CN116043521A - 水性碳纤维及其制备方法、分散体系和燃料电池碳纤维纸 - Google Patents
水性碳纤维及其制备方法、分散体系和燃料电池碳纤维纸 Download PDFInfo
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Abstract
本发明公开了水性碳纤维及其制备方法、分散体系和燃料电池碳纤维纸,涉及燃料电池技术领域。该水性碳纤维的制备方法其包括将碳纤维进行预处理后,再采用上浆剂进行上浆处理,其中,预处理包括低温氧化处理、电解处理和液相氧化处理中的至少一种;上浆剂的组分包括水性聚合物、粘接剂、乳化剂和水。本申请可以赋予碳纤维电性,增强碳纤维的亲水性,使其在水中具有更好的开纤性,并且能达到在低浓度的情况下完全分散的效果,减少了对分散剂的需求,此外,本申请提供的水性碳纤维减少了脱胶工序,在改善纤维分散性的同时能够保证碳纸的强度,有利于节约成本;而本申请提供的水性碳纤维的分散体系,可达到较高的碳纤维分散浓度。
Description
技术领域
本发明涉及燃料电池技术领域,具体而言,涉及水性碳纤维及其制备方法、分散体系和燃料电池碳纤维纸。
背景技术
质子交换膜燃料电池发电作为新一代发电技术,其广阔的应用前景可与计算机技术相媲美,主要由质子膜、催化剂层、气体扩散层、双极板构成。其中气体扩散层是重要组成部分,其主要作用除附着催化剂、支撑质子交换膜外,还需要协助隔板向内气体扩散、向外排水以及电流导出,因此需要具有一定的机械强度,并且要求高孔隙率和导电性,从而不影响气体的通过并尽可能的降低内电阻。
目前,用高性能碳纤维纸制作为质子交换膜燃料电池(PEMFC)的气体扩散层已得到了广泛的应用。近年来,国内出现了不少有关碳纤维纸的相关文章以及专利,其中,湿法造纸技术是较为普遍的制备方法。就传统造纸而言,纤维分散是成纸的关键步骤,直接决定了纸页的物理性能。同理,碳纤维纸的制备也是一样。
中国专利CN102936867B公布了燃料电池电极多孔扩散层材料碳纤维纸的制备工艺。其工艺采用湿法造纸技术将经表面脱胶处理的碳纤维与导电炭黑原木浆混合抄造制备得到碳纤维纸,其虽得到良好性能的碳纤维纸,但是碳纤维表面脱胶处理不但会损伤碳纤维强度而且会存在一定比例上浆剂脱除不完全而导致纤维分散困难,最终会影响碳纤维纸的物理性能。此外,原木浆纤维的存在使得碳纤维纸的导电性能下降。中国专利CN108914681A以聚丙烯腈基碳纤维为主要增强体,中间相沥青基碳纤维为功能添加剂,酚醛树脂为粘结剂制备一种高性能碳纤维纸。其在保证碳纤维纸良好的机械性能的前提下,提高其导电、导热性能。上述研究均存在共同缺陷,即需要脱胶工序以及添加分散剂来达到好的分散效果,最终受益于制备良好性能的质子交换膜燃料电池用碳纤维纸。
目前,采用湿法造纸技术抄造原纸过程中,提高分散性主要通过碳纤维脱胶处理和浆内添加大量的分散剂两种方法来实现。但是脱胶处理必然会对碳纤维有损伤,导致碳纸强度降低;而大量的分散剂使用在一定程度上使得成纸时滤水速度慢,影响在纸机生产上的抄造。
鉴于此,特提出本发明。
发明内容
本发明的目的在于提供一种水性碳纤维及其制备方法,获得的水性碳纤维表面具有亲水基团或水溶性上浆剂,易于分散。
本发明的目的在于提供一种水性碳纤维的分散体系,其分散效果等级佳,并且适用于从高浓度体系直接加水稀释至低浓度体系,用于碳纸原纸的抄造,省去了脱胶工序,且节省储存空间,易于流转。
本发明的目的在于提供一种燃料电池碳纤维纸。
本发明是这样实现的:
第一方面,本发明提供一种水性碳纤维的制备方法,其包括:将碳纤维进行预处理后,再采用上浆剂进行上浆处理,
其中,所述预处理包括低温氧化处理、电解处理和液相氧化处理中的至少一种;所述上浆剂的组分包括质量比为(10~20):(1~5):(5~20):(60~90)的水性聚合物、乳化剂、粘接剂和水。
在可选的实施方式中,所述低温氧化处理包括将所述碳纤维于300~500℃的空气氛围中灼烧0.1~5h;
优选地,所述电解处理包括选用酸性电解质或中性电解质作为电解液,进行电解处理0.1~5h;
优选地,所述酸性电解质包括硫酸、硝酸或者两者混合液;
优选地,所述中性电解质包括硫酸钠、硝酸钾或者两者混合物;
优选地,所述液相氧化处理包括采用氧化剂处理0.1~5h;其中,所述氧化剂包括高锰酸钾、双氧水和过硫酸盐中的至少一种。
在可选的实施方式中,所述水性聚合物包括聚氧化乙烯、聚乙二醇、聚丙烯酸树脂、阴离子聚丙烯酸钠、阴离子聚丙烯酰胺、阳离子聚丙烯酰胺、两性聚丙烯酰胺、阳离子淀粉、阴离子淀粉和两性淀粉中的至少一者;
优选地,所述粘接剂为热固性的水溶性树脂;
优选地,所述水溶性树脂包括环氧氯丙烷树脂、脲醛树脂和三聚氰胺树脂中的至少一种;
优选地,所述乳化剂包括十二烷基硫酸钠盐、硬脂酸钠盐、N-十二烷基二甲胺和聚氧乙烯醚类中的一种。
在可选的实施方式中,所述碳纤维为PAN基碳纤维,所述碳纤维的丝束范围为3K-50K,优选为12K或24K。
第二方面,本发明提供一种水性碳纤维,其采用如前述实施方式任一项所述的水性碳纤维的制备方法制备而成。
第三方面,本发明提供一种水性碳纤维的分散体系,其采用如前述实施方式所述的水性碳纤维短切形成短切亲水性碳纤维,随后于分散液中分散而成。
在可选的实施方式中,所述短切亲水性碳纤维的长度为3~15mm,优选为4~10mm。
在可选的实施方式中,所述碳纤维与所述分散液的质量比为(1~10):(2000~10000);
优选地,所述分散液包括表面活性剂、高分子聚合物的水溶液中的一种或两者的组合;
优选地,所述表面活性剂包括脂肪醇类表面活性剂、硅醇类表面活性剂或硬脂酸盐类表面活性剂;更优选地,所述表面活性剂为聚醚改性硅油;
优选地,所述高分子聚合物包括聚氧化乙烯、阴离聚丙烯酰胺、阳离子聚丙烯酰胺和聚丙烯酸钠中的一种;
优选地,所述高分子聚合物的分子量为300万~2000万,更优选为600万~1500万。
第四方面,本发明提供一种燃料电池碳纤维纸,其采用如前述实施方式任一项所述的水性碳纤维的分散体系制备而成。
本发明具有以下有益效果:
本申请提供的水性碳纤维的制备方法,通过对碳纤维进行低温氧化处理、电解处理和液相氧化处理中的至少一种的预处理和特定上浆剂的上浆处理,可以赋予碳纤维电性,增强碳纤维的亲水性,使其在水中具有更好的开纤性,并且能达到在低浓度的情况下完全分散的效果,减少了对分散剂的需求,从而避免了对生产运转的负面影响;此外,本申请提供的水性碳纤维减少了脱胶工序,在改善纤维分散性的同时能够保证碳纸的强度,有利于节约成本;而本申请提供的水性碳纤维的分散体系,可以针对碳纤维的电性特性,采用相应的碳纤维分散液,可达到较高的碳纤维分散浓度,并且可以直接加水稀释的便利效果,提升了在生产过程中操作的便利性,有利于节降生产设备的投资。
附图说明
为了更清楚地说明本发明实施例的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,应当理解,以下附图仅示出了本发明的某些实施例,因此不应被看作是对范围的限定,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他相关的附图。
图1为碳纤维的分散等级为1级时的效果示意图;
图2为碳纤维的分散等级为2级时的效果示意图;
图3为碳纤维的分散等级为3级时的效果示意图;
图4为碳纤维的分散等级为4级时的效果示意图;
图5为碳纤维的分散等级为5级时的效果示意图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚,下面将对本发明实施例中的技术方案进行清楚、完整地描述。实施例中未注明具体条件者,按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者,均为可以通过市售购买获得的常规产品。
本发明提供一种水性碳纤维,其制备方法包括如下步骤:
(1)将碳纤维进行预处理
碳纤维为PAN基碳纤维,碳纤维的丝束范围为3K-50K,优选为12K或24K。
预处理包括低温氧化处理、电解处理和液相氧化处理中的至少一种。低温氧化处理包括将碳纤维于300~500℃的空气氛围中灼烧0.1~5h;电解处理包括选用酸性电解质或中性电解质作为电解液,进行电解处理0.1~5h;液相氧化处理包括采用氧化剂处理0.1~5h。
其中,酸性电解质包括但不限于硫酸、硝酸或者两者混合液;中性电解质包括硫酸钠、硝酸钾或者两者混合物;氧化剂包括高锰酸钾、双氧水和过硫酸盐中的至少一种。
(2)采用上浆剂进行上浆处理。
上浆剂的组分包括水性聚合物、乳化剂、粘接剂和水,其比例范围为10~20:1~5:5~20:60~90。
其中,水性聚合物包括但不限于聚氧化乙烯、聚乙二醇、聚丙烯酸树脂、阴离子聚丙烯酸钠、阴离子聚丙烯酰胺、阳离子聚丙烯酰胺、两性聚丙烯酰胺、阳离子淀粉、阴离子淀粉和两性淀粉中的至少一者;
乳化剂包括但不限于阴离子乳化剂、阳离子型乳化剂或非离子型乳化剂中的一种;优选地,乳化剂包括但不限于十二烷基硫酸钠盐、硬脂酸钠盐、N-十二烷基二甲胺和聚氧乙烯醚类中的一种。
粘接剂为热固性的水溶性树脂;水溶性树脂包括但不限于环氧氯丙烷树脂、脲醛树脂和三聚氰胺树脂中的至少一种。
本申请中,通过对碳纤维进行预处理和上浆处理,可以赋予碳纤维电性,增强碳纤维的亲水性,使其在水中具有更好开纤性,并且能达到在低浓度的情况下完全分散的效果,减少了对分散剂的需求,从而避免了对生产运转的负面影响。
此外,本发明还提供一种水性碳纤维的分散体系,其采用如前述实施方式的水性碳纤维短切形成长度为3~15mm(优选为4~10mm)的短切亲水性碳纤维,随后于分散液中分散而成,碳纤维与分散液的质量比为1~10:2000~10000。
分散液包括表面活性剂、高分子聚合物的水溶液中的一种或两者的组合,其中表面活性剂与高分子聚合物的含量比例为(0.1~1g/L):(0.1~10g/L);其中,表面活性剂包括但不限于脂肪醇类表面活性剂、硅醇类表面活性剂或硬脂酸盐类表面活性剂;更优选地,表面活性剂为聚醚改性硅油;高分子聚合物包括但不限于聚氧化乙烯、阴离子聚丙烯酰胺、阳离子聚丙烯酰胺和聚丙烯酸钠中的一种;高分子聚合物的分子量为300万~2000万,更优选为600万~1500万。
本申请制备的水性碳纤维,针对碳纤维的电性特性,采用相应的碳纤维分散液,可达到较高的碳纤维分散浓度,并且可以直接加水稀释的便利效果,提升了在生产过程中操作的便利性,有利于节降生产设备的投资。
第四方面,本发明提供一种燃料电池碳纤维纸,其采用如前述实施方式任一项的水性碳纤维的分散体系制备而成。
以下结合实施例对本发明的特征和性能作进一步的详细描述。
实施例1
本实施例提供了一种水性碳纤维,其制备方法包括:将碳纤维于400℃下进行低温氧化预处理0.5h后,再采用上浆剂(聚氧化乙烯、脲醛树脂和聚氧乙烯醚的质量比为15:8:1)进行上浆处理,经短切后得长度为3mm/6mm/9mm的水性碳纤维,其在水中的开纤性评估纤维分散距离分别为25cm/18cm/11cm。
按照上述实施例1的制备方法,通过改变预处理工艺和上浆处理工艺,分别获得实施例2-实施例8的水性碳纤维以及对比例1-对比例3的水性碳纤维,具体工艺参数请参阅表1。
表1.实施例1-8和对比例1-3的处理情况和开纤性统计表
从上表可以看出,经过本申请的预处理和上浆剂处理,可以使得摊位在水中的开纤维性更佳,显著优于对比例1。
分散实验
将上述实施例1-8以及对比例1-3制备获得的碳纤维中切分为长度6mm的短切亲水性碳纤维作为分散体系考察的碳纤维分散于不同的分散液中,具体地:
分散液1仅包括水,碳纤维的分散浓度为0.01%;
分散液2包括聚醚改性硅油0.5g、聚氧化乙烯1g和水10000ml;
分散液3包括聚醚改性硅油0.5g、阴离子聚丙烯酰胺1g和水10000ml;
分散液4包括聚醚改性硅油0.5g、阳离子聚丙烯酰胺1g和水10000ml;
分散液5包括聚醚改性硅油0.5g、阴离子聚丙烯酰胺1g和水10000ml;
分散液6包括聚醚改性硅油0.5g、阴离子聚丙烯酰胺2g和水10000ml;
分散液7包括聚醚改性硅油0.5g、阴离子聚丙烯酰胺5g和水10000ml;
分散液8包括聚醚改性硅油0.5g、阴离子聚丙烯酰胺10g和水10000ml;
分散液9包括聚醚改性硅油0.5g、阳离子聚丙烯酰胺1g和水10000ml;
分散液10包括聚醚改性硅油0.5g、阳离子聚丙烯酰胺2g和水10000ml;
分散液11包括聚醚改性硅油0.5g、阳离子聚丙烯酰胺5g和水10000ml;
分散液12包括聚醚改性硅油0.5g、阳离子聚丙烯酰胺10g和水10000ml;
分散效果评估方法:
首先准备一个1L玻璃烧杯,在容器中加入1L分散剂体系。将碳纤维切成6mm长度的短切碳纤维试样。
根据所要配制的碳纤维分散液浓度,称取一定质量的短切碳纤维作为试样,将短切碳纤维加入分散体系中,在超声作用下,分散5min,观查碳纤维的分散情况。从絮聚严重到无絮聚,将碳纤维的分散分为5个等级,分别用1~5个等级来判定,1级最差,纤维絮聚严重,5级最好,基本无纤维束。分散示意图请参阅图1-图5。
不同实施例和对比例所使用的分散液以及碳纤维用量统计如表2,最终分散体系和分散效果等级请参阅表2。
表2.不同碳纤维在不同分散液中的分散效果
从上表可以看出,本实施例提供的碳纤维的分析效果佳,且可以达到较高的碳纤维分散浓度。
综上所述,本申请提供的水性碳纤维的制备方法,通过对碳纤维进行低温氧化处理、电解处理和液相氧化处理中的至少一种的预处理和特定上浆剂的上浆处理,可以赋予碳纤维电性,增强碳纤维的亲水性,使其在水中具有更好的开纤性,并且能达到在低浓度的情况下完全分散的效果,减少了对分散剂的需求,从而避免了对生产运转的负面影响;此外,本申请提供的水性碳纤维减少了脱胶工序,在改善纤维分散性的同时能够保证碳纸的强度,有利于节约成本;而本申请提供的水性碳纤维的分散体系,可以针对碳纤维的电性特性,采用相应的碳纤维分散液,可达到较高的碳纤维分散浓度,并且可以直接加水稀释的便利效果,提升了在生产过程中操作的便利性,有利于节降生产设备的投资。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种水性碳纤维的制备方法,其特征在于,其包括:将碳纤维进行预处理后,再采用上浆剂进行上浆处理,
其中,所述预处理包括低温氧化处理、电解处理和液相氧化处理中的至少一种;所述上浆剂的组分包括质量比为(10~20):(1~5):(5~20):(60~90)的水性聚合物、粘接剂、乳化剂和水。
2.根据权利要求1所述的水性碳纤维的制备方法,其特征在于,所述低温氧化处理包括将所述碳纤维于300~500℃的空气氛围中灼烧0.1~5h;
优选地,所述电解处理包括选用酸性电解质或中性电解质作为电解液,进行电解处理0.1~5h;
优选地,所述酸性电解质包括硫酸、硝酸或者两者混合液;
优选地,所述中性电解质包括硫酸钠、硝酸钾或者两者混合物;
优选地,所述液相氧化处理包括采用氧化剂处理0.1~5h;其中,所述氧化剂包括高锰酸钾、双氧水和过硫酸盐中的至少一种。
3.根据权利要求1所述的水性碳纤维的制备方法,其特征在于,所述水性聚合物包括聚氧化乙烯、聚乙二醇、聚丙烯酸树脂、阴离子聚丙烯酸钠、阴离子聚丙烯酰胺、阳离子聚丙烯酰胺、两性聚丙烯酰胺、阳离子淀粉、阴离子淀粉和两性淀粉中的至少一种;
优选地,所述粘接剂为热固性的水溶性树脂;
优选地,所述水溶性树脂包括环氧氯丙烷树脂、脲醛树脂和三聚氰胺树脂中的至少一种;
优选地,所述乳化剂包括十二烷基硫酸钠盐、硬脂酸钠盐、N-十二烷基二甲胺和聚氧乙烯醚类中的一种。
4.根据权利要求1所述的水性碳纤维的制备方法,其特征在于,所述碳纤维为PAN基碳纤维,所述碳纤维的丝束范围为3K-50K,优选为12K或24K。
5.一种水性碳纤维,其特征在于,其采用如权利要求1-4任一项所述的水性碳纤维的制备方法制备而成。
6.一种水性碳纤维的分散体系,其特征在于,其采用如权利要求5所述的水性碳纤维短切形成短切亲水性碳纤维,随后于分散液中分散而成。
7.根据权利要求6所述的水性碳纤维的分散体系,其特征在于,所述短切亲水性碳纤维的长度为3~15mm,优选为4~10mm。
8.根据权利要求6所述的水性碳纤维的分散体系,其特征在于,所述碳纤维与所述分散液的质量比为(1~10):(2000~10000)。
9.根据权利要求6所述的水性碳纤维的分散体系,其特征在于,所述分散液包括表面活性剂0.1~1.0g/L和高分子聚合物0.1~10g/L的一种或两者的组合;
优选地,所述表面活性剂包括脂肪醇类表面活性剂、硅醇类表面活性剂或硬脂酸盐类表面活性剂;更优选地,所述表面活性剂为聚醚改性硅油;
优选地,所述高分子聚合物包括聚氧化乙烯、阴离聚丙烯酰胺、阳离子聚丙烯酰胺和聚丙烯酸钠中的一种;
优选地,所述高分子聚合物的分子量为300万~2000万,更优选为600万~1500万。
10.一种燃料电池碳纤维纸,其特征在于,其采用如权利要求5-9任一项所述的水性碳纤维的分散体系制备而成。
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