CN1472135A - 用于燃料电池的碳纳米管及其制备方法以及采用它的燃料电池 - Google Patents
用于燃料电池的碳纳米管及其制备方法以及采用它的燃料电池 Download PDFInfo
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Abstract
本发明提供用于燃料电池的碳纳米管,其制备方法,以及使用碳纳米管作为电极的燃料电池。碳纳米管的内外壁用纳米级金属催化剂颗粒均匀掺杂至0.3~5mg/cm2的程度。碳纳米管是利用化学气相沉积或等离子体增强的化学气相沉积在碳基材上生长的。由于碳纳米管具有较大的比表面积,金属催化剂颗粒均匀地分布于其内外壁上,所以当使用碳纳米管作为燃料电池的电极时,电极中的反应效率达到最大。利用该方法制备的碳纳米管可用于形成较大的电极。生长在碳基材上的碳纳米管可容易地应用于燃料电池的电极,同时带来经济上的利益和整个电极制造工艺的简化。采用碳纳米管作为其电极的燃料电池的性能也得到提高。
Description
技术领域
本发明涉及碳纳米管,更具体地,本发明涉及用于燃料电池的碳纳米管,其直接生长在碳基材上,其内外壁均匀地掺杂了金属催化剂颗粒,及制备碳纳米管的方法,以及采用碳纳米管作为电极的燃料电池。
背景技术
最近,随着环境和能源枯竭问题,以及燃料电池汽车商业化的发展,急切需要开发能够在环境温度下以较高能量效率工作的可靠的、高性能的燃料电池,并且需要开发能够提高燃料电池效率的聚合物膜。
燃料电池是一种新的产能系统,其通过燃料与氧化性气体的电化学反应将所产生的能量直接转化成电能。这种燃料电池可以分为具有熔融碳酸盐的燃料电池,其可在500~700℃的高温下工作;具有磷酸的燃料电池,其可以在200℃左右工作;碱性电解液燃料电池,其可在室温至100℃工作;及固体聚合物电解液(SPE)燃料电池,其可在环境温度至约100℃工作。
SPE燃料电池包括采用氢气作为燃料的质子交换膜燃料电池(PEMFC),及利用直接施用于阳极的液体甲醇溶液作为燃料的直接甲醇燃料电池(DMFC)。
SPE燃料电池,其作为可代替矿物燃料的下一代的清洁能源,具有高的能量密度和高的能量转化效率。另外,SPE燃料电池可以在环境温度下工作并且容易密封和小型化,所以它们可以广泛地应用于无污染的交通工具、家用发电系统、移动通讯设备、医疗设备、军事设施、空间设备等领域。
作为通过氢与氧的电化学反应产生直流电的发电机,PEMFC的基本结构如图1所示。参照图1,PEMFC具有位于阳极与阴极之间的质子交换膜11。质子交换膜11以50~200μm的厚度构成SPE。阳极和阴极分别包括提供反应气体或液体的阳极和阴极衬里层14和15,以及发生氧化/还原反应的催化剂层12和13,形成催化剂电极(下文中将阳极和阴极称为“催化剂电极”)。在图1中,附图标记16代表具有气体注入孔并充当集电体的碳片。
随着将作为反应气体的氢提供给具有上述结构的PEMFC,氢分子通过阳极的氧化反应分解为质子和电子。这些质子通过质子交换膜11到达阴极。同时在阴极中,氧分子从阳极获得电子并通过反应还原为氧离子。这些氧离子与来自阳极的质子反应产生水。
如图1所示,在PEMFC的气体扩散电极中,催化剂层12和13分别形成在阳极和阴极衬里层14和15上。阳极和阴极衬里层14和15是由碳布(carbon cloth)或复写纸(carbon paper)构成的。阳极和阴极衬里层14和15的表面经过处理,以便反应气体和水容易在反应前后透过质子交换膜11。
DMFC具有类似于上述PEMFC的结构,但却使用液体甲醇溶液代替氢作为燃料。随着将甲醇溶液提供给阳极,在催化剂存在下发生氧化反应,产生质子,电子和二氧化碳。尽管DMFC的能量效率比PEMFC低,但是采用液体燃料的DMFC使其更容易应用于便携式的电子设备中。
有关高能量密度和高功率的燃料电池的电极,燃料,电解液膜的研究一直在积极地进行。另外,已经试图增加电极中所用催化剂的活性。由于催化剂的活性与其反应表面积成正比,所以必须通过减小催化剂颗粒的直径至几个纳米并将这种纳米级催化剂颗粒均匀地分布在电极上来提高反应表面积。
通常,催化剂如铂是以糊状物均匀地施用于多孔碳基材的电极衬里层上。然而,催化剂在电极衬里层中的分散并不均匀,且碳载体的表面积和导电性也不足够大。
日本待审专利公开2000-63112公开了一种制造单壁碳纳米管的方法,其中通过CO2激光器照射含金属的碳源将痕量的金属引入碳纳米管中。在该方法中,激光器的使用限制了生长碳纳米管的面积。为了应用于燃料电池,需要额外的用碳纳米管的糊状物涂布电极的步骤,这使整个燃料电池的制造工艺复杂化。
发明内容
本发明提供直接生长在碳基材上的碳纳米管,其内外壁上均匀地掺杂了直径为几个纳米或更小的催化剂颗粒。
本发明还提供制备上述生长在碳基材上的碳纳米管的方法。
本发明还提供效率得到提高的燃料电池,其是由上述生长在用于电极的碳基材上的碳纳米管构成。
一方面,本发明提供生长在碳基材上的碳纳米管,其内外壁均匀掺杂了0.3~5g/cm2程度的纳米级金属催化剂颗粒。
另一方面,本发明提供制备生长在碳基材上的碳纳米管的方法,包括:将金属催化剂颗粒均匀地分布在碳基材上;及在大气压下以恒定的速度提供碳源气体,并使之在400~900℃下与金属催化剂颗粒反应1~120分钟,以在碳基材上生长碳纳米管。
再一方面,本发明提供燃料电池,其采用上述生长在用于电极的碳基材上的碳纳米管。
附图说明
通过详细地描述其示例性的实施方案,同时参照附图,本发明的上述及其它特征和优点将是显而易见的。在附图中:
图1是燃料电池的构造;
图2是示出金属催化剂颗粒均匀分布于碳基材上的扫描电子显微镜(SEM)照片;
图3是用于本发明燃料电池的碳纳米管的SEM照片;
图4是用于本发明燃料电池的分叉的碳纳米管的透射电子显微镜(TEM)照片;
图5示出了用于本发明的制造碳纳米管的方法中的反应系统;及
图6逐步地图示了本发明的制备碳纳米管的方法,其中(a)图示了均匀地分布催化剂颗粒于碳基材上,(b)图示了直接在碳基材上生长碳纳米管,用催化剂颗粒充当碳纳米管生长的晶种,(c)图示了调整所生长的碳纳米管的密度,及(d)图示了调整碳纳米管的生长,以形成分叉的碳纳米管。
具体实施方式
本发明的特征在于碳纳米管直接生长在碳基材上。因此,其上生长本发明的碳纳米管的碳基材可容易地应用于燃料电池。而且,根据本发明,碳纳米管不是向上生长,而是在碳基材上生长时分叉,因而增加了其反应表面积。碳纳米管的内外壁均匀地掺杂了一元的、二元的、三元的或更多元的直径为几个纳米的催化剂颗粒,其选自Pt,Ru,Fe和Co。因此,当将本发明的这种碳纳米管用于燃料电池时,燃料电池的电极反应效率达到最大。此外,根据本发明,随着碳纳米管的生长,金属催化剂颗粒沿着碳纳米管的内外壁均匀地分布并且稳定地固定在其上,从而不受外力的影响。
图3是根据本发明的碳纳米管的扫描电子显微镜(SEM)照片。从图3可以看出,本发明的碳纳米管是分叉生长的而不是一直朝上生长的,所以其表面积变大。
图4是本发明的分叉碳纳米管的透射电子显微镜(TEM)照片。在图4中,大量的金属催化剂颗粒均匀地分布于碳纳米管的内外壁上,其中吸附在外壁上的金属催化剂颗粒图示成黑点,吸附在内壁上的金属催化剂颗粒图示成灰点。根据本发明,优选金属催化剂颗粒的分散程度为0.3~5mg/cm2。如果金属催化剂颗粒的分散度小于所述的下限,则金属催化剂颗粒的活性不充分。如果金属催化剂颗粒的分散度大于所述的上限,则它们易于结块,抑制碳纳米管的生长。
现将参照图6逐步地解释本发明的制备用作催化剂载体的碳纳米管的方法。在本发明的制备碳纳米管的方法中,在将金属催化剂颗粒均匀分布于碳基材上之后,如图6的(a)所示,在大气压下以恒定的速度提供碳源气体,并使之在400~900℃下反应1~120分钟,以在碳基材上生长碳纳米管,如图6的(b)所示。当碳纳米管生长到一定程度,如图6的(c)所示,可以提供氢气或氨气,以制备分叉的碳纳米管,如图6的(d)所示。在碳纳米管生长时,多数金属催化剂颗粒吸附在碳纳米管的内外壁上。然而,当利用还原性气体如氢气或氨气进行侵蚀时,一些金属催化剂颗粒则可能充当碳纳米管分叉的晶核。因此,可以制备本发明的分叉的碳纳米管。具体地,氢气将氧化态的金属催化剂颗粒转化成还原态,进而增加催化剂颗粒的活性,导致分叉碳纳米管的生长。作为选择,分叉碳纳米管还可以这样生长,即适当地调节碳源气体的流速以及反应温度和时间,使得金属性碳纳米管可以沿着生长着的碳纳米管迁移。
在制备用本发明的燃料电池的碳纳米管的方法中,将金属催化剂颗粒均匀地分散在碳基材上可以通过电泳,热喷射,溅射,化学气相沉积(CVD),以及本领域的技术人员公知的任何其它技术来实现。
图5示出了制备本发明的碳纳米管的方法中使用的反应系统。将裸露的碳基材4插到石英船5的切口中。将其中插有裸露碳基材4的石英船5放置在反应器2的中央。在图5中,附图标记3代表加热单元。在大气压下将氩气或氮气提供到石英管中,之后,在大气压下以恒定的速度提供碳源气体并使之在400~900℃下反应1~120分钟,以在碳基材上生长碳纳米管。适宜的可用于本发明的碳源气体,可以是本领域的技术人员常用的任何气体,其中优选的碳源气体包括乙烯,一氧化碳,二氧化碳和甲烷。如果反应温度低于400℃,则生成碳颗粒而不是纳米管。如果反应温度高于900℃,则金属碳颗粒的活性降低,且碳纳米管颗粒的生长速度大大地降低。优选碳源气体以10~1000sccm的速度提供。如果碳源气体的流速低于10sccm,则碳源气体的量不足以生长碳纳米管。如果碳源气体的流速大于1000sccm,则由于供给过量的碳源气体使不合乎需要的碳颗粒附着在所生长的碳纳米管上。
如上所述,根据本发明的碳纳米管生长在碳基材上。这种碳基材可以是碳布或复写纸。其上已生长了本发明的碳纳米管的碳基材可以很容易地用作燃料电池的电极,从而简化了整个制造燃料电池电极的工艺。在常规的电极制造工艺中,将催化剂糊或者催化剂与碳纳米管的糊涂布在电极衬里层如碳布上。换言之,常规的电极制造工艺是复杂的,因为其包括单独的处理电极基材,用催化剂掺杂电极基材,及形成完整电极的步骤。但是,根据本发明,在碳纳米管直接形成在可用作电极的碳基材上的同时,催化剂颗粒均匀地分布在生长的碳纳米管上。结果,大大地简化了电极制造工艺,进而降低了产品的成本。
在制备用于本发明的燃料电池中的碳纳米管的方法中,可以用等离子体增强的化学气相沉积(PECVD)代替普通的CVD。在PECVD中,当碳源气体提供给事先放置了金属催化剂的反应器的两个电极之间时,将微波或无线电波施加给反应器,以将碳源气体活化成等离子体状态,并借助于活化能在电极上生长碳纳米管。“等离子体”统指气体分子受辉光放电所产生的高能自由电子轰击时所产生的气体离子和自由电子。
燃料电池根据电解液的种类可以分为碱性燃料电池,磷酸燃料电池,熔融碳酸盐燃料电池,固体氧化物燃料电池,及固体聚合物电解液(SPE)燃料电池。碱性燃料电池,磷酸燃料电池,及SPE燃料电池需要铂催化剂。根据本发明的直接生长于碳基材上的碳纳米管可以用作碱性燃料电池,磷酸燃料电池,及SPE燃料电池(PEMFC和DMFC)的电极。
现将参照下列实施例更详尽地描述本发明。下面的实施例仅用于说明目的,而不是对本发明的范围的限制。
实施例1
通过电泳将作为金属催化剂的铂(Pt)在充当碳基材的防水复写纸上分散1分钟,并利用扫描电子显微镜(SEM)-能散光谱(EDS)确认Pt颗粒的均匀分散。结果示于图2中。将其上已经均匀分布了Pt颗粒的碳基材插到石英船中并放置在反应器的中央。在大气压下将反应器用氩气以5000sccm吹扫,同时将反应器的温度升高至500℃。当反应器的温度达到500℃时,在大气压下向反应器中以10sccm的速度提供作为碳源气体的乙炔60分钟,以合成碳纳米管。下一步,在大气压下以300sccm向反应器中提供氩气的同时,将碳纳米管的温度降低至室温,得到均匀掺杂了1mg/cm2的Pt颗粒的碳纳米管。
实施例2
按与实施例1相同的方式合成碳纳米管,只是用Fe2O3代替Pt作为催化剂。结果得到均匀掺杂了2mg/cm2的Fe颗粒的碳纳米管。
实施例3
按与实施例1相同的方式合成分叉的碳纳米管,只是在提供碳源气体以使碳纳米管生长至一定程度之后10分钟,以50sccm向反应器中提供氢气20分钟。结果得到均匀掺杂了2mg/cm2催化剂颗粒的分叉的碳纳米管。
如上所述,本发明的内外壁均匀掺杂了直径几个纳米的金属催化剂颗粒的碳纳米管,直接生长在碳基材上,具有较宽的比表面积,特别是碳纳米管是分叉的时候,因此当本发明的碳纳米管用作燃料电池的电极时,其电极反应效率达到最大。另外,由于碳纳米管直接生长于可以用作电极的碳基材上,所以其上生长了碳纳米管的碳基材可以很容易地以低成本用作燃料电池的电极,无需复杂的电极制造工艺。此外,由于可以使用一元的,二元的,三元或更多元的金属元素作为催化剂,所以根据本发明的生长在碳基材上的碳纳米管除了阳极之外还可以用于阴极。当在本发明的方法中采用CVD或PECVD在碳基材上生长分叉的碳纳米管时,生长于碳基材上的分叉的碳纳米管具有更大的表面积,所以它们可用作更有效的电极。与常规的燃料电池相比,使用其上生长了本发明的碳纳米管的碳基材作为电极的燃料电池的性能可以得到提高。
尽管已经参照其示例性的实施方案对本发明进行了具体的说明,但是本领域的技术人员应当理解,可以在形式和内容上作出各种改变,而不脱离下列权利要求书中所规定的本发明的构思和范围。
Claims (13)
1.一种用于燃料电池的碳纳米管,其直接生长在碳基材上,其内外壁均匀地掺杂了纳米级金属催化剂颗粒至0.3~5mg/cm2的程度。
2.根据权利要求1的碳纳米管,其中所述金属催化剂颗粒源于选自Pt,Ru,Fe,Co,及前述元素的合金或混合物中的至少一种。
3.根据权利要求1的碳纳米管,其中所述碳基材为碳布或复写纸。
4.根据权利要求1的碳纳米管,其中所述碳纳米管是分叉的。
5.一种制备碳纳米管的方法,该方法包括:
(a)将金属催化剂颗粒均匀地分布在碳基材上;及
(b)在大气压下以恒定的速度提供碳源气体,并使碳源气体与金属催化剂颗粒在400~900℃下反应1~120分钟。
6.根据权利要求5的方法,其中所述碳源气体为乙烯,一氧化碳,二氧化碳或甲烷。
7.根据权利要求5的方法,其中所述步骤(a)的将金属催化剂颗粒均匀地分布在碳基材上是通过电泳,热喷射,溅射或者化学气相沉积进行的。
8.根据权利要求5的方法,其中所述步骤(b)还包括施用微波或无线电波,以将碳源气体活化成等离子状态。
9.根据权利要求5的方法,其中所述步骤(b)进一步包括调节反应条件,使所生长的碳纳米管分叉。
10.根据权利要求9的方法,其中所述调节反应条件包括在提供碳源气体约10分钟之后提供还原性气体。
11.根据权利要求10的方法,其中所述还原性气体为氢气或氨气。
12.根据权利要求9的方法,其中调节反应条件包括调节碳源气体的流速以及反应的温度和时间。
13.一种燃料电池,其使用根据权利要求1~4中任一项的生长在碳基材上用于电极的碳纳米管。
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Also Published As
Publication number | Publication date |
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US7585584B2 (en) | 2009-09-08 |
CN1240612C (zh) | 2006-02-08 |
US8083905B2 (en) | 2011-12-27 |
JP3705795B2 (ja) | 2005-10-12 |
KR100759547B1 (ko) | 2007-09-18 |
US20100018851A1 (en) | 2010-01-28 |
KR20040011181A (ko) | 2004-02-05 |
JP2004059428A (ja) | 2004-02-26 |
US20040018416A1 (en) | 2004-01-29 |
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