903A CN 1624013 A CN1624013 A CN 1624013A
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金度鈗
郑珉周
郑明燮
文奉锡
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Samsung SDI Co Ltd
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Abstract

本发明提供一种包含端磺酸基的聚合物,其具有高离子电导率和良好的结构稳定性,即使在低湿度条件下也不分解,而且便宜。本发明还提供一种聚合物电解液以及采用该电解液的电池。该聚合物的侧链上具有含端磺酸基的取代基,所述取代基具有上面的式(1),式中n为1~5的数值。

Description

包含端磺酸基的聚合物、 聚合物电解液及采用它的燃料电池
                          技术领域
本发明涉及一种包含端磺酸基的聚合物、聚合物电解液和采用该聚合物电解液的燃料电池。更具体地,本发明涉及这样的包含端磺酸基的聚合物:其具有高离子电导率和良好的结构稳定性,即使在低湿度条件下也不分解,而且便宜,以及聚合物电解液和采用它的燃料电池。
                          背景技术
燃料电池是一种新的贮存能量系统,其中化学能通过燃料与氧的电化学反应而转化成电能。由于它们不是基于卡诺(Carnot)循环,所以它们是未来的清洁能源,具有比采用化石燃料的能源更高的理论发电效率,而且不大量地排放环境污染物。除了工业、家庭和运输应用外,这种燃料电池可以用作小型电气/电子设备(特别是便携式设备)的电源。
燃料电池可分为在大约500~700℃的较高温度下工作的熔融碳酸盐燃料电池,在大约200℃下工作的磷酸电解液电池,及在室温或大约100℃下工作的碱性电解液燃料电池和聚合物电解液膜(PEM)燃料电池。燃料电池的工作温度和构成材料依据电池中所用电解液的类型而确定。
根据向阳极提供燃料的方式,燃料电池可分为其中燃料经燃料转化炉转化成富氢气体之后再提供给阳极的外转化炉型,及燃料以气态或液态直接提供给阳极的直接燃料供给型或内转化炉型。
直接液体燃料供给型的燃料电池的代表性实例是直接甲醇燃料电池(DMFC)。DMFC一般采用甲醇水溶液作燃料,采用具有氢离子导电性的聚合物电解液膜作为电解液。众所周知,由于DMFC无需外转化炉,并且采用方便处理的燃料,所以它们具有最高的电势,可用作为便携式电源。
DMFC中发生的电化学反应如下:燃料在阳极被氧化,且氧在阴极通过与氢离子反应而被还原成水。
阳极反应:
阴极反应:
总反应:
从上述反应方程式中可以看出,一个甲醇分子与一个水分子在阳极反应,产生一个二氧化碳分子,六个氢离子,及六个电子。所产生的氢离子通过聚合物电解液迁移至阴极,并在阴极与氧和通过外电路提供的电子反应,生成水。概括DMFC中的总反应,通过甲醇与氧反应产生水和二氧化碳。结果,与甲醇燃烧热相当的绝大部分能量被转化成电能。
具有氢离子导电性的聚合物电解液膜充当阳极氧化反应所生成的氢离子迁移至阴极的途径,并且充当阳极与阴极之间的隔板。聚合物电解液膜应当满足下列要求:具有足够高的离子电导率,以促进大量氢离子的迅速迁移;电化学稳定性;适用于隔板的机械强度;工作温度下的热稳定性;易于加工成薄膜,以便能够降低其对离子传导的阻力;及被液体浸渍时的非溶胀性。
氟化聚合物膜,如Nafion(Dupont的商标)、Assiflex(Asahi Chemicals的商标)和Flemion(Asahi Glass的商标),是目前能够得到的用于燃料电池的聚合物膜。这些氟化聚合物膜在低温时可以较好地工作,但是在至少130℃的高温下失去其中所含的水,导致离子通道结构被破坏,影响离子导电性。就DMFC而言,会发生通过膜的甲醇泄漏,而且实用性低。此外,由于其价格高,氟化聚合物膜难于商业化。
为了解决这些问题,已经进行了很多研究工作,目的是寻找一种比Nafion便宜的聚合物膜,例如US 5422411中公开的三氟苯乙烯共聚物。然而,该便宜的聚合物膜的机械性能和形成薄膜的能力差。此外,采用磺化芳族聚合物如聚酰亚胺或聚醚砜的系统非常脆,难于成膜。为提供离子导电性而引入的磺酸基(-SO3H)增加了系统的脆性,因而无法形成稳定的膜。为了克服这些缺点,不得不降低聚合物的磺化率或者增加膜的厚度。这种情况下,膜的离子交换能力显著降低,因此,采用该电解液膜的燃料电池的性能降低。
                          发明内容
本发明提供一种具有高离子电导率的包含端磺酸基的聚合物。
本发明又提供一种制备上述聚合物的方法。
本发明也提供一种采用上述聚合物的聚合物电解液。
本发明还提供一种采用上述聚合物的燃料电池。
一方面,本发明提供一种聚合物,其侧链上具有含端磺酸基的取代基,所述取代基具有下面的式(1):
Figure A20041008590300081
式中n为1~5的数值。
另一方面,本发明提供一种侧链上具有上述式(1)的取代基的聚合物的制备方法,该方法包括:通过溴甲基二羟基苯与苄基溴的一釜反应,在具有羟基的聚合物的侧链上提供高度接枝(hyper-branch);及用磺酸基取代高度接枝的氢原子。
又一方面,本发明提供一种侧链上具有上述式(1)的取代基的聚合物的制备方法,该方法包括:使具有羟基的聚合物与具有下面式(7)的单体反应,以向聚合物的侧链引入高度接枝;及用磺酸基取代所述高度接枝的氢原子:
式中n为1~5的数值。
再一方面,本发明提供一种通过交联上述聚合物而得到的聚合物电解液。
还一方面,本发明提供一种采用上述聚合物电解液的燃料电池。
                         具体实施方式
下文中将更详细地说明本发明。
根据本发明,聚合物的侧链被至少具有两个苯基的枝聚物(dendrimer)所取代,且该聚合物被磺化。然后,可以得到具有许多磺酸基的聚合物,该聚合物具有高离子电导率。此外,利用交联剂,通过交联该聚合物,可以制得几乎不溶胀且在在低湿度条件下也具有高离子电导率的聚合物电解液,而且可以利用该聚合物电解液制造燃料电池。
根据本发明的聚合物电解液的聚合物的侧链上,具有下面式(1)的包含端磺酸基的取代基:
Figure A20041008590300091
式中n为1~5的数值。
上述聚合物可以是具有下面式(2)的聚合物:
式中R1,R2,R3,R4,R5,R6,及R7各自独立地为氢原子,取代或未取代的C1-6烷基,或卤原子;n为10~1000的数值;及R为具有上述式(1)的取代基。
上面具有式(2)的聚合物还可以包含具有下面式(3)的重复单元:
式中R8,R9,R10,R11,R12,R13,及R14各自独立地为氢原子,取代或未取代的C1-6烷基,或卤原子。
特别地,具有上述式(2)的进一步包含具有式(3)的重复单元的聚合物,还可以是具有下面式(4)的聚合物:
式中R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,及R14各自独立地为氢原子,取代或未取代的C1-6烷基,或卤原子;n为5~1000的数值;m为5~1000的数值;m/n为0.001~5的数值;及R为具有上述式(1)的取代基。
此外,具有上述式(1)所示取代基的聚合物也可以是具有下面式(5)或式(6)的聚合物:
Figure A20041008590300111
式中Ar为四价的芳族或脂族有机基团;X为单键,-O-,-S-,C1-6亚烷基,
Figure A20041008590300113
n为3~1000的数值;及R为具有上述式(1)的取代基。
式中Ar1为单键,取代或未取代的C1-6亚烷基,或取代或未取代的C6-20亚芳基;X为单键,-O-,-S-,C1-6亚烷基,
Figure A20041008590300115
n为3~1000的数值;及R为具有上述式(1)的取代基。
四价芳族有机基团的实例包括具有下面式(5a)至(5f)的官能团:
Figure A20041008590300117
侧链上具有上述式(1)所示的取代基的聚合物可以通过诸如下述实施例所示的多种方法制备。
制备侧链上具有上述式(1)所示的取代基的聚合物的方法之一包括:通过甲基二羟基苯与苄基溴的一釜反应,在具有羟基的聚合物的侧链上提供高度接枝;及用磺酸基取代高度接枝的氢原子。
制备侧链上具有上述式(1)所示的取代基的聚合物的另一支方法包括:使具有羟基的聚合物与具有下面式(7)的单体反应,以向聚合物侧链引入高度接枝;及用磺酸基取代高度接枝的氢原子。
Figure A20041008590300131
式中n为1~5的数值。
根据本发明,还可以利用交联剂,通过交联所述聚合物来制备聚合物电解液,该聚合物电解液几乎不溶胀,即使在低湿度条件下也具有高离子电导率。交联剂的实例包括但不限于H3PO4和/或4-羟甲基咪唑。
现将详述采用根据本发明实施方案的聚合物电解液的燃料电池。
根据本发明的聚合物电解液可应用于各种类型的燃料电池,例如,以氢为燃料的聚合物电解液膜燃料电池(PEMFC),及以甲醇蒸气和水蒸气的混合物或甲醇水溶液为燃料的直接甲醇燃料电池(DMFC)。具体地,本发明的聚合物电解液可以应用于采用甲醇水溶液的DMFC。
本发明提供一种燃料电池,包括氧在其中被还原的阴极,燃料在其中被氧化的阳极,及介于阴极与阳极之间的电解液,其中该电解液是根据本发明实施方案的聚合物电解液。
阴极包括催化氧之还原反应的催化剂层。催化剂层包括催化剂颗粒和具有阳离子交换基团的聚合物。催化剂的实例为碳载的Pt(Pt/C)催化剂。
阳极包括催化燃料之氧化反应的催化剂层,所述容量的实例包括氢、天然气、甲醇、乙醇等。催化剂层包括催化剂颗粒和具有阳离子交换基团的聚合物。催化剂的具体实例包括Pt/C催化剂,碳载的Pt-Ru催化剂等。具体地,当直接向阳极提供有机燃料而不是氢时,可以使用碳载的Pt-Ru催化剂。
用于阴极和阳极的催化剂包括催化金属颗粒及催化剂载体。作为催化剂载体,可以使用具有导电性并且具有能够承载催化金属颗粒的微孔的固体粉末,如碳粉末。碳粉末的实例包括碳黑,Ketzen碳黑,乙炔黑,活性碳粉末,碳纳米纤维粉末,及其混合物。作为具有阳离子交换基团的聚合物,可以使用上述的聚合物。
阴极和阳极的催化剂层分别与聚合物电解液接触。
除催化剂层之外,阴极和阳极各自可进一步包含气体扩散层。气体扩散层由导电性多孔材料构成。气体扩散层充当集电体以及反应物和产物的进/出途径。作为气体扩散层,可以使用碳纸(carbon paper)。优选碳纸是防水的,更优选防水碳纸上涂有防水的碳黑层。防水碳纸包括疏水聚合物层,如聚四氟乙烯(PTFE)。疏水聚合物是熔结的。气体扩散层是防水的,以确保极性的液体反应物和气体反应物的进/出途径。在具有防水碳黑层的防水碳纸中,防水碳黑层包含碳黑和疏水聚合物如PTFE作为疏水粘合剂。防水碳黑层涂布在上述防水碳纸的侧面。防水碳黑层的疏水聚合物是熔结的。
阴极和阳极可以通过各种公知的方法制备,没有特殊的限制。
可提供给本发明之燃料电池的阳极的燃料的实例包括氢、天然气、甲醇、乙醇等。
包含极性有机燃料和水的液体燃料可以提供给阳极。极性有机燃料的实例包括甲醇、乙醇等。液体燃料可以是甲醇水溶液。
现将参照下述实施例更详细地说明本发明。下面的实施例仅用于说明,而不是对本发明的范围的限制。
实施例1
在氮气氛下,于装有搅拌器的三颈反应烧瓶中,将3.2g第二代枝聚物C2-Br溶解于四氢呋喃,并向溶液中加入0.5g的聚羟基苯乙烯、1.2g的K2CO3和0.2g的18-冠醚-6并混合,同时保持反应混合物的温度为80℃。反应12小时之后,将所得产物倒入水与甲醇的1∶1混合物中,以形成沉淀。过滤沉淀物,得到聚合物粉末。将所得聚合物粉末在真空烘箱中于60℃下干燥24小时。该聚合物具有下面的式(8)。产物经IR光谱分析时,位于3300~3600cm-1的OH基团峰消失,表明合成了具有下面式(8)的聚合物。
Mn:52800
Mw:102100
Tg:125℃
实施例2
将得自实施例1的聚合物粉末溶解于硫酸溶液并在80℃下反应12小时,然后将反应产物倒入乙醚中,以形成沉淀。过滤沉淀物并将其溶解于水中。该溶液通过透析膜进行纯化,得到具有下面式(9)的聚合物。产物经IR光谱分析时,在1238~1136cm-1处出现了-SO3H峰,表明已经合成了具有下面式(9)的聚合物。
Figure A20041008590300161
实施例3
在氮气氛下,于装有搅拌的三颈反应烧瓶中,将2.4g的聚羟基苯乙烯、4.1g的3,5-二羟基苄基溴、5.0g的K2CO3和0.6g的18-冠醚-6溶解于DMSO中,并在100℃下反应1小时。向反应物中加入7.5g的苄基溴和10.0g的K2CO3,并于100℃下加热48小时。将所得产物在水中进行沉淀并过滤,得到聚合物粉末。将所得聚合物粉末在真空烘箱中于60℃下干燥24小时。
所得聚合物具有下面的式(10)。产物经IR光谱分析时,位于3300~3600cm-1的OH基团峰消失,表明合成了具有下面式(10)的聚合物。
Mn:38200
Mw:76800
Tg:132℃
实施例4
将得自实施例3的聚合物粉末溶解于硫酸溶液中,并于80℃下反应12小时,然后将反应产物倒入乙醚中,以形成沉淀。过滤沉淀物,并将其溶解于水中。该溶液经透析膜纯化,得到具有下面式(11)的聚合物。产物经IR光谱分析时,在1211~1132cm-1处出现-SO3H峰,表明已经合成了具有下面式(11)的聚合物。
Figure A20041008590300181
实施例5
在氮气氛下,于装有搅拌的三颈反应烧瓶中,将4.0g的聚酰亚胺和5.0g的第二代枝聚物C2-Br溶解于NMP,并向该溶液中加入1.5g的三乙胺,然后反应12小时。将所得产物倒入水与甲醇的4∶1混合物中,以形成沉淀。过滤沉淀物,得到聚合物粉末。将所得的聚合物粉末在真空烘箱中于60℃下干燥24小时。所得聚合物具有下面的式(12)。
Mn:4830
Mw:10200
Tg:166℃
实施例6
将得自实施例5的聚合物粉末溶解于硫酸溶液中,并于80℃下反应12小时,然后将反应产物倒入乙醚中,以形成沉淀。过滤沉淀物并将其溶解于水中。通过透析膜纯化该溶液,得到具有下面式(13)的聚合物。产物经IR光谱分析时,在1220~1128cm-1处出现-SO3H峰,表明合成了具有下面式(13)的聚合物。
Figure A20041008590300191
实施例7
将得自实施例2的聚合物电解液与用作交联剂的H3PO4和4-羟甲基咪唑在180℃的加热板上热处理30分钟,得到所需的聚合物电解液膜。
实施例8
将得自实施例6的聚合物电解液与用作交联剂的H3PO4和4-羟甲基咪唑在180℃的加热板上热处理30分钟,得到所需的聚合物电解液膜。
聚合物电解液性能的评价
利用Solatron 1260阻抗计,分别测量得自实施例7和8的聚合物电解液以及Nafion 115的离子电导率,所得结果列于下面的表1中。
             表1
    离子电导率(S/cm)
    80℃     120℃
  实施例7     0.07     0.05
  实施例8     0.05     0.01
  Nafion 115     0.1     0
从表1可以看出,实施例7和8的聚合物电解液均具有比Nafion 115高的离子电导率。
机械强度的评价
利用SHIMADZU AGS-G UTM测量实施例7和8的聚合物电解液膜的拉伸模量。实施例7的聚合物电解液膜具有38%的拉伸模量,实施例8的聚合物电解液膜具有15%的拉伸模量。
如上所述,根据本发明的聚合物的侧链上具有包含端磺酸基的取代基,因而可以获得高离子电导率。此外,通过交联该聚合物可以得到聚合物电解液,所述电解液几乎不溶胀,即使在低湿度条件下也具有高离子电导率。因此,利用该电解液可以得到电性能及机械性能均得到改善的燃料电池。
尽管已经参照其示例性实施方案具体地给出和说明了本发明,但是本领域的技术人员应当理解,在不脱离权利要求书中所定义的本发明的构思和范围的情况下,可以在形式和内容上对其作出各种改变。

Claims (10)

1.一种聚合物,其侧链上具有含端磺酸基的取代基,所述取代基具有下面的式(1):
Figure A2004100859030002C1
式中n为1~5的数值。
2.根据权利要求1的聚合物,其具有下面的式(2):
式中R1,R2,R3,R4,R5,R6,及R7各自独立地为氢原子,取代或未取代的C1-6烷基,或卤原子;n为10~1000的数值;及R为具有权利要求1中的式(1)的取代基。
3.根据权利要求2的聚合物,其中该具有式(2)的聚合物进一步包含具有下面式(3)的重复单元:
式中R8,R9,R10,R11,R12,R13,及R14各自独立地为氢原子,取代或未取代的C1-6烷基,或卤原子。
4.根据权利要求3的聚合物,其中所述进一步包含具有式(3)之重复单元的具有式(2)的聚合物,具有下面的式(4):
式中R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,及R14各自独立地为氢原子,取代或未取代的C1-6烷基,或卤原子;n为5~1000的数值;m为5~1000的数值;m/n为0.001~5的数值;及R为具有权利要求1中的式(1)的取代基。
5.根据权利要求1的聚合物,其具有下面的式(5):
式中Ar为四价的芳族或脂族基团;X为单键,-O-,-S-,C1-6亚烷基,
Figure A2004100859030004C1
Figure A2004100859030004C2
n为3~1000的数值;及R为具有权利要求1中的式(1)的取代基。
6.根据权利要求的聚合物,其具有下面的式(6):
式中Ar1为单键,取代或未取代的C1-6亚烷基,基片取代或未取代的C6-20亚芳基;X为单键,-O-,-S-,C1-6亚烷基, 为3~1000的数值;及R为具有权利要求1中的式(1)的取代基。
7.一种制备聚合物的方法,该聚合物的侧链上具有权利要求1中的式(1)所示的取代基,该方法包括:
通过溴甲基二羟基苯与苄基溴的一釜反应,为具有羟基的聚合物的侧链提供高度接枝(hyper-branch);及
用磺酸基取代所述高度接枝的氢原子。
8.一种制备聚合物的方法,该聚合物的侧链上具有权利要求1中的式(1)所示的取代基,该方法包括:
使具有羟基的聚合物与具有下面式(7)的单体反应,以向聚合物的侧链引入高度接枝;及
用磺酸基取代所述高度接枝的氢原子:
Figure A2004100859030005C1
式中n为1~5的数值。
9.一种聚合物电解液,其是通过交联权利要求1~6中任一项的聚合物而得到的。
10.一种燃料电池,其采用权利要求9的聚合物电解液。
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US7547748B2 (en) 2009-06-16
US20080199757A1 (en) 2008-08-21
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CN1289550C (zh) 2006-12-13
USRE42299E1 (en) 2011-04-19
JP2005126721A (ja) 2005-05-19
US20050112440A1 (en) 2005-05-26
US7378471B2 (en) 2008-05-27
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