CN108878898A - 具有分离的电解质分布的燃料电池及其制造方法 - Google Patents
具有分离的电解质分布的燃料电池及其制造方法 Download PDFInfo
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- CN108878898A CN108878898A CN201810414243.8A CN201810414243A CN108878898A CN 108878898 A CN108878898 A CN 108878898A CN 201810414243 A CN201810414243 A CN 201810414243A CN 108878898 A CN108878898 A CN 108878898A
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Classifications
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- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
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- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
- C08J5/225—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231 containing fluorine
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- H—ELECTRICITY
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- H—ELECTRICITY
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Abstract
一种制造燃料电池的方法,包括以下步骤:包括:(a)将碳纳米管(CNT)与初始分散液混合,其中所述初始分散液包含离聚物;(b)加热并搅拌初始分散液以形成CNT‑离聚物复合物悬浮液;(c)在形成CNT‑离聚物复合物悬浮液后,将CNT‑离聚物复合物悬浮液与电极催化剂溶液混合以形成电极浆料,其中电极催化剂溶液包括炭黑粉末和由炭黑粉末负载的催化剂;以及(d)将质子交换膜用电极浆料涂覆以形成燃料电池电极。
Description
背景技术
本发明涉及燃料电池,并且更具体地涉及具有分离的电解质分布的燃料电池电极及其制造方法。
燃料电池膜电极组件通常包括夹在负极与正极之间的聚合物电解质膜。在燃料电池操作期间,例如氢气的燃料气体在负极上被氧化,而例如氧气的氧化剂气体在正极上被还原。负极和正极上的电化学氧化还原反应通常由金属催化剂(例如铂)催化。可以高效率地从燃料电池中的这种电化学反应产生电。反应气体(燃料气体或氧化剂气体)具有快速的传输速率和最小的动力学障壁以到达薄电极层中的反应部位,在给定的电池电压下产生更高的电流密度。另外,催化剂通常均匀分布在整个单层电极配置中以确保均匀的电流分布。
发明内容
在燃料电池中,离聚物必须均匀分布在整个电极中以确保足够的质子传输到所有的铂表面。然而,先前的研究表明,铂表面上的离聚物吸附导致反应氧气传输到铂表面的阻力增加,并且当从表面除去离聚物时,可以减轻损失。此外,因为离聚物在燃料电池操作条件下相对流动,所以控制局部离聚物分布是具有挑战性的。本发明描述了具有分离的电解质分布的燃料电池,其允许离聚物在正极层中均匀分布而不涂覆所有铂(Pt)表面。因此,在本发明的燃料电池中,在所有铂表面上发生足够的氧和质子传输以保持良好的高功率性能。另外,本公开描述了制造这种燃料电池的方法。
在通过使用下述方法制造的燃料电池电极中,使离聚物与碳纳米管(CNT)强缔合以使离聚物与铂表面之间的相互作用最小化。代替在一个步骤中将催化剂与离聚物一起混合,在加入催化剂前,先在独立的容器中使离聚物与CNT结合。在预混合步骤期间,使用用于CNT和离聚物的不良溶剂来产生强缔合的CNT-离聚物复合物,将其收集用于随后的浆料制备。这种复合物在水中会充分分散(变黑)并且稳定数日。因为离聚物缠绕在CNT周围,所以CNT与离聚物之间发生强缔合。使用该方法制造的具有正极的燃料电池在高电流密度下测试期间表现出性能的改善(即在2.5A/cm2下40-60mV)。具体地,通过下述方法制造的本发明的电极平衡质子传导和氧气传输,以在燃料电池中的电化学反应期间使能量转换最大化。
制造燃料电池的方法包括以下步骤:(a)将碳纳米管(CNT)与初始分散液混合,其中该初始分散液包含离聚物;(b)加热并搅拌该初始分散液以形成CNT-离聚物复合物悬浮液;(c)在形成CNT-离聚物复合物悬浮液之后,将CNT-离聚物复合物悬浮液与电极催化剂溶液混合以形成电极浆料,其中电极催化剂溶液包括炭黑粉末和负载在炭黑粉末上的催化剂;和(d)用电极浆料涂覆质子交换膜以形成燃料电池电极。
离聚物包含在离聚物分散液中。该方法可以进一步包括将水,正丙醇和离聚物分散液混合以形成初始分散液。将水,正丙醇和离聚物分散液混合包括搅拌水,正丙醇和离聚物分散液。将碳纳米管与初始分散液混合包括将碳纳米管加入初始分散液中,同时搅拌初始分散液。碳纳米管可以是石墨化碳纳米管。初始分散液可以包括80克水,8克正丙醇和1.8克石墨化碳纳米管。碳纳米管可以是直径在10纳米与20纳米之间的多壁碳纳米管。
在该方法中,加热并搅拌初始分散液可以包括用在约350转/分钟旋转的磁力搅拌器搅拌初始分散液。加热并搅拌初始分散液可以包括将初始分散液加热至50摄氏度至100摄氏度范围内的温度。加热和搅拌初始分散液可以包括同时加热并搅拌初始分散液2.5小时。该方法可以进一步包括在同时加热并搅拌初始分散液2.5小时之后,在不加热初始分散液的情况下继续搅拌初始分散液16小时。该方法可以进一步包括在不加热初始分散液的情况下使初始分散液通过自然对流冷却16小时。催化剂可以包括多个铂纳米颗粒,并且铂纳米颗粒沉积在炭黑粉末上以形成负载催化剂的炭黑粉末。将CNT-离聚物复合物与电极催化剂溶液混合包括将负载催化剂的炭黑粉末与水,正丙醇和CNT-离聚物复合物悬浮液混合以形成分离的离聚物电极浆料。分离的离聚物电极浆料可包含3.81克负载催化剂的炭黑粉末,8.3克正丙醇,32.73克水和56克CNT-离聚物复合物悬浮液。该方法可以进一步包括在含有ZrO2珠的聚合物瓶中混合分离的离聚物电极浆料。混合分离的离聚物电极浆料包括滚动聚合物瓶。每个ZrO2珠可以具有5毫米的直径。该方法还包括在电极浆料仍然湿润的同时用电极浆料涂覆质子交换膜,并且使电极浆料干燥以形成燃料电池电极。
本发明还涉及燃料电池。在一些实施例中,燃料电池包括质子传导聚合物电解质膜和设置在质子传导聚合物电解质膜上的电极。电极包括含有碳纳米管的CNT-离聚物复合物和与碳纳米管偶联的离聚物。电极还包括与CNT-离聚物复合物偶联的炭黑粉末和由炭黑粉末负载的多个铂纳米颗粒。每个碳纳米管具有在10至20纳米范围内的直径。CNT-离聚物复合物可以包括磺化四氟乙烯基氟聚合物共聚物。质子传导聚合物电解质膜可以包含磺化四氟乙烯基氟聚合物共聚物。
结合附图,根据用于执行本发明的最佳模式的以下具体实施方式,本发明的上述特征和优点以及其他特征和优点是显而易见的。
附图说明
图1是根据本发明的实施例的燃料电池的示意性横截面图。
图2是在区域2附近截取的图1中所示的燃料电池的一部分的示意性放大图。
图3是用于制造燃料电池电极的方法的流程图,其包括(1)制备碳纳米管(CNT)-离聚物复合物悬浮液;(2)制备电极浆料;以及(3)用电极浆料涂覆质子交换膜(PEM)和/或气体扩散层。
图4为用于制备CNT-离聚物复合物悬浮液和后续涂覆的方法的示意图。
图5是用于制备CNT-离聚物复合物悬浮液的方法的流程图。
图6是用于制备电极浆料的方法的流程图。
具体实施方式
图1是如下详细描述的包括具有层状电极的膜电极组件(MEA)12的示例性燃料电池14的示意性横截面图。MEA12夹在第一气体扩散层11与第二气体扩散层13之间。膜组件包括夹在负极层3与正极层2之间的质子传导聚合物电解质膜(PEM)1。负极层3和正极层2中的每一个都是电极4。
PEM 1也可以被称为质子交换膜并且限定第一膜表面16和与第一膜表面16相对的第二膜表面18。负极层3被设置在第一膜表面16上,正极层2被设置在第二膜表面18上。PEM1可以包括适用于燃料电池14的任何聚电解质。聚合物电解质可以包括基于烃和氟碳的树脂。基于烃的电解质树脂可以包括含酚醛,磺酸,磺酰胺,芳族酮,羧酸的树脂;例如苯酚-甲醛,聚苯乙烯,苯乙烯-二乙烯基苯共聚物,苯乙烯-二乙烯基苯-氯乙烯三元共聚物等的缩合树脂。基于氟碳的聚合物电解质可以包括全氟磺酸聚合物,例如四氟乙烯-全氟磺酰基乙氧基乙烯基醚四氟乙烯-羟基化(全氟乙烯基醚)共聚物和磺化全氟环丁烷共聚物。在某些情况下,还使用具有磺酸、羧酸、磺酰胺、磺酰亚胺和/或磷酸官能团的氟碳型树脂。基于氟碳的树脂通常表现出优异的对通过氧,过氧化物,强酸和强碱的氧化的抗性,并且可用于其中例如PTFE(聚四氟乙烯)取向的多孔膜或纤维基质的强化型非电解质材料用作机械框架的纯净和复合物电解质膜。例如,具有磺酸基官能团的碳氟型树脂是由Dupont以商品名出售的基于磺化四氟乙烯的氟聚合物-共聚物。可用于PEM 1的其他基于氟碳的聚合物电解质树脂包括含有芳基全氟烷基磺酰亚胺阳离子交换基团的烯烃的(共)聚合物。一种这样的树脂是p-STSI,一种衍生自具有下式的苯乙烯基三氟甲基磺酰亚胺(STSI)的自由基聚合的离子导电材料:苯乙烯基-SO2-NH-SO2CF3。具有约400至约1000的当量重量(EW)的聚合物电解质可用于在燃料电池14中铸造PEM 1。
PEM 1可以由包含聚合物电解质的组合物铸造或以其他方式形成。可以使用溶液、分散液、乳液、聚合物熔体、颗粒混合物或纯液体混合物形式的聚合物电解质组合物来制备膜。取决于混合物的形式和具体组成,可以使用普通技术人员已知的各种膜形成方法。非限制性的示例性膜形成方法可以包括通过狭缝模头挤出、溶液铸造、固定间隙涂覆、喷雾铸造、浸涂、拉伸杆涂覆、压延、刷涂、浸渍增强片材和吹塑。
燃料电池14还包括第一气体流量分配器层5和第二气体分配层6,每个具有相应的气体流量通道8和7。任选地,第一冷却剂板9可以被放置在第一气体分配层5上,并且第二冷却剂板10可以被放置在第二气体分配层6上用于温度控制。作为非限制性示例,第一气体流量分配器层5和第二气体分配层6可以是全部或部分由石墨、碳复合物材料、碳纤维复合物材料、不锈钢板、钛板、铝合金板和镀金的金属板制成的板。
第一气体扩散层11和第二气体扩散层13可以包括导电多孔基质和任选的微孔层。导电多孔基质可以包括例如多孔导电泡沫(例如碳泡沫,金属泡沫等),导电纤维基质或导电颗粒聚集体多孔层。碳纤维基质可以包括碳纸、碳纤维非织造片材、碳纤维织造布和碳纤维编织布中的至少一种。例如,由SGL集团以商品名出售的碳布和纸材可用于第一气体扩散层11和第二气体扩散层13。微孔层可以包含导电颗粒、疏水剂和任选的聚合物电解质。微孔层可以为气体渗透、水管理和增强与相邻催化剂电极层的紧密电接触提供合适的孔径。导电颗粒可以包括碳颗粒和任何其他导电惰性材料,例如贵金属/过渡金属及其氧化物。碳颗粒可以包括由Cabot Corporation以商品名XC-72出售的炭黑粉末,乙炔黑和石墨。疏水剂可以包括但不限于偏二氟乙烯、四氟乙烯、乙烯、丙烯和六氟丙烯的聚合物和共聚物。例如聚偏二氟乙烯(PVDF),聚四氟乙烯(PTFE)或聚(四氟乙烯-共-乙烯)的分散液(例如溶液,悬浮液或胶体)可用作疏水剂。
参照图1和图2,在某些实施例中,负极层3和正极层2中的每一个可以是单层超薄电极4。每个电极4可以包括催化剂20和催化剂载体材料22。在本发明中,术语“催化剂”意指能够催化燃料电池负极上的半电池氢氧化和/或燃料电池正极上的半电池氧还原反应的材料。在一些实施例中,催化剂20可以包括铂和/或其任何合金。催化剂20可以包括二元合金或三元合金。非限制性二元催化剂可以包括由化学式中的一个表示的合金:PtxCoy,PtxRuy,PrxMny,PtxNiy,PtxIry,和PtxFey,其中x和y是约0.01至1的实数。非限制性三元催化剂可以包括由通式Pt(M1)x(M2)y表示的合金,其中M1和M2是过渡金属元素,x和y是约0.01至3的实数。M1和M2的实例包括但不限于Fe、Co、Mn、Ni、Ru、Pd、Ir或Cu。可以在电极4中使用包含Pt,Mn和Co的三元合金,其中Pt与合并的Mn和Co的比例为1:0.1至1:3。当Pt包含在催化剂20中时,基于电极4的活性面积的铂的量可以在0.05mg/cm2至约0.4mg/cm2的范围内。基于组合的催化剂和载体重量的铂的百分比可以在约10%至95%,15%至50%或20%至30%的范围内,这取决于所使用的催化剂载体材料22的类型和电极4的厚度。当炭黑或其他无机材料用作催化剂载体时,Pt的重量百分比可以在10%至约40%的范围内。如上所述,催化剂20可以包括铂和/或其任何合金,并且可以使用约0.1纳米至约1000纳米的平均粒径。因此,催化剂20包含铂纳米颗粒26。如本文所用,术语“铂纳米颗粒”意指包含铂和/或其任何合金并具有约1纳米至约1000纳米的平均尺寸的颗粒。电极4通常具有小于约20微米、15微米、10微米或5微米的厚度。
催化剂载体材料22支撑催化剂20(例如,铂纳米颗粒26)并且可以包括炭黑粉末28。因此,铂纳米颗粒26可以由炭黑粉末28支撑。炭黑粉末28可以包括平均粒径在约1纳米与1000纳米之间的颗粒。可以使催化剂载体材料22的初级颗粒松散地彼此粘附以形成聚集体,并且使聚集体形成团块。因此,在聚集体或团块结构内有大量空隙和孔。孔的量和大小取决于粒径和颗粒如何组织形成聚集体。具有高表面积的催化剂载体材料22通常在具有层状电极构造的燃料电池14中提供期望的多孔结构和性能特征。合适的催化剂载体材料22可具有大于约30m2/g、250m2/g、500m2/g、1000m2/g或1500m2/g的Brunauer-Emmett-Teller(BET)表面积。催化剂载体材料22可以包括例如炭黑,石墨化碳和/或用有机亲水基团表面改性的炭黑。可以对催化剂载体材料22施加特定的处理以增加或减少可用于沉积催化剂的活性中心的数量。可以对炭黑进行化学改性以引入作为铂锚定位点的官能团。也可以对炭黑表面进行化学改性以包含用以提高亲水性的亲水性有机基团。例如,炭黑在高温下在酸存在下的表面氧化可在碳表面上产生亲水羧酸基团(-COOH或其盐)。炭黑与芳族磺酸叠氮化物(预先形成或原位形成)的反应允许在碳表面上连接亲水芳族磺酸基团。芳族磺酸叠氮化物可以由通用化学式X-N+2—Ar—SO3H表示,其中Ar是芳族基团(例如亚苯基或萘并噻吩基团),X是阴离子,以及—N+2—是叠氮基团。炭黑粉末28的一个实例由Cabot Corporation以商品名XC-72出售。炭黑还可以被氧化物,氢氧化物,金属氧氮化物和掺杂的金属氧化物改性或者与其组合。非限制性无机氧化物,氧氮化物和氢氧化物可以包括硅、钛、铝、镁、锆、钌、锌、铌、钽、钼和锡的氧化物,氧氮化物和氢氧化物。也可以使用氧化物,氧氮化物和氢氧化物的各种混合物。此外,可以将亲水性聚合物或聚合物电解质沉积或附着到载体材料表面上以增强第二电极层的亲水性。
每个电极4还可以包括偶联到催化剂载体材料22(例如,炭黑粉末28)的碳纳米管(CNT)-离聚物复合物30。CNT-离聚物复合物30包含离聚物和与离聚物混合的碳纳米管。“离聚物”在本文中被称为具有用于提供离子导电性的移动离子物质的聚合物电解质。例如,质子导电离聚物特别适用于氢或直接甲醇燃料电池,其中质子物质在正常操作中产生并通过PEM 1传导。示例性离聚物包括全氟磺酸聚合物、四氟乙烯-全氟-3,6-二氧杂-4-甲基-7-辛烯磺酸共聚物和由Dupont以商品名出售的基于磺化四氟乙烯的氟聚合物-共聚物。另外,离聚物可以是由Asahi Kasei Chemicals Corporation以商品名出售的四氟乙烯-全氟乙烯基醚磺酸共聚物或由Asahi Glass Co.Ltd以商品名出售的四氟乙烯-全氟乙烯基醚磺酸共聚物。。。离聚物可以通过将以磺酸基团封端的全氟乙烯基醚基团结合到四氟乙烯主链上来制备。离聚物的特征在于其当量(EW),其定义为每摩尔磺酸基团的离聚物重量。合适的离聚物可具有约400至1500的EW值。也可以使用烃基离聚物,例如聚(苯乙烯磺酸)、磺化PPBP聚(4-苯氧基苯甲酰基-1,4-亚苯基)、磺芳基化PBI聚(苄基咪唑)和磺化PEEK(聚(醚醚酮)。可以将上述不同的离聚物组合并包含在电极4中。CNT-离聚物复合物30中的每个碳纳米管具有10纳米至20纳米的直径。选择具有高石墨化和适当直径(即10-20nm)的CNT以促进与离聚物的密切结合。仔细选择溶剂系统也是重要的。在一些实施例中,CNT-离聚物复合物30的碳纳米管可以是具有高石墨化的多壁碳纳米管(MWCNT)。例如,MWCNT中的石墨烯层的数量可以是约35。
在具有少量铂的燃料电池正极中,观察到高功率下的性能大损失。这是由于对反应气体和质子输送到铂表面的需求增加。先前的研究表明,铂表面上的离聚物吸附是这种氧输送损失的主要来源,并且当从表面去除离聚物时,损失可以减轻。另外,为了使电极在高功率下运行,离聚物必须均匀分布以确保足够的质子传输到所有的铂表面。此外,因为离聚物在燃料电池操作下相对流动,所以控制局部离聚物分布是具有挑战性的。本发明的燃料电池14促进了分离的电解质分布,由此允许燃料电池将离聚物均匀地分布在铂表面上。因此,在本发明的燃料电池14中,在整个铂表面上发生足够的质子传输。为了实现所需的质子传输,本发明的燃料电池14应该使用下面描述的方法制造。
在通过使用下述方法100制成的燃料电池电极4中,离聚物与碳纳米管(CNT)密切结合以使离聚物与铂表面之间的相互作用最小化。代替在一个步骤中将催化剂20与离聚物一起混合,在加入催化剂前,先在独立的容器中使离聚物与CNT结合。在预混合步骤中,使用用于CNT和离聚物的不良溶剂,以仅收集密切结合的CNT-离聚物复合物用于进一步的浆料制备。因为离聚物缠绕在CNT周围,所以这种CNT-离聚物复合物具有密切结合。该方法的燃料电池测试表明在高电流密度下的性能得到改善(即在2.5A/cm2下40-60mV)。具体地,通过下面描述的方法100制造的本发明的电极4平衡质子传导和氧气传输,以便在电化学反应期间使能量转换最大化。
图3是示出用于制造燃料电池14和电极4的方法100的流程图。方法100从步骤102开始,其中CNT-离聚物复合物如下面详细讨论的那样制备。然后,方法100继续到步骤104,其中制备电极浆料。为了制备电极浆料,将CNT-复合物30与催化剂20和催化剂载体材料22混合。在制备电极浆料后,方法100继续到步骤106,将PEM 1用电极浆料涂覆。具体地,将PEM1的第一膜表面16和第二膜表面18用电极浆料涂覆。替代地或另外地,可以将第一气体扩散层11和第二气体扩散层13用电极浆料涂覆。
参照图4和5,步骤102需要制备CNT-离聚物复合物30并且包括几个子步骤。首先,在子步骤202中,将水、丙醇和离聚物分散液在第一容器32(例如烧瓶)中混合在一起以形成初始分散液34。在本发明中,术语“分散液”包括溶液、胶体和悬浮液。因为离聚物分散液包含离聚物,所以初始分散液包含离聚物。作为非限制性实例,将八十(80)克水,八(8)克正丙醇和二十二点三二(22.32)克离聚物分散液在第一容器32中混合在一起。在某些实施例中,离聚物分散液包含二十一点五(21.5)重量百分比(wt%)的离聚物和七十八点五(78.5)重量百分比(wt%)的溶剂,并且溶剂包括六十(60)重量百分比(wt%)的正丙醇和四十(40)重量百分比(wt%)的水。例如,离聚物分散液可以是由Dupont以商品名D2020出售的基于磺化四氟乙烯的氟聚合物-共聚物分散液。为了混合水、丙醇和离聚物分散液34,可以将磁力搅拌器36在第一容器32内旋转,如图4所示。然后,在子步骤204中,将碳纳米管31加入第一容器32中的初始分散液34中,同时搅拌初始分散液34以形成混合物38。例如,可以将一点八(1.8)克石墨化碳纳米管加入初始分散液34中。石墨化碳纳米管31可以是直径在10纳米与20纳米之间的多壁碳纳米管。选择具有高石墨化并具有适当直径(即10-20nm)的CNT 31以促进与离聚物的密切结合。
接下来,在子步骤206中,同时搅拌和加热混合物38。在某些实施例中,搅拌混合物38,使磁力搅拌器36以约三百五十(350)转/分钟(rpm)旋转,并加热至50摄氏度至100摄氏度范围内的温度以促进混合。例如,可以将混合物38加热至约八十(80)摄氏度。混合物38的加热和搅拌同时进行两个半(2.5)小时以确保适当的混合。然后,在子步骤208中,使混合物38冷却,同时搅拌混合物38过夜。换句话说,在将初始分散液同时加热并搅拌约两个半(2.5)小时后,将初始分散液搅拌约十六(16)个小时而不加热初始分散液,同时,使初始分散液通过自然对流冷却以形成CNT-离聚物复合物悬浮液。
参考图3、4和6,在形成CNT-离聚物复合物悬浮液后,方法100继续至步骤104,其中形成电极浆料。步骤104包括几个子步骤。在子步骤302中,将CNT-离聚物复合物悬浮液在第二容器(未示出)中与水、丙醇和催化剂混合以形成分离的离聚物电极涂层。作为非限制性实例,可以将五十六(56)克CNT-离聚物复合物悬浮液与三点八一(3.81)克催化剂,八点三(8.3)克正丙醇和三十二点七三(32.73)克水混合。在该子步骤中,可能需要搅拌以将CNT-离聚物复合物悬浮液与水、丙醇和催化剂适当混合。如上所述,催化剂20可以包括沉积在炭黑粉末28上的多个铂纳米颗粒26。然后,在子步骤304中,将分离的离聚物电极涂层的形式从第二容器(未示出)转移到含有ZrO2珠的聚合物瓶中。ZrO2珠可以具有五(5)毫米的直径。接下来,在子步骤306中,将含有分离的离聚物电极涂层和ZrO2珠的聚合物瓶以六十(60)RPM滚动约二十四(24)小时以形成电极浆料。
然后,如以上关于步骤106所讨论的那样,在电极浆料仍然是湿润的同时,将PEM 1和/或第一气体扩散层11和第二气体扩散层13用电极浆料涂覆,以形成厚度约三十六(36)微米的薄层。同样在步骤106中,使电浆料的湿层干燥(通过自然对流)以形成电极4。使用方法100制造的燃料电池14使离聚物与铂的相互作用最小化,同时保持高效和有效的质子传输,由此提高高功率燃料电池性能。
虽然已经详细描述了用于执行发明的最佳模式,但是本发明所涉及领域的技术人员将认识到用于在所附权利要求的范围内实施本发明的各种替代设计和实施例。
Claims (10)
1.一种制造燃料电池电极的方法,其包括:
将碳纳米管(CNT)与初始分散液混合,其中所述初始分散液包含离聚物;
加热并搅拌所述初始分散液以形成CNT-离聚物复合物悬浮液;
在形成CNT-离聚物复合物悬浮液后,将CNT-离聚物复合物悬浮液与电极催化剂溶液混合以形成电极浆料,其中所述电极催化剂溶液包含炭黑粉末和由所述炭黑粉末负载的催化剂;以及
将质子交换膜用所述电极浆料涂覆以形成所述燃料电池电极。
2.根据权利要求1所述的方法,其中所述离聚物包含在离聚物分散液中,并且所述方法还包括将水,正丙醇和所述离聚物分散液混合以形成所述初始分散液。
3.根据权利要求2所述的方法,其中:
混合所述水,所述正丙醇和所述离聚物分散液包括搅拌所述水,正丙醇和所述离聚物分散液;
将所述碳纳米管与所述初始分散液混合包括在搅拌所述初始分散液的同时将所述碳纳米管加入所述初始分散液中;以及
所述碳纳米管是石墨化碳纳米管。
4.根据权利要求3所述的方法,其中所述初始分散液包含80克所述水,8克所述正丙醇和1.8克所述石墨化碳纳米管。
5.根据权利要求4所述的方法,其中所述碳纳米管是直径在10纳米至20纳米范围内的多壁碳纳米管。
6.根据权利要求5所述的方法,其中加热并搅拌所述初始分散液包括使用以350转/分钟旋转的磁力搅拌器搅拌所述初始分散液。
7.根据权利要求6所述的方法,其中加热并搅拌所述初始分散液包括将所述初始分散液加热至50摄氏度至100摄氏度范围内的温度。
8.根据权利要求7所述的方法,其中加热并搅拌所述初始分散液包括同时加热并搅拌所述初始分散液2.5小时。
9.根据权利要求8所述的方法,还包括在同时加热并搅拌所述初始分散液2.5小时后,继续搅拌所述初始分散液16小时而不加热所述初始分散液。
10.根据权利要求9所述的方法,还包括通过自然对流使所述初始分散液冷却。
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US20200176785A1 (en) * | 2017-07-19 | 2020-06-04 | Korea Institute Of Energy Research | Electrode manufacturing method to suppress rearrangement of ionomers due to elution of platinum of polymer electrolyte membrane fuel cell |
US10777821B2 (en) * | 2018-03-22 | 2020-09-15 | Kabushiki Kaisha Toshiba | Catalyst, anode, membrane electrode assembly, water electrolysis cell, stack, water electrolyzer, and hydrogen utilizing system |
KR102260508B1 (ko) * | 2019-12-10 | 2021-06-07 | 현대모비스 주식회사 | 연료전지용 촉매, 이를 포함하는 연료전지용 전극 및 이를 포함하는 막전극접합체 |
DE102020200686A1 (de) | 2020-01-22 | 2021-07-22 | Robert Bosch Gesellschaft mit beschränkter Haftung | Verfahren zum Betrieb einer Brennstoffzelle und elektrochemisches System |
US20220109136A1 (en) * | 2020-10-01 | 2022-04-07 | GM Global Technology Operations LLC | Electrode assembly and method of making the same |
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CN101626081A (zh) * | 2008-07-10 | 2010-01-13 | 通用汽车环球科技运作公司 | 膜电极的结构增强 |
US20120301663A1 (en) * | 2010-03-26 | 2012-11-29 | Aisin Seiki Kabushiki Kaisha | Carbon nanotube composite and method for making the same |
CN103270008A (zh) * | 2010-12-20 | 2013-08-28 | 纳幕尔杜邦公司 | 离聚物和离子传导性组合物 |
CN104521047A (zh) * | 2012-08-02 | 2015-04-15 | 丰田自动车株式会社 | 燃料电池用电极以及燃料电池用电极、膜电极接合体和燃料电池的制造方法 |
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DE102013007199A1 (de) | 2013-04-25 | 2014-06-12 | Daimler Ag | Membranelektrodenanordnung und Brennstoffzelle |
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CN101626081A (zh) * | 2008-07-10 | 2010-01-13 | 通用汽车环球科技运作公司 | 膜电极的结构增强 |
US20120301663A1 (en) * | 2010-03-26 | 2012-11-29 | Aisin Seiki Kabushiki Kaisha | Carbon nanotube composite and method for making the same |
CN103270008A (zh) * | 2010-12-20 | 2013-08-28 | 纳幕尔杜邦公司 | 离聚物和离子传导性组合物 |
CN104521047A (zh) * | 2012-08-02 | 2015-04-15 | 丰田自动车株式会社 | 燃料电池用电极以及燃料电池用电极、膜电极接合体和燃料电池的制造方法 |
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DE102018111254B4 (de) | 2022-09-08 |
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DE102018111254A1 (de) | 2018-11-15 |
US10320004B2 (en) | 2019-06-11 |
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