CN100421292C - 制备金属催化剂和电极的方法 - Google Patents
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Abstract
本发明提供一种制备金属催化剂的方法,以及一种利用由此制得的金属催化剂制备电极的方法,其中所述金属催化剂具有传导性催化剂材料和形成在该传导性催化剂材料表面上的质子传导性材料涂层,所述制备金属催化剂的方法包括:混合传导性催化剂材料、离聚物和第一溶剂;将所得的混合物浇铸到担载层上并干燥所得到的产物,从而形成包含传导性催化剂的薄膜;及把该包含传导性催化剂的薄膜从担载层上分离,并研磨包含传导性催化剂的薄膜。该金属催化剂具有均匀涂有质子传导性材料的传导性催化剂颗粒,从而容易形成和控制用于电化学反应的三相界面、便于气体反应物穿过在催化剂颗粒上形成的质子传导性材料的薄涂层以接近催化剂,并且有效地传递由电化学反应产生的质子。当利用该催化剂制备电极时,可以形成理想的三相界面电极结构,并且包括该电极的燃料电池可以具有改善的性能,如高效率。
Description
技术领域
本发明涉及一种金属催化剂和利用包括它的电极的燃料电池,更具体地,本发明涉及一种在电化学反应中具有改善的催化效率并具有促进气体反应物渗透的结构的金属催化剂,及一种利用包括该金属催化剂的电极的燃料电池,该燃料电池具有改善的性能,如高效率。
背景技术
燃料电池作为一种可以替代矿物燃料的未来清洁能源出现。
燃料电池是一种通过氢和氧的电化学反应产生直流电的发电系统,并且其包括膜电极组件(MEA),该膜电极组件具有插入在阳极和阴极之间的电解液和用于传递气体的流场板。电极包括形成在由炭纸或炭布制得的担载层上的催化剂层。然而,在催化剂层中,气体反应物很难到达催化剂,并且由电化学反应产生的质子不能快速地移动。因而催化剂没有有效地用于电极中。
阴极和阳极是通过浇铸含有催化剂和离聚物的浆料在气体扩散层上作为担载层,及干燥所得到的产物形成催化剂层而制备的。
当电极的催化剂层以这种方式制备时,将离聚物掺杂在催化剂中或者简单地将其与催化剂混合,离聚物降低了催化剂的分散性质并导致催化剂层中催化剂和离聚物严重的聚结。结果,由于次生孔隙(secondary pore)和不均匀的离聚物引起的未反应催化剂的增加导致催化剂利用率降低、燃料供应路径缺乏和燃料的渗透性降低,从而显著地降低了燃料电池的性能。此外,难于形成和控制用于电化学反应的三相界面,并且催化效率降低。
发明内容
本发明提供一种金属催化剂及其制备方法,其中所述催化剂通过具有理想的三相界面结构而具有改善的催化效率,该理想的三维界面结构可以使气体反应物容易接近催化剂,并快速地传递电化学反应产生的质子,一种通过包括利用该金属催化剂的催化剂层制备效率得到改善的电极的方法,及一种利用根据该方法制得的电极的燃料电池。
根据本发明的一个方面,提供一种制备金属催化剂的方法,该金属催化剂具有传导性催化剂材料和形成在该传导性催化剂材料表面上的质子传导性材料涂层,该方法包括:混合传导性催化剂材料、离聚物和第一溶剂;将所得的混合物浇铸到担载层上,并干燥所得到的产物,从而形成包含传导性催化剂的薄膜;把该包含传导性催化剂的薄膜从担载层上分离,并研磨包含传导性催化剂的薄膜。
根据本发明的另一方面,提供一种制备电极的方法,该方法包括:混合金属催化剂与憎水粘合剂和第二溶剂,所述金属催化剂具有传导性催化剂材料和形成在该传导性催化剂材料表面上的质子传导性材料涂层,从而得到形成催化剂层的组合物;将该形成催化剂层的组合物涂布在电极担体上,并干燥形成催化剂层的组合物。
根据本发明的另一方面,提供一种利用根据上述方法制得的电极的燃料电池。
附图说明
通过参考附图详述其示例性实施方案,本发明的上述和其它特点和优点将更加显而易见,其中:
图1A和1B是本发明的金属催化剂和常规金属催化剂的结构示意图;
图2是根据本发明制备电极的过程示意图;及
图3是根据实施例5至8制得的燃料电池中电极的电流和电压(I-V)之间的关系图。
具体实施方式
以下,将更详细地描述本发明。
本发明的金属催化剂具有传导性催化剂材料和形成在该传导性催化剂材料上的质子传导性材料涂层。该质子传导性材料是选自酸掺杂的聚苯并咪唑(PBI)、聚醚酮、聚醚酰亚胺、聚砜、全氟磺酸和上述离聚物中的至少一种离聚物。
在本发明中,首先将质子传导性材料,例如磷酸掺杂的聚苯并咪唑薄薄地涂布到传导性催化剂材料的表面上,并且将该涂布的传导性催化剂材料与憎水粘合剂混合。然后,将该混合物涂布到电极担载层上形成电极。该电极易于形成用于电化学反应的三相界面,帮助气体反应物穿过催化剂上的薄涂层接近催化剂,及有效地传递由电化学反应产生的质子。
酸没有限制,可以是例如磷酸。
传导性催化剂材料的实例包括Pt、Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Cu、Ag、Au、Sn、Ti、Cr、其混合物、其合金及具有担载在其上的这些元素的碳材料。
优选地,传导性催化剂材料是碳担载的Pt(Pt/C),质子传导性材料是磷酸掺杂的PBI。
在本发明的金属催化剂中,质子传导性材料的含量优选为1~50重量份,特别优选为3~10重量份,相对于每100重量份的传导性催化剂材料。当质子传导性材料的含量小于1重量份时,由于不能在催化剂层中形成三相界面,催化剂的效率降低。当质子传导性材料的含量大于50重量份时,传导性催化剂上的质子传导性材料的厚涂层减缓气体反应物向催化剂的扩散。
参考图1A将描述本发明的金属催化剂的结构。这里,碳担载的Pt(Pt/C)催化剂用作催化剂,聚苯并咪唑(PBI)用作质子传导性材料。
在金属催化剂10中,碳11涂有PBI 12,Pt颗粒13位于碳11的表面上。虽然它在图1A中未示出,但是Pt颗粒13还是薄薄地涂有多孔的PBI。
虽然它在图1A中未示出,但是当PBI掺杂酸如磷酸时,H3PO4通过氢键键结到PBI的N-H位置以形成质子传递路径。碳11起到电子传递路径的作用,并且质子通过磷酸传递。
图1B图示了常规的金属催化剂的结构。
参考图1B,在常规的金属催化剂10中,Pt颗粒13位于碳11的表面上,PBI 12邻近于碳11。在该结构中,PBI和Pt/C的分散性质恶化,并且难于得到用于电化学反应的三相界面,从而催化效率降低。
现在将更详细地描述制备金属催化剂的方法和利用由此制得的金属催化剂的电极的制备方法。
图2图示了制备金属催化剂和利用该金属催化剂的电极的过程。
首先,向第一溶剂中加入传导性催化剂材料和离聚物并搅拌均匀混合。
然后,将该混合物浇铸到担载层上并干燥。干燥温度为80~120℃。
担载层没有限制,可以是Teflon薄板、聚酯薄膜、玻璃基板、聚对苯二甲酸乙二醇酯薄板等。
把所得到的产物从担载层上分离得到包含传导性催化剂的薄膜。研磨并筛分包含传导性催化剂的薄膜得到具有特殊粒度的粉末。粒度优选为50~70μm。
在上述过程之后,如果必要,进行酸处理以使得金属催化剂具有质子传导性。为此使用磷酸或类似的酸。酸的含量为200~1000mol%,优选为200~750mol%,相对于100摩尔的离聚物。
离聚物的实例包括聚苯并咪唑(PBI)、聚醚酮、聚醚酰亚胺、聚砜、全氟磺酸等。该离聚物的含量为1~50重量份,相对于每100重量份的传导性催化剂材料。
第一溶剂分散并溶解传导性催化剂材料和离聚物。第一溶剂的实例包括N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)、三氟乙酸(TFA)等。第一溶剂的含量为900~4000重量份,相对于每100重量份的离聚物。当第一溶剂的含量小于900重量份时,没有充分地溶解质子传导性材料并且传导性催化剂材料分散不均匀。当第一溶剂的含量大于4000重量分时,干燥需要花费太长时间。
通过进行上述方法,可以得到具有涂有质子传导性材料的传导性催化剂的金属催化剂。涂层可以是不连续或连续薄膜的形式。
将上述的金属催化剂、憎水粘合剂和第二溶剂混合并浇铸到电极担载层上。干燥该混合物制得电极。使用炭纸或炭布作为电极担载层。
憎水粘合剂的实例包括聚四氟乙烯(PTFE)和氟化乙烯丙烯(FEP)。憎水粘合剂的含量优选为1~40重量份,相对于每100重量份的金属催化剂。当憎水粘合剂的含量不在上述范围时,不能获得电极的令人满意的质子传导性和导电性。
根据憎水粘合剂选择第二溶剂,并且没有限制,只要该溶剂不溶解质子传导性材料并且可以溶解或分散憎水粘合剂。第二溶剂的实例是氟基有机溶剂。第二溶剂的含量为500~10000重量份,相对于每100重量份的金属催化剂。
用于干燥过程的条件没有限制,但是干燥通常在60~150℃下进行。当干燥温度不在上述范围内时,干燥不能很好地完成并且碳载体被氧化,其不是优选的。
然后,如果必要,所制得的电极可以搀有酸如磷酸。酸含量为200~1000mol%,优选为200~750mol%,基于电极中质子传导性材料。
当涂有PBI的金属催化剂颗粒搀有磷酸时,H3PO4通过氢键结合到PBI的N-H位置,从而形成质子传导路径。
现在将详述本发明的燃料电池。
本发明的燃料电池包括阴极、阳极和插入阴极与阳极之间的电解液膜。阴极和阳极的至少一个包含如上所述的本发明的担载催化剂。
本发明的燃料电池可以包括,例如,磷酸燃料电池(PAFC)、质子交换膜燃料电池(PEMFC)或者直接甲醇燃料电池(DMFC)。这些燃料电池的结构和制备没有限制,因为在多种文献中已经具体描述了它们,所以在此不再描述。
将参考下面实施例更详细地描述本发明。下面实施例仅是为了说明性目的,而不意味着限制本发明的范围。
实施例1
混合1.0g的Pt/C、0.05g的PBI和1.45ml的NMP,并在室温下以250搅拌约3小时。将该混合物浇铸到Teflon薄板上并在120℃和真空下干燥1小时。研磨并筛分干燥所得到的产物,从而得到粒度为50~70μm的PBI涂布的Pt/C。
向PBI涂布的Pt/C中加入0.032g磷酸(200mol%PA,相对于100摩尔的PBI),使得PBI具有质子传导性。然后,将掺杂的催化剂与cytop(商品名,得自日本Asahi Glass)和溶剂混合,并且在室温下搅拌该混合物约3小时,以制得浆料形式的形成催化剂层的组合物。
利用具有约120缝隙的涂布器将该浆料涂布到炭纸上,然后在80℃下干燥3小时,在120℃下干燥1小时,从而制得电极。
实施例2
按照与实施例1相同的方法制备电极,所不同的是,使用0.064g磷酸(400mol%PA,相对于100摩尔的PBI)。
实施例3
按照与实施例1相同的方法制备电极,所不同的是,使用0.160g磷酸(1000mol%PA,相对于100摩尔的PBI)。
实施例4
按照与实施例1相同的方法制备电极,所不同的是,使用0.352g磷酸(2200mol%PA,相对于100摩尔的PBI)。
实施例5
利用包含实施例1的金属催化剂的电极和PBI电解液膜制备燃料电池。分别使用氢和空气作为燃料和氧化剂。
实施例6~8
按照与实施例5相同的方法制备电极,所不同的是,分别使用实施例2、3和4中的金属催化剂替换实施例1中的催化剂。
对于根据实施例5~8制备的燃料电池,检测单元电池的电流-电压特性(I-V),结果示于图3中。在图3中,PA200、PA400、PA1000和PA2200分别是实施例5~8的结果。
参考图3,利用具有掺杂量为200mol%磷酸,基于100摩尔的质子传导性材料的电极的燃料电池,在0.3A/cm2的电流密度和0.549V的电压下,表现出最好的性能。可以看出,磷酸掺杂量越高,在气体扩散控制区域中的燃料电池的性能就越差。
如上所述,本发明的金属催化剂具有均匀涂有质子传导性材料的传导性催化剂颗粒,从而容易形成和控制用于电化学反应的三相界面、使气体反应物穿过在催化剂颗粒上形成的质子传导性材料的薄涂层容易接近催化剂,并且有效地传递由电化学反应产生的质子。当利用该催化剂制备电极时,可以形成理想的三相界面电极结构,并且包括该电极的燃料电池能够具有改善的性能如高效率。
尽管已经具体参考其示例性的实施方案说明和描述了本发明,但是本领域的技术人员会理解其中可以进行各种形式和细节的变化,而不脱离如所附的权利要求书阐述的本发明的构思和范围。
Claims (13)
1. 一种制备金属催化剂的方法,该金属催化剂具有传导性催化剂材料和形成在该传导性催化剂材料表面上的质子传导性材料涂层,该方法包括:
混合传导性催化剂材料、离聚物和第一溶剂;
将所得的混合物浇铸到担载层上,并干燥所得到的产物,从而形成包含传导性催化剂的薄膜;及
把该包含传导性催化剂的薄膜从担载层上分离,并研磨包含传导性催化剂的薄膜,
其中所述第一溶剂是选自N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)和三氟乙酸(TFA)中的至少一种;
其中所述离聚物是选自聚苯并咪唑、聚醚酮、聚醚酰亚胺、聚砜和全氟磺酸中的至少一种;及
其中所述传导性催化剂材料为Pt、Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Cu、Ag、Au、Sn、Ti、Cr,这些元素的混合物,这些元素的合金,或者担载有这些元素的碳材料。
2. 根据权利要求1的制备金属催化剂的方法,还包括用酸处理研磨所得到的产物。
3. 根据权利要求2的制备金属催化剂的方法,其中所述酸是磷酸,且该酸相对于100mol离聚物的含量为200~750mol%。
4. 根据权利要求1的制备金属催化剂的方法,其中所述离聚物的含量为1~50重量份,相对于每100重量份的传导性催化剂材料。
5. 根据权利要求1的制备金属催化剂的方法,其中所述第一溶剂的含量为900~4000重量份,相对于每100重量份的离聚物。
6. 根据权利要求1的制备金属催化剂的方法,其中所述传导性催化剂材料为碳担载的Pt(Pt/C),所述质子传导性材料是磷酸掺杂的聚苯并咪唑。
7. 一种根据权利要求1至6中任一项的方法制备的金属催化剂。
8. 一种制备电极的方法,该方法包括:
混合金属催化剂与憎水粘合剂和第二溶剂,得到形成催化剂层的组合物,所述金属催化剂具有传导性催化剂材料和形成在该传导性催化剂材料表面上的质子传导性材料涂层;及
将所述形成催化剂层的组合物涂布在电极担体上,并干燥形成催化剂层的组合物。
9. 根据权利要求8的制备电极的方法,还包括用酸处理所得到的产物。
10. 根据权利要求9的制备电极的方法,其中所述酸是磷酸,且该酸相对于100摩尔的质子传导性材料的含量为200~750mol%。
11. 根据权利要求8的制备电极的方法,其中所述憎水粘合剂是聚四氟乙烯(PTFE)和氟化乙烯丙烯(FEP),憎水粘合剂的含量为1~40重量份,相对于每100重量份的金属催化剂。
12. 根据权利要求8的制备电极的方法,其中所述干燥在60~150℃下进行。
13. 一种燃料电池,其采用根据权利要求11至15中任一项的方法制备的电极。
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US20060110632A1 (en) | 2006-05-25 |
CN1776945A (zh) | 2006-05-24 |
KR100612873B1 (ko) | 2006-08-14 |
KR20060056451A (ko) | 2006-05-24 |
JP2006147563A (ja) | 2006-06-08 |
US20120021338A1 (en) | 2012-01-26 |
US8039414B2 (en) | 2011-10-18 |
US8623572B2 (en) | 2014-01-07 |
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