CN116762183A - 高纯度气体扩散层 - Google Patents
高纯度气体扩散层 Download PDFInfo
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- CN116762183A CN116762183A CN202180085494.6A CN202180085494A CN116762183A CN 116762183 A CN116762183 A CN 116762183A CN 202180085494 A CN202180085494 A CN 202180085494A CN 116762183 A CN116762183 A CN 116762183A
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- fibers
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- carbon
- gas diffusion
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Classifications
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
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Abstract
本发明涉及一种制造高纯度气体扩散层的方法、可根据这种方法获得的气体扩散层以及一种包括这种气体扩散层的燃料电池。通过含水流体射流的作用将包含碳纤维和/或碳纤维前体的纤维网加固成无纺布,其中所使用的水在25摄氏度时的电导率最高为250microsiemens/cm。
Description
发明领域
本发明涉及一种制造高纯度气体扩散层的方法、可根据这种方法获得的气体扩散层以及一种包括这种气体扩散层的燃料电池。
背景技术
燃料电池利用燃料(特别是氢)与氧发生化学反应生成水来产生电能。在氢氧燃料电池中,氢或含氢气体混合物被提供给阳极,在阳极处发生电化学氧化并释放电子(H2→2H++2e-)。通过一个以气密方式将反应区彼此分开并使其电绝缘的膜,将质子从阳极区输送到阴极区。阳极处所提供的电子通过外导体电路被输送到阴极。氧或含氧气体混合物被提供给阴极,由此在吸收电子的情况下将氧还原。在此过程中所形成的氧阴离子与通过膜被输送过来的质子发生反应并生成水(1/2O2+2H++2e-→H2O)。
许多应用领域(特别是汽车动力传动系)会使用低温质子交换膜燃料电池(PEMFC,proton exchange membrane fuel cells,又称聚合物电解质膜燃料电池(polymerelectrolyte membrane fuel cells)),其核心部件是只允许质子(或水合氢离子H3O+)和水通过且在空间上将氧化剂(一般是大气中的氧气)与还原剂分开的聚合物电解质膜(PEM,Polymer-Elektrolyt-Membran)。在气密电绝缘质子传导膜的阳极侧和阴极侧上施加有催化剂层,该催化剂层形成电极,通常含有铂以作为催化活性金属。实际的氧化还原反应和电荷分离是在催化剂层中进行。膜和催化剂层形成一个又称催化剂涂层膜(CCM,catalystcoated membrane)的组件。CCM两侧设有气体扩散层(Gasdiffusionslage,GDL),该气体扩散层能稳定电池结构并承担反应气体、水、热和电流的输送功能和分配功能。膜、电极和气体扩散层形成膜电极组件(MEA,membrane electrode assembly)。膜电极组件之间设有集流板(所谓的双极板),这些集流板具有为相邻的阴极和阳极提供工艺气体的通道,通常还具有内部冷却通道。
位于集流板与催化剂层之间的气体扩散层对燃料电池的功能和性能具有至关重要的作用。例如,在电极反应中消耗和产生的工艺组分必须由气体扩散层输送,并且必须从集流板/双极板的宏观结构被均匀分配到催化剂层的微观结构上。在半电池反应中形成和消耗的电子必须以尽可能少的电压损失传导到集流板。反应过程中产生的热量必须消散到集流板中的冷却剂中,因此GDL的材料也须具有足够的导热性。此外,GDL还须在宏观结构化的集流板与催化剂层之间起机械平衡作用。
用于燃料电池的气体扩散层一般由碳纤维基材构成,通常用含氟聚合物(例如PTFE)对该碳纤维基材进行疏水处理,而后平面涂布微孔层(MPL,Lage)。MPL通常由作为粘合剂的含氟聚合物(例如PTFE)和多孔的导电碳材料(例如炭黑或石墨粉)组成。目前,以下三种材料被用作GDL的碳纤维基材:
-碳纤维纸(湿法成网和化学粘合的碳纤维无纺布,具有经碳化的化学粘合剂),
-碳纤维织物(例如由已氧化但尚未碳化的聚丙烯腈纤维纱线制成,纱线经织造后被碳化或石墨化),
-碳纤维无纺布(例如由氧化的聚丙烯腈制成的无纺布,干法成网,经梳理和水刺,随后被校准厚度和碳化)。
众所周知,燃料电池会因引入不参与电极过程的外来离子而受到污染。例如,已经有关于双极板材料对电池性能的影响以及从双极板引入燃料电池的MEA的阳离子和阴离子对电池性能的影响的研究。其他来源,特别是金属阳离子的来源,是来自于电池的其余材料、系统组件(如槽罐、热交换器、管道等)、提供给阴极的空气流和制造或运输过程中的氢气的杂质的排放。引入的金属离子的一个可能问题是,它们很容易被电解质膜吸收。其原因是金属阳离子对全氟阳离子交换膜的磺酸基的亲合力很强,通常大于质子对磺酸基的亲合力。
现在已发现,GDL也会在MEA加载外来离子方面起一定作用。因此,需要有离子(特别是金属阳离子)浓度极低的气体扩散层及其制造方法。GDL应特别具有低浓度的阳离子,如技术用水中通常所包含的阳离子,如钙离子、镁离子、钠离子和钾离子。同时,GDL的其余机械性能不应发生不利的变化。
为了制造碳纤维无纺布,可以通过含水流体射流的作用来加固由碳纤维或碳纤维前体制成的无纺布。这种用流体射流或流体流进行无纺布加固的水刺工艺,包括用过热蒸汽射流进行水刺,是本领域技术人员已知的。一种特殊的无纺布机械加固方法是水刺法,也就是压力提高到大约20bar至超过400bar的水通过多个喷嘴流到待加固的无纺布上。其中,水射流的脉冲力致使纤维被机械锚固于产品中。这种方法所使用的工具是所谓的水针板(Düsenstreifen),可以安装成一排或多排。每一排都有大量的喷嘴。最大喷嘴数可以达到每板20000个喷嘴,其中典型的喷嘴直径范围为0.05mm至0.3mm。
WO 0231841描述一种导电无纺布,这种无纺布是以由碳纤维的预氧化纤维所制成的纤维网为原料,通过在100bar至300bar的压力下用高压流体射流加固纤维网,将已加固的纤维无纺布致密化,随后在保护气氛中以800℃至2500℃的温度进行碳化和/或石墨化而获得。
DE 10 2006 060 932 A1描述了包括纤维和涂层的温度稳定的结构,其中该涂层共价地粘合到纤维表面。具体来说,这种结构是经过氟化烃的等离子体涂布处理的导电无纺布,适合作为燃料电池的气体扩散层。为了制造导电无纺布,以成网工艺将碳纤维或碳纤维前体制成纤维网,并且通过高压流体射流的作用将其加固,然后进行预干燥、轧光和碳化。
US 2019/0165379 A1描述一种基于碳纤维无纺布的、用于气体扩散层的材料,该碳纤维无纺布在平面内具有高克重区域和低克重区域,其中无纺布的至少一个表面具有凹凸不平的图案,该图案与纤维的重量分布无关。这种无纺布的制造包含了水射流工艺。
前述文献均未提供关于水射流处理中所使用的水的质量相关的信息。
现在已发现,如果通过水性流体射流的作用将由碳纤维或碳纤维前体制成的干法成网无纺布加固,就能制造出高纯度的碳纤维无纺布。出人意料的是,正是通过水刺法工艺才成功制造出离子浓度极低的高纯度无纺布,而这些无纺布可被进一步加工成离子浓度同样很低的GDL。有利的是,所获得的无纺布的特点是具有非常少的所谓的水针板缺陷(Düsenstreifenfehler)。这种水针板缺陷可能产生于水针板的个别喷嘴被堵塞时。
发明内容
本发明的第一主题是一种用于制造燃料电池的气体扩散层的方法,其中,
a)提供纤维组合物,该纤维组合物包含碳纤维和/或碳纤维的前体,
b)对步骤a)中所提供的纤维组合物实施用于制造纤维网的工艺,
c)通过含水流体射流的作用将纤维网加固成无纺布,其中所使用的水在25℃时的电导系数最高为250microsiemens/cm,
d)视需要对在步骤c)中得到的所述无纺布进行热处理和/或机械处理,以进行干燥和/或进一步加固,
e)如果步骤a)中所使用的所述纤维组合物包含碳纤维的前体,则在至少1000℃的温度下将所述无纺布热解。
在一种特定的实施方式中,用疏水剂整理来自步骤c)、步骤d)或步骤e)(即取决于这些步骤中哪些步骤被实施,在这些步骤中的最后一个步骤之后))的无纺布(=步骤f)。
在另一种特定的实施方式中,以微孔层涂布来自步骤c)、步骤d)、步骤e)或步骤f)(即取决于这些步骤中哪些步骤被实施,在这些步骤中的最后一个步骤之后)的无纺布(=步骤g)。
本发明还涉及一种离子浓度极低的、通过含水流体射流的作用而加固的纤维网(水刺无纺布)。因此,一种可通过包括以下步骤的方法而获得的无纺布也是本发明的主题:
a)提供纤维组合物,该纤维组合物包含碳纤维和/或碳纤维的前体,
b)对步骤a)中所提供的纤维组合物实施用于制造纤维网的工艺,
c)通过含水流体射流的作用将纤维网加固成无纺布,其中所使用的水在25℃时的电导率最高为250microsiemens/cm。
关于步骤a)、步骤b)和步骤c),请充分参考以下对这些步骤的阐述。
本发明的另一个主题是一种如上文和下文所述的气体扩散层或可通过如上文和下文所述的方法而获得的气体扩散层。
本发明的另一个主题是一种燃料电池,包括至少一个如上文和下文所述的气体扩散层或可通过如上文和下文所述的方法而获得的气体扩散层。
具体实施方式
根据本发明的方法所获得的气体扩散层具有以下优点:
-以干法成网碳纤维为原料通过水刺法而获得的碳纤维无纺布和基于此的GDL的特点是离子浓度非常低。
-以干法成网碳纤维前体为原料通过水刺法和随后的碳化或石墨化而获得的无纺布和基于此的GDL的特点也是离子浓度非常低。
-根据本发明的方法通过水刺法而获得的无纺布具有非常少的所谓水针板缺陷。
-与现有技术中以往所使用的GDL相比,根据本发明的GDL具有相当好的机械性能。
-与基于传统GDL的燃料电池相比,基于本发明的GDL的燃料电池具有更长的使用寿命。
根据本发明的气体扩散层和可以根据本发明的方法获得的气体扩散层包含作为平面状导电材料的碳纤维无纺布。碳纤维无纺布和气体扩散层是基本上呈二维平坦延伸且厚度相对较小的平面状结构。气体扩散层的基面一般与相邻的具有催化剂层的膜的基面以及燃料电池中的相邻集流板的基面基本相一致。气体扩散层的基面的形状例如可以是多边形(n边形,n≥3,例如三角形、四边形、五边形、六边形等)、圆形、圆弓形(例如半圆形)、椭圆形或椭圆弓形。该基面优选呈矩形或圆形。
气体扩散层的制造
步骤a)
在根据本发明的方法的步骤a)中,提供包含碳纤维和/或碳纤维的前体的纤维组合物。
以其总重量为参照,优选的碳纤维至少90wt%由碳构成,优选至少92wt%由碳构成。在一种特定的实施方式中,可以使用经石墨化处理的碳纤维。这些碳纤维具有更高的碳含量,特别是至少95wt%由碳构成。
合适的碳纤维前体是来自合成来源或天然来源的纤维,这些纤维可以通过一个或多个处理步骤转变为碳纤维(碳化)。举例而言,这样的纤维包括聚丙烯腈均聚物和共聚物纤维(PAN纤维)、酚醛树脂纤维、聚酯纤维、聚烯烃纤维、纤维素纤维、芳纶纤维、聚醚酮纤维、聚醚酯酮纤维、聚醚砜纤维、聚乙烯醇纤维、木质素纤维、沥青纤维及其混合物。优选地,步骤a)中所提供的纤维组合物包含作为前体纤维的PAN纤维或者由作为前体纤维的PAN纤维组成。在第一种优选实施方式中,步骤a)中所提供的纤维组合物包括PAN纤维和与之不同的纤维,后者优选选自酚醛树脂纤维、聚酯纤维、聚烯烃纤维、纤维素纤维、芳纶纤维、聚醚酮纤维、聚醚酯酮纤维、聚醚砜纤维、聚乙烯醇纤维、木质素纤维、沥青纤维及其混合物。以碳纤维前体为参照,这样的另外的聚合物的含量优选不超过50wt%,特别优选地不超过25wt%。在第二种优选实施方式中,步骤a)中所提供的纤维组合物完全由PAN纤维组成。
合适的PAN纤维选自PAN均聚物、PAN共聚物及其混合物。PAN共聚物以聚合方式包含至少一种共聚单体(Comonomer),所述共聚单体优选选自(甲基)丙烯酰胺、丙烯酸烷基酯、羟烷基丙烯酸酯、烷基醚丙烯酸酯、聚醚丙烯酸酯、烷基乙烯基醚、乙烯基卤化物、乙烯基芳族化合物、乙烯基酯、乙烯不饱和二羧酸及其单酯和二酯以及上述物质的混合物。所述共聚单体选自例如丙烯酰胺、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸正丁酯、丙烯酸正辛酯、丙烯酸月桂酯、丙烯酸硬脂酯、丙烯酸-2-乙基己酯、丙烯酸苄酯、丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、丙烯酸-4-羟基丁酯、丙烯酸2-甲氧基乙酯、丙烯酸4-甲氧基丁酯、丙烯酸二乙二醇乙醚酯、丙烯酸-2-丁氧基乙酯、乙基乙烯基醚、丙烯酸、甲基丙烯酸、衣康酸、衣康酸单甲酯、衣康酸单月桂酯、富马酸二甲酯、苯乙烯、乙酸乙烯酯、溴乙烯、氯乙烯等。如果在步骤a)中将聚丙烯腈共聚物纤维用作碳纤维前体,则以用于聚合的单体总重量为参照,共聚单体的占比最高为20wt%,优选最高为10wt%。优选地,在步骤a)中将聚丙烯腈均聚物纤维用作碳纤维前体。
例如,PAN聚合物可以作为溶液通过湿纺和凝固被纺成长丝,并合并成绳(纤维束)。PAN共聚物通常比PAN均聚物的熔点低,因此不仅适用于湿纺工艺,也适用于熔纺工艺。通常在含氧气氛中以大约180℃至300℃的高温下对以这种方式获得的PAN纤维进行氧化环化(也被简称为氧化或稳定化)。由此产生的化学交联有助于改善纤维的形状稳定性。
氧化环化时所得到的纤维可以在步骤a)中用作碳纤维的前体,而无需进一步的处理。也可以对氧化环化时所得到的纤维实施至少一个处理步骤,该处理步骤优选选自清洁、涂布至少一种上浆剂、干燥以及这些处理步骤中至少两个的组合。为了清洁电化学氧化后的纤维,可以对其进行洗涤处理。洗涤是专门用来去除纤维碎片的。洗涤后通常会有一个干燥步骤。为了改变表面特性,可在纤维上至少部分地涂布至少一种上浆剂。举例而言,上浆剂可以在适当的溶剂中以溶液的形式使用,或以分散体的形式使用。为了施加涂层,可以使纤维例如穿过上浆浴。在步骤c)的水刺法过程中,浆料会至少部分地从纤维上脱落。如果在步骤c)中用于加固纤维网的水至少部分地被回收,那么对水刺法的废水进行处理可能是有利的,在处理过程中,包含在废水中的浆料被部分或完全去除。
在为纤维涂布至少一种上浆剂后,通常会对其进行(进一步)干燥。举例而言,可以用热空气、热板、加热辊或热辐射器来进行干燥。
以这种方式得到的碳纤维前体可以在根据本发明的方法的步骤a)中用作纤维组合物并且可被进一步加工。作为替代方案,可以在至少1000℃的温度下将包含PAN纤维或由PAN纤维组成的纤维组合物热解,其中PAN前体转变为碳纤维。关于热解条件,请参考以下对步骤e)的阐述。以这种方式得到的碳纤维同样可在根据本发明的方法的步骤a)中用作纤维组合物并且可被进一步加工。
步骤b)
在根据本发明的方法的步骤b)中,对步骤a)中所提供的纤维组合物实施用于制造纤维网(碳纤维无纺布或碳纤维前体无纺布)的工艺。合适的无纺布制造工艺是本领域技术人员已知的,例如记载于H.Fuchs,W.Albrecht,《Vliesstoffe(无纺布)》,2.Aufl.2012(2012年第二版),S.121ff(第121页及以下),Wiley-VCH中。这些工艺包括例如干法工艺、湿法工艺、挤压工艺和溶剂工艺。在一个优选实施方案中,在步骤b)中对步骤a)中所提供的纤维组合物实施干法成网工艺,以制造纤维网。原则上可以按照梳理工艺或空气动力工艺来制造干法成网无纺布。梳理工艺是使用起绒机或梳理机来形成纤维网,空气动力工艺则是借助空气来用纤维形成无纺布。如果需要,可以将纤维网分多层叠在一起,形成无纺布。步骤b)中的干法成网工艺可以包括对性能的改变,其方式例如是拉伸无纺布。举例而言,借此可以实现无纺布的厚度校准和/或纤维网的预加固。
步骤c)
在根据本发明的方法的步骤c)中,通过含水流体射流的作用将在步骤b)中得到的纤维网加固成无纺布。在此,含水流体射流也包括流体流和蒸汽射流。
原则上,用于实现这一目的的已知机械加固工艺(又称水刺工艺,Spunlace-Verfahren)适合用来进行水刺法。使用过热蒸汽射流来加固无纺布的蒸汽射流技术原则上也是适用的。这类工艺是本领域技术人员已知的。在一种特定的无纺布机械加固方法中,通过大量喷嘴将压力提高到大约20bar至500bar的水引到待加固的无纺布上。这些喷嘴在所谓的水针板中布置成一排或多排。这些水针板的每一排都有大量喷嘴。最大喷嘴数可以达到每板20000个喷嘴,其中典型的喷嘴直径范围为0.05mm至0.5mm。喷嘴孔径的公差通常都很小,例如小于2mm。为了获得无缺陷的无纺布,有必要使喷嘴的孔径在操作过程中不发生变化,特别是使喷嘴不关闭。
现在已发现,用于加固纤维网(无纺布)的水的电导率对于用该纤维网所制成的燃料电池用气体扩散层的质量至关重要。因此,根据本发明的方法的一个关键特征是,在步骤c)中用于加固无纺布的水在25℃时的电导率最高为250microsiemens/cm(μS/cm)。步骤c)中所使用的水优选地在25℃时的电导率最高为200microsiemens/cm,特别优选地在25℃时的电导率最高为150microsiemens/cm,特别地在25℃时的电导率最高为100microsiemens/cm。
电导率是离子浓度(即溶解在一定量水中的解离物质的比例)的综合指标。这里的电导率取决于多种因素,包括溶解物质的浓度及其解离程度、所形成的阳离子和阴离子的价态和迁移率、以及温度。电导率的测量是基于对待分析水样的欧姆电阻或电阻倒数(即电导系数(单位为西门子S=Ω-1))的测定。可以使用市售电导率测量仪(电导计)来测量电导率。测量值通常以S/cm(西门子/厘米)为单位,对于低离子负荷的水样则以μS/cm(微西门子/厘米)为单位。
工业制程的工艺用水和操作用水一般来自于公共饮用水网或者是从水井、河流和湖泊中提取。饮用水和对水质要求很高的工艺用水,通常要对其成分进行检查,必要时还要进行水处理。不同应用领域对水的纯度要求极为不同。例如,饮用水是一种无色透明的液体,没有气味,不含有害的微生物和物质,但富含重要的矿物质和盐分。这种水具有食品级质量,但对于许多技术应用领域来说不一定适用。例如,根据德国饮用水条例(TrinkwV2001,2016年3月10日的新版本),电导率的极限值是25℃时2790microsiemens/cm。德国自来水厂供应的自来水在25℃时的电导率为250microsiemens/cm至1000microsiemens/cm,具体视硬度等级而定。主要的无机阳离子是Na+、K+、Ca2+和Mg2+。
为了提供本发明在步骤c)中所使用的水,可以对现有的饮用水或工艺用水进行处理以降低离子浓度。这种处理包括离子交换、电去离子、膜法(如纳滤、反渗透和电渗析)、热处理(如闪蒸)等。
优选采用纳滤、反渗透或这些工艺的组合来降低离子浓度。纳滤和反渗透都是使待处理的水在高于渗透压的压力下穿过半透膜,获得离子浓度降低的渗透物。纳滤是在比反渗透更低的压力下进行的,因此其净化能力比反渗透低,但在许多情况下是足够的。也可以先通过纳滤进行预净化,而后通过反渗透进一步降低离子浓度。
步骤c)中所使用的水的Na+离子含量优选地最高为200wppm,特别优选地最高为25wppm。
步骤c)中所使用的水的K+离子含量优选地最高为200wppm,特别优选地最高为10wppm。
步骤c)中所使用的水的Mg2+离子含量优选地最高为10wppm。
步骤c)中所使用的水的Ca2+离子含量优选地最高为200wppm,特别优选地最高为40wppm。
在根据本发明的方法的一种特定实施方式中,在步骤c)中用于加固纤维网的水被部分或完全回收。因此,根据本发明的方法可以减少水刺法的新水需求和待处理的废水量。可以确保用于处理纤维网的水始终具有处于本发明范围内的电导率,而且还可以避免纤维网被水刺法废水中所包含的组分污染。为此,可以对水刺法的废水进行部分或全部的处理和/或交换。
对水刺法废水的处理和/或交换可以连续或间歇进行。
以下方法是优选的:通过含水流体射流的作用将纤维网加固成无纺布,从纤维网的处理中排出废水流,确定废水流的电导率的设定值,测定废水流的电导率的实际值,在实际值与设定值的偏差达到极限值之后,对废水流至少部分地进行处理和/或与离子浓度更低的水交换,并且将废水流至少部分地送回到对纤维网的处理中。
为了进行处理,可以如前所述对废水流进行离子浓度的降低。此外,还可以进一步净化废水流,以便例如去除纤维和纤维碎片。
步骤d)
视需要可以对在步骤c)中得到的无纺布进行热处理和/或机械处理,以进行干燥和/或进一步加固。合适的干燥方法是对流干燥、接触干燥、辐射干燥及其组合。
优选以轧光方式对在步骤c)中得到的无纺布进行处理。轧光可以使无纺布进一步热加固,同时进行厚度校准。在此过程中,也可以将多个无纺布层连接在一起。在一种特定的实施方式中,在步骤c)中得到的无纺布包含有用作粘合纤维且通常可碳化的热塑性纤维。在此情况下,可以在步骤d)中对无纺布进行热轧光加固,并形成粘合点,在这些粘合点上纤维被塑化并熔接在一起(热粘合)。
步骤e)
如果步骤a)中所使用的纤维组合物包含碳纤维的前体,则在步骤e)中以至少1000℃的温度将无纺布热解。根据热解时的温度,对碳化和石墨化进行了区分。碳化是指在惰性气氛中以大约1000℃至1500℃的温度进行处理,以便脱去挥发性产物。通过石墨化(即在惰性气体中加热至约2000℃至3000℃)则能得到所谓的高模量纤维或石墨纤维。在热解过程中,碳含量例如从以低于1000℃的温度进行处理时的大约67wt%上升到以高于2000℃的温度进行处理时的大约99wt%。具体来说,通过石墨化得到的纤维纯度高,重量轻,强度高,并且具有非常好的导电性和导热性。
步骤f)
可选地,在步骤c)、步骤d)或步骤e)之后,可用至少一种添加剂整理无纺布。这些添加剂优选选自疏水剂f1)、电导率改善添加剂f2)、不同于f1)和f2)的其他添加剂f3)及其混合物。
优选用疏水剂f1)涂布和/或浸渍(整理)无纺布,该疏水剂包含至少一种含氟聚合物。优选地,该含氟聚合物选自聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)、全氟烷氧基聚合物(PFA)及其混合物。全氟烷氧基聚合物例如是四氟乙烯(TFE)和全氟烷氧基乙烯基醚,如全氟乙烯基丙醚的共聚物。优选使用聚四氟乙烯作为含氟聚合物。
以无纺布的质量为参照,含氟聚合物f1)的质量占比优选为0.5%至40%,特别优选为1%至20%,特别是1%至10%。在一种特定的实施方式中,含氟聚合物是PTFE,以无纺布的质量为参照,其质量占比为0.5%至40%,优选为1%至20%,特别是1%至10%。
即使没有电导率改善添加剂,无纺布也往往会由于所使用的碳纤维而已经具有良好的导电性和导热性。然而,为了改善导电性和导热性,可以进一步用至少一种电导率改善添加剂f2)来整理无纺布。优选用选自以下的电导率改善添加剂f2)整理无纺布:金属颗粒、炭黑、石墨、石墨烯、碳纳米管(CNT)、碳纳米纤维及其混合物。优选地,电导率改善添加剂f2)包含炭黑或由炭黑构成。举例而言,用至少一种电导率改善添加剂f2)对无纺布所进行的整理可以与用聚合物f1)和/或其他添加剂f3)所进行的整理一起进行。优选用水性分散体整理无纺布。
优选地,以无纺布的质量为参照,电导率改善添加剂f2)的质量占比为0.5%至45%,优选为1%至25%。在一种特定的实施方式中,电导率改善添加剂f2)包含炭黑或由炭黑构成,以无纺布的质量为参照,其质量占比为0.5%至45%,优选为1%至25%。
可进一步用至少一种其他添加剂f3)整理无纺布。这些添加剂例如包含不同于组分f1)和f2)的聚合物粘合剂、表面活性物质等。合适的粘合剂f3)例如是呋喃树脂等。具体来说,可进一步用至少一种不同于f1)的聚合物整理无纺布,其中优选使用高性能聚合物。其他聚合物f3)优选选自聚芳醚酮、聚苯硫醚、聚砜、聚醚砜、部分芳基化(共)聚酰胺、聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺及其混合物。举例而言,用至少一种添加剂f3)对无纺布所进行的整理可以与用聚合物f1)和/或电导率改善添加剂f2)所进行的整理一起进行。接下来可视需要将粘合剂f3)固化。举例而言,该固化可以在用聚合物f1)进行整理后与干燥和/或烧结一起进行,或与之分开进行。
优选地,以无纺布的质量为参照,其他添加剂f3)的总质量占比为0%至80%,优选为0%至50%。如果无纺布包含至少一种另外的其他添加剂f3),则以无纺布的质量为参照,其他添加剂f3)的总质量占比为0.1%至80%,优选为0.5%至50%。
无纺布优选具有在50μm至500μm,特别优选100μm至400μm范围内的厚度。这个厚度涉及的是无纺布未经整理时的未压缩状态,即在GDL被装入燃料电池之前。
可以通过本领域技术人员已知的施加方法用组分f1)、f2)和/或f3)对无纺布进行整理,特别是如涂布和/或浸渍。优选采用选自浸轧、涂刷、喷涂、面轧及其组合的工艺来涂布和/或浸渍无纺布。
在浸轧工艺中,导引无纺布穿过具有含添加剂溶液或分散体的浸轧机(浸渍槽),而后借助辊对将无纺布挤压到期望的添加剂施加量,所述辊对可调节压力,必要时还可调节间隙。
涂刷工艺有凹版印刷和丝网印刷之分。凹版印刷例如将带有或不带有支撑刮刀的刀刃状研磨钢带作为刮刀。支撑刮刀的作用是从压印滚筒的连接条上擦除(刮除)多余的含添加剂溶液或分散体。而在丝网印刷中,刮刀则通常由具有磨尖或磨圆边缘的橡胶或塑料制成。
喷涂工艺是借助至少一个喷嘴(具体是至少一个缝式喷嘴)将含有添加剂的溶液或分散体施加在待整理的无纺布上。
面轧工艺(舔液辊)优选用于涂布水平运行的网状材料底面。涂布介质可以反向或同向地被施加到产品网上。通过转印辊可以实现施加量较小的间接涂布。
在一种特定的实施方式中,对在根据本发明的方法的步骤f)中用组分f1)、f2)和/或f3)整理过的无纺布进行干燥和/或热处理。适合用来对已用含有添加剂的溶液或分散体涂布和/或浸渍过的无纺布进行干燥和/或热处理的工艺基本上是已知的。优选在20℃至250℃的温度范围内,特别优选在40℃至200℃的温度范围内进行干燥和/或热处理。进一步地,可以在降低的压力下进行干燥。
步骤g)
在一种优选实施方式中,根据本发明的气体扩散层由基于无纺布和无纺布的一个表面上的微孔层(MPL)的两层层状复合物组成。为了制造气体扩散层,可相应地以微孔层涂布在步骤c)、步骤d)、步骤e)或步骤f)中得到的无纺布。
与大孔无纺布相比,MPL是微孔的,其孔径一般远低于一微米,优选为最大900nm,特别优选为最大500nm,尤其为最大300nm。MPL的平均孔径优选在5nm至200nm,特别优选10nm至100nm的范围内。可以用压汞法测定平均孔径。MPL在由聚合物粘合剂构成的基质中包含导电碳颗粒,优选是炭黑或石墨。优选的粘合剂是前述含氟聚合物,特别是聚四氟乙烯(PTFE)。
微孔层优选具有在10μm至100μm(微米),特别优选20μm至50μm范围内的厚度。这个厚度涉及的是微孔层B)的未压缩状态,即在GDL被装入燃料电池之前。
根据本发明的气体扩散层优选具有在80μm至1000μm,特别优选100μm至500μm范围内的厚度(无纺布和MPL的总厚度)。这个厚度涉及的是GDL的未压缩状态,即在GDL被装入燃料电池之前。
本发明的另一个主题是一种燃料电池,包括至少一个如上文所述的气体扩散层或可通过如上文所述的方法而获得的气体扩散层。原则上,根据本发明的气体扩散层适用于所有常见的燃料电池类型,特别是低温质子交换膜燃料电池(PEMFC)。请充分参考前文中针对燃料电池的构造所做的阐述。
附图说明
图1示出未经处理的无纺布和用不同电导率的水加固的无纺布的金属含量(Ca2+、Na+、Mg2+和K+)。
图2示出用不同电导率的水加固的基础无纺布、用所述基础无纺布通过碳化得到的碳纤维无纺布和施加MPL后得到的气体扩散层的Ca2+离子和Na+离子的含量。
图3与图2相类似,示出Ca2+离子和Na+离子的含量总和。
下面将借助实施例对本发明进行说明,这些实施例不应理解为限制性的。
实施例
用ICP-AES法(电感耦合氩等离子体原子发射光谱法)测定由氧化聚丙烯腈纤维制成的基础无纺布、由此产生的碳化无纺布和GDL的金属含量(Ca2+、Na+、Mg2+和K+)。可以按照沉积物、淤泥和土壤的酸消解方法EPA3050A对样品进行预处理(消解)。这个过程包括以下步骤:
1.)在95℃下进行15分钟的硝酸消解。
2.)在继续消解1小时的同时进一步添加硝酸。
3.)从加热板上取下;添加去离子水和20%的过氧化氢溶液。
4.)在加热板上再次加热约15分钟,在气泡完全停止形成后,再度从加热板上取下。
5.)添加浓盐酸,再次消解1小时。
使用电导率符合下表1的水来进行水刺法。比较用水1对应的是传统的无纺布水刺法工艺中所常用的工艺用水。对于2和3这两个批次的水,以纳滤方式降低离子浓度。
表1
水的批次 | 电导率[microsiemens/cm] |
V1(比较) | 290 |
2 | 100 |
3 | 22 |
制造实施例
为了制造基础无纺布,将由100%氧化的聚丙烯腈纤维制成的干法成网纤维网放置在梳理设备上。将纤维网送入加固单元,在所述加固单元中,借助高能水射流在第一阶段和第二阶段分别以约100bar和约200bar的压力将纤维两面交错和交织。使用符合表1的水质。将无纺布干燥并卷起,其中水刺法和干燥后的克重为150g/m2。随后对无纺布进行厚度校准,从而将水刺无纺布的厚度减小至0.25mm。然后将无纺布送入碳化单元,在所述碳化单元中,在氮气气氛中于约1000℃至1400℃下进行碳化。
用浸渍组合物整理无纺布,以固体物质计,该浸渍组合物包含70%的炭黑和30%的PTFE。通过用浸轧机以水性分散体进行浸渍的方式进行整理,整理重量占GDL基材质量的15%(相当于15g/m2)。然后在180℃下干燥,在400℃下烧结。而后将在蒸馏水中包含2.0wt%的PTFE和7.8wt%的碳的MPL浆料施加在以这种方式得到的基材上。随后将无纺布在160℃下干燥,并在400℃下烧结。由此产生的MPL负载为24g/m2。
Claims (18)
1.一种用于制造燃料电池的气体扩散层的方法,其中,
a)提供纤维组合物,所述纤维组合物包含碳纤维和/或碳纤维的前体,
b)对步骤a)中所提供的所述纤维组合物实施用于制造纤维网的工艺,
c)通过含水流体射流的作用将所述纤维网加固成无纺布,其中所使用的水在25℃时的电导率最高为250microsiemens/cm,
d)视需要对在步骤c)中得到的所述无纺布进行热处理和/或机械处理,以进行干燥和/或进一步加固,
e)如果步骤a)中所使用的所述纤维组合物包含碳纤维的前体,则在至少1000℃的温度下将所述无纺布热解。
2.根据权利要求1所述的方法,其中进一步用至少一种添加剂整理在步骤c)、步骤d)或步骤e)中得到的所述无纺布(步骤f)),所述添加剂优选选自疏水剂f1)、电导率改善添加剂f2)、其他添加剂f3)及其混合物。
3.根据权利要求1或2所述的方法,其中进一步以微孔层涂布在步骤c)、步骤d)、步骤e)或步骤f)中得到的所述无纺布(步骤g))。
4.根据上述权利要求中任一项所述的方法,其中步骤a)中所提供的所述纤维组合物包含碳纤维的前体,所述碳纤维的前体选自非氧化聚丙烯腈纤维、氧化聚丙烯腈纤维及其混合物。
5.根据权利要求1至4中任一项所述的方法,其中步骤a)中所提供的所述纤维组合物进一步包含其他纤维,所述其他纤维选自酚醛树脂纤维、聚酯纤维、聚烯烃纤维、纤维素纤维、芳纶纤维、聚醚酮纤维、聚醚酯酮纤维、聚醚砜纤维、聚乙烯醇纤维、木质素纤维、沥青纤维及其混合物。
6.根据权利要求1至4中任一项所述的方法,其中步骤a)中所提供的所述纤维组合物由聚丙烯腈纤维组成,特别是由聚丙烯腈均聚物纤维组成。
7.根据上述权利要求中任一项所述的方法,其中在步骤b)中对步骤a)中提供的所述纤维组合物实施干法成网工艺,以制造纤维网。
8.根据上述权利要求中任一项所述的方法,其中在步骤c)中用于加固所述纤维网的水在25℃时的电导率最高为200microsiemens/cm,优选地,在25℃时的电导率最高为150microsiemens/cm。
9.根据上述权利要求中任一项所述的方法,其中在步骤c)中用于加固所述纤维网的水至少部分地被回收。
10.根据权利要求9所述的方法,其中通过含水流体射流的作用将纤维网加固成无纺布,从所述纤维网的处理中排出废水流,确定所述废水流的电导率的设定值,测定所述废水流的电导率的实际值,在所述实际值与所述设定值的偏差达到极限值之后,对所述废水流至少部分地进行处理和/或与离子浓度更低的水交换,并且将所述废水流至少部分地送回到对所述纤维网的处理中。
11.根据上述权利要求中任一项所述的方法,其中在步骤d)中以轧光方式进一步加固在步骤c)中得到的所述无纺布。
12.根据权利要求2至11中任一项所述的方法,其中所述疏水剂f1)包含至少一种含氟聚合物。
13.根据权利要求2至12中任一项所述的方法,其中所述电导率改善添加剂f2)选自金属颗粒、炭黑、石墨、石墨烯、碳纳米管(CNT)、碳纳米纤维及其混合物。
14.根据权利要求2至13中任一项所述的方法,其中所述其他添加剂f3)选自不同于所述组分f1)和f2)的聚合物粘合剂、表面活性物质及其混合物。
15.根据权利要求2至14中任一项所述的方法,其中在步骤f1)中用疏水剂涂布和/或浸渍期间或之后,对所述无纺布进行热处理。
16.一种可通过包括以下步骤的方法而获得的无纺布:
a)提供纤维组合物,所述纤维组合物包含碳纤维和/或碳纤维的前体,
b)对步骤a)中所提供的所述纤维组合物实施用于制造纤维网的工艺,
c)通过含水流体射流的作用将所述纤维网加固成无纺布,其中所使用的水在25℃时的电导率最高为250microsiemens/cm。
17.一种可通过如权利要求1至15中任一项所述的方法而获得的气体扩散层。
18.一种燃料电池,其包括至少一个可通过如权利要求1至15中任一项所述的方法而获得的气体扩散层。
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