CN111549573A - 一种质子交换膜氢燃料电池用炭纸及制备方法 - Google Patents

一种质子交换膜氢燃料电池用炭纸及制备方法 Download PDF

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CN111549573A
CN111549573A CN202010388692.7A CN202010388692A CN111549573A CN 111549573 A CN111549573 A CN 111549573A CN 202010388692 A CN202010388692 A CN 202010388692A CN 111549573 A CN111549573 A CN 111549573A
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carbon
fuel cell
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exchange membrane
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吴刚平
刘玉婷
朱宏
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

本发明属于导电性材料制备方法技术领域，具体涉及一种质子交换膜氢燃料电池用炭纸及制备方法。所述质子交换膜氢燃料电池用炭纸，可解决炭纸中碳纤维难以均匀分布的问题，提高炭纸的导电性。其制备步骤为：将分散剂1、炭化纤维的混合物放入水中，打浆使得炭化纤维丝分散均匀，形成悬浮液；向悬浮液中加入分散剂2，继续搅拌使炭化纤维分散均匀，形成均一的悬浮液；采用湿法抄纸方法将悬浮液进行抄纸；将湿法抄纸抄成的纸用粘结剂进行浸渍；将浸渍粘结剂的纸进行固化；将得到的纸炭化处理，得到质子交换膜氢燃料电池用炭纸。

Description

一种质子交换膜氢燃料电池用炭纸及制备方法
技术领域
本发明属于导电性材料制备方法技术领域，具体涉及一种质子交换膜氢燃料电池用炭纸及制备方法。
背景技术
质子交换膜氢燃料电池的气体扩散层需同时具有集电、气体传输、气流分配等功能。由此，构成气体扩散层的碳纤维纸层材料中，要求同时具有高导电性、高气体扩散性、高气体分配性等性能。
作为质子交换膜燃料电池的气体扩散层用炭纸，日本公开特许专利第6-20710号公报记载，将短切碳纤维随机分散形成碳纤维纸，并进而由炭素材料结合起来，形成具有多孔质结构的碳纤维纸材料。然而，由于通常的碳纤维在制备过程中经过1300℃以上高温炭化，导致碳纤维表面呈现类石墨结构，一般碳纤维的碳含量≥92wt％，氮含量≤5wt％；由于该碳纤维的表面能低，使其难以在水中均匀分散，进而难以制备得到碳纤维均匀分布的炭纸，难以显著提高炭纸的导电性。
发明内容
针对上述问题本发明提供了一种质子交换膜氢燃料电池用炭纸及制备方法，可解决纤维难以均匀分散的问题，提高炭纸的导电性。
为了达到上述目的，本发明采用了下列技术方案：
一种质子交换膜氢燃料电池用炭纸，由炭化纤维经分散、抄纸、并用粘结剂粘结、固化、炭化制成，且其中炭化纤维的碳含量为60～90wt％，氮含量为7～20wt％。这种炭化纤维的表面具有较丰富亲水官能团，使得炭化纤维在水中较容易均匀分散，可通过通常的抄纸方法得到炭化纤维原纸；由于纤维分布均匀，将该炭化纤维原纸通过粘结剂粘结、炭化后可得到导电性良好的炭纸。另一方面，采用炭化纤维作为抄纸原料，由于炭化纤维在制备过程中炭化温度较低(通常≤1000℃)，因而炭纸的制备成本可大幅度降低。
一种质子交换膜氢燃料电池用炭纸的制备方法，包括以下步骤：
步骤1，将分散剂1、炭化纤维的混合物放入水中，打浆使得炭化纤维丝分散形成悬浮液；
步骤2，向悬浮液中加入分散剂2，继续搅拌使炭化纤维分散均匀，形成均一的悬浮液；
步骤3，采用湿法抄纸方法将悬浮液进行抄纸，得到炭化纤维原纸；
步骤4，将炭化纤维原纸用粘结剂进行浸渍并干燥；
步骤5，将浸渍粘结剂并干燥后的炭化纤维原纸进行固化；
步骤6，将固化后的炭纤维原纸在氮气气氛保护下进行炭化处理，得到质子交换膜氢燃料电池用炭纸。
步骤1中所述炭化纤维的碳含量为60～90wt％，氮含量为7～20wt％，该炭化纤维在水中的分散性较好，有利于得到纤维分布均匀的原纸；如果炭化纤维中碳含量低于60wt％，由于在步骤5中的炭化过程中产生较大热收缩，导致炭纸的质量变差；如果碳含量高于90wt％，将导致炭化纤维在水中的分散性变差，难以得到导电性良好的碳纸。如果炭化纤维中氮含量低于7wt％，碳纤维的水分散性变差，如果氮含量高于20wt％，则在炭化过程中热变形过大，导致炭纸质量变差。
进一步，所述步骤1中炭化纤维的长度为1～30mm。如果炭化纤维的长度小于1mm，将导致炭纸的机械性能变差，如果炭化纤维的长度高于30mm，将导致炭化纤维在水中的分散性变差，难以抄造成纸。
进一步，所述步骤1中分散剂1为离子型分散剂，包括十二烷基苯磺酸钠、酰基羟乙基磺酸钠、聚丙烯酸钠、N-烷基三甲基氯化铵、N-烷基氨基酸、N-烷基甜菜碱、咪唑啉羧酸盐中的一种或两种以上任意比例的混合物；
进一步，所述步骤1中分散剂1的用量为水用量的0.002～0.5wt％，炭化纤维的用量为水用量的0.01～0.5wt％，如果分散剂1的用量低于水用量的0.002wt％，将导致吸附不充分，分散能力不足，炭化纤维在水中难以有效分散；如果分散剂1的用量超过水用量的0.5wt％，将造成分散剂的浪费。如果炭化纤维的用量低于水用量的0.01wt％，将导致制备成本提高，如果炭化纤维的用量高于0.5wt％，将导致炭化纤维分散困难，得到的炭纸质量变差。
进一步，所述步骤2中分散剂2为非离子型分散剂，包括多聚磷酸酯、聚氧乙烯胺、聚乙烯亚胺、聚氧乙烯烷基酚、聚氧乙烯酯、聚乙烯醇、聚乙二醇、丙三醇、聚氧乙烯、聚丙烯酰胺、脂肪族聚氧乙烯醚、羧甲基纤维素中的一种或两种以上任意比例的混合物。
进一步，所述步骤2中分散剂2的用量为水用量的0.01～1wt％，如果分散剂2的用量低于水用量的0.01wt％，将分散能力不足，炭化纤维在水中难以有效分散；如果分散剂2的用量超过水用量的1wt％，将造成分散剂的浪费。
进一步，所述步骤4中粘结剂为酚醛树脂、水解度为10～90％的聚丙烯腈树脂、壳聚糖树脂、呋喃树脂、三聚氰胺、沥青、苯并噁嗪树脂中的一种或两种以上任意比例混合物的溶液，所述溶液的溶剂为水、甲醇或乙醇，粘结剂浓度为1～100g/L。如果粘结剂在水、甲醇或乙醇中的浓度低于1g/L，将导致炭化纤维之间未有效粘结，导致炭纸的导电性下降；如果粘结剂在水、甲醇或乙醇中浓度高于100g/L，过量的粘结剂将可能堵塞纸中的孔隙，导致炭纸的透气性能下降。
进一步，所述粘结剂还包括炭素材料，用量为粘结剂中溶质总量的5～80wt％；所述炭素材料为碳纳米管、石墨、石墨烯、炭黑、富勒烯中的任意一种或几种任意比例的混合物。如果粘结剂中炭素材料的比率低于5wt％，将导致炭纸的导电性下降，如果粘结剂中炭素材料的比率高于80wt％，将导致粘结剂不能有效粘结炭化纤维，同样导致炭纸的导电性下降。
再进一步，所述步骤4中干燥的温度为80～300℃，时间为2～30min。如果干燥的温度低于80℃，将导致难以充分干燥；如果干燥温度高于300℃，将导致粘结剂发生部分热解，影响炭纸的质量。如果干燥时间少于2min，将导致干燥时间不够，溶剂难以完全挥发；如果干燥时间高于30min，将导致制备时间增加，增加了制备成本。
再进一步，所述步骤5中固化温度为160～300℃，时间为30秒～20分钟，固化时施加在炭化纤维原纸纸面的压力为0.2～5MPa。如果固化温度低于160℃，将导致粘结剂固化不充分，导致炭化过程中热分解过多，导致炭纸质量变差；如果固化温度高于300℃，将导致能源浪费，成本增加。如果固化时间少于30秒，将导致粘结剂固化不充分，如果固化时间高于20分钟，将导致炭纸的制备成本增加。如果施加在纸面的压力小于0.2MPa，将导致炭纸的粗糙度增加，如果压力大于5MPa，将导致成本增加。
更进一步，所述步骤6中炭化处理的温度为1400～2200℃，时间为5秒～20分钟。如果炭化温度低于1400℃，将导致粘结剂不能有效被炭化，导致炭纸的导电性难以提高；如果炭化温度高于2200℃，将导致制备成本提高；如果炭化时间少于5秒钟，将导致粘结剂不能有效炭化，导致炭纸的导电性不高，如果炭化时间多于20分钟，将导致炭纸的制备成本提高。
与现有技术相比本发明具有以下优点：
传统的炭纸制备过程中采用碳含量超过92wt％、氮含量低于5wt％的碳纤维作为原材料，通过在水中分散，形成碳纤维原纸，进而与酚醛树脂等粘结剂浸胶、炭化，制成炭纸。但这种方法中，由于碳纤维表面亲水官能团少，难以在水中均匀分散，因而难以形成均匀分布的纸结构，进而在炭化后，炭纸的导电性不高。
在新的方法中，由于采用碳含量为70～90wt％，氮含量为7～20wt％的炭化纤维作为原料，炭化纤维表面含有较丰富的含氧、含氮官能团，与水的亲和性较好，因而在水中分散性较好，较易形成均匀的纸结构，通过浸胶、固化、炭化制成炭纸后，由于炭纸中均匀分布的炭化纤维转化为碳纤维，因而导电性显著提高。该方法避免了直接使用成品碳纤维带来的分散难的问题。
具体实施方式
实施例1
一种质子交换膜氢燃料电池用炭纸的制备方法，包括以下步骤：
在1000mL去离子水中，加入0.02g十二烷基硫酸钠、0.1g含碳量为60wt％、含氮量20wt％的长度为6mm的炭化纤维，通过3000rpm打浆5分钟使得炭化纤维分散形成悬浮液，然后向悬浮液中加入1g聚氧乙烯胺，以800rpm搅拌10分钟使炭化纤维分散均匀，形成稳定悬浮液；采用湿法抄纸方法将悬浮液进行抄纸制造，得到炭化纤维原纸。
在500mL甲醇中加入20g酚醛树脂粉末和1.0g碳纳米管，搅拌均匀，配置成酚醛树脂粘结剂溶液。将炭化纤维原纸在上述酚醛树脂粘结剂溶液中浸渍5分钟后取出，在120℃下烘干10分钟；之后在热压机上进行固化处理，温度160℃，压力0.2MPa，时间10min。将固化后的纤维原纸在氮气气氛保护下进行炭化，炭化温度为1400℃，时间为20min，得到质子交换膜氢燃料电池用炭纸。所得炭纸的性能如表1所示。由表可见，所得炭纸较好的气体透过性、较高的导电性和较小的表面粗糙度，可以满足作为氢燃料电池气体扩散层使用的要求。
实施例2
在1000mL去离子水中，加入5g聚丙烯酸钠、5g含碳量为85wt％、含氮量9wt％的长度为1mm的炭化纤维，通过3000rpm打浆5分钟使得炭化纤维分散形成悬浮液，然后向悬浮液中加入10g聚乙二醇，以800rpm搅拌10分钟使炭化纤维分散均匀，形成稳定悬浮液；采用湿法抄纸方法将悬浮液进行抄纸制造，得到炭化纤维原纸。
在500mL乙醇中加入25g壳聚糖粉末和3g石墨烯，搅拌均匀，配置成粘结剂溶液。将炭化纤维原纸在上述粘结剂溶液中浸渍5分钟后取出，在80℃下烘干30分钟；之后在热压机上进行固化处理，温度180℃，压力0.5MPa，时间20min。将固化后的纤维原纸在氮气气氛保护下进行炭化，炭化温度为2200℃，时间为5秒钟，得到质子交换膜氢燃料电池用炭纸。所得炭纸的性能如表1所示。由表可见，所得炭纸较好的气体透过性、较高的导电性和较小的表面粗糙度，可以满足作为氢燃料电池气体扩散层使用的要求。
实施例3
在1000mL去离子水中，加入2.5g十二烷基苯磺酸钠、3g含碳量为90wt％、含氮量7wt％的长度为20mm的炭化纤维，通过3000rpm打浆5分钟使得炭化纤维分散形成悬浮液，然后向悬浮液中加入5g羧甲基纤维素，以800rpm搅拌10分钟使炭化纤维分散均匀，形成稳定悬浮液；采用湿法抄纸方法将悬浮液进行抄纸制造，得到炭化纤维原纸。
在500mL甲醇中加入50g呋喃树脂粉末和10g石墨，搅拌均匀，配置成粘结剂溶液。将炭化纤维原纸在上述粘结剂溶液中浸渍5分钟后取出，并在300℃下烘干2分钟；之后在热压机上进行固化处理，温度250℃，压力1.0MPa，时间10min。将固化后的纤维原纸在氮气气氛保护下进行炭化，炭化温度为2000℃，时间为10秒钟，得到质子交换膜氢燃料电池用炭纸。所得炭纸的性能如表1所示。由表可见，所得炭纸较好的气体透过性、较高的导电性和较小的表面粗糙度，可以满足作为氢燃料电池气体扩散层使用的要求。
实施例4
在1000mL去离子水中，加入0.2g酰基羟乙基磺酸钠、2g含碳量为80wt％、含氮量14wt％的长度为30mm的炭化纤维，通过3000rpm打浆5分钟使得炭化纤维分散形成悬浮液，然后向悬浮液中加入0.1g聚丙烯酰胺，以800rpm搅拌10分钟使炭化纤维分散均匀，形成稳定悬浮液；采用湿法抄纸方法将悬浮液进行抄纸制造，得到炭化纤维原纸。
在500mL去离子水中加入0.5g水解度为10％的聚丙烯腈树脂和0.4g炭黑，搅拌均匀，配置成粘结剂溶液。将炭化纤维原纸在粘结剂溶液中浸渍5分钟后取出，并在300℃下烘干2分钟，将炭化纤维原纸在上述粘结剂树脂溶液中浸渍5分钟后取出，并在100℃下烘干10分钟，之后在热压机上进行固化处理，温度300℃，压力5.0MPa，时间30秒。将固化后的纤维原纸在氮气气氛保护下进行炭化，炭化温度为2200℃，时间为5秒钟，得到质子交换膜氢燃料电池用炭纸。所得炭纸的性能如表1所示。由表可见，所得炭纸较好的气体透过性、较高的导电性和较小的表面粗糙度，可以满足作为氢燃料电池气体扩散层使用的要求。
实施例5
在1000mL去离子水中，加入3g N-烷基甜菜碱、3g含碳量为80wt％、含氮量14wt％的长度为15mm的炭化纤维，通过3000rpm打浆5分钟使得炭化纤维分散形成悬浮液，然后向悬浮液中加入2g聚氧乙烯，以800rpm搅拌10分钟使炭化纤维分散均匀，形成稳定悬浮液；采用湿法抄纸方法将悬浮液进行抄纸制造，得到炭化纤维原纸。
在500mL去离子水中加入10.0g水解度为90％的聚丙烯腈树脂和6.0g富勒烯C-60，搅拌均匀，配置成粘结剂溶液。将炭化纤维原纸在粘结剂溶液中浸渍5分钟后取出，并在300℃下烘干2分钟；之后在热压机上进行固化处理，温度220℃，压力3.0MPa，时间5min。将固化后的纤维原纸在氮气气氛保护下进行炭化，炭化温度为2000℃，时间为10秒钟，得到质子交换膜氢燃料电池用炭纸。所得炭纸的性能如表1所示。由表可见，所得炭纸较好的气体透过性、较高的导电性和较小的表面粗糙度，可以满足作为氢燃料电池气体扩散层使用的要求。
实施例6
在1000mL去离子水中，加入4g N-烷基氨基酸、3g含碳量为80wt％、含氮量14wt％的长度为15mm的炭化纤维，通过3000rpm打浆5分钟使得炭化纤维分散形成悬浮液，然后向悬浮液中加入8g丙三醇，以800rpm搅拌10分钟使炭化纤维分散均匀，形成稳定悬浮液；采用湿法抄纸方法将悬浮液进行抄纸制造，得到炭化纤维原纸。
在500mL去离子水中加入5.0g水解度为60％的聚丙烯腈树脂和4.0g碳纳米管，搅拌均匀，配置成粘结剂溶液。将炭化纤维原纸在粘结剂溶液中浸渍5分钟后取出，并在120℃下烘干10分钟；之后在热压机上进行固化处理，温度280℃，压力3.0MPa，时间10min。将固化后的纤维原纸在氮气气氛保护下进行炭化，炭化温度为2000℃，时间为10秒钟，得到质子交换膜氢燃料电池用炭纸。所得炭纸的性能如表1所示。由表可见，所得炭纸较好的气体透过性、较高的导电性和较小的表面粗糙度，可以满足作为氢燃料电池气体扩散层使用的要求。
其中，表1中孔隙率、厚度方向透气率、电阻率及表面粗糙度均按照中华人民共和国国家标准GB/T 20042.7-2014测试得到。
表1炭纸的性能数据
Figure BDA0002484818510000091

Claims (10)

1.一种质子交换膜氢燃料电池用炭纸，其特征在于，所述质子交换膜氢燃料电池用炭纸由炭化纤维经分散、抄纸、并用粘结剂粘结、固化、炭化制成，且其中炭化纤维的碳含量为60～90wt％，氮含量为7～20wt％。
2.一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，包括以下步骤：
步骤1，将分散剂1、炭化纤维的混合物放入水中，打浆使得炭化纤维丝分散形成悬浮液；
步骤2，向悬浮液中加入分散剂2，继续搅拌使炭化纤维分散均匀，形成均一的悬浮液；
步骤3，采用湿法抄纸方法将悬浮液进行抄纸，得到炭化纤维原纸；
步骤4，将炭化纤维原纸用粘结剂进行浸渍并干燥；
步骤5，将浸渍粘结剂并干燥后的炭化纤维原纸进行固化；
步骤6，将固化后的炭纤维原纸在氮气气氛保护下进行炭化处理，得到质子交换膜氢燃料电池用炭纸。
3.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述步骤1中炭化纤维的长度为1～30mm。
4.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述步骤1中分散剂1为离子型分散剂，包括十二烷基苯磺酸钠、酰基羟乙基磺酸钠、聚丙烯酸钠、N-烷基三甲基氯化铵、N-烷基氨基酸、N-烷基甜菜碱、咪唑啉羧酸盐中的一种或两种以上任意比例的混合物；
所述步骤1中炭化纤维的用量为水用量的0.01～0.5wt％，分散剂1的用量为水用量的0.002～0.5wt％。
5.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于：所述步骤2中分散剂2为非离子型分散剂，包括多聚磷酸酯、聚氧乙烯胺、聚乙烯亚胺、聚氧乙烯烷基酚、聚氧乙烯酯、聚乙烯醇、聚乙二醇、丙三醇、聚氧乙烯、聚丙烯酰胺、脂肪族聚氧乙烯醚、羧甲基纤维素中的一种或两种以上任意比例的混合物。
分散剂2的用量为步骤1水用量的0.01～1wt％。
6.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述步骤4中粘结剂为酚醛树脂、水解度为10～90％的聚丙烯腈树脂、壳聚糖树脂、呋喃树脂、三聚氰胺、沥青、苯并噁嗪树脂中的一种或两种以上任意比例混合物的溶液，所述溶液的溶剂为水、甲醇或乙醇，粘结剂浓度为1～100g/L。
7.根据权利要求6所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述粘结剂还包括炭素材料，用量为粘结剂中溶质总量的5～80wt％；所述炭素材料为碳纳米管、石墨、石墨烯、炭黑、富勒烯中的任意一种或几种任意比例的混合物。
8.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述步骤4中干燥的温度为80～300℃，时间为2～30min。
9.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述步骤5中固化温度为160～300℃，时间为30秒～20分钟，固化时施加在炭化纤维原纸纸面的压力为0.2～5.0MPa。
10.根据权利要求2所述的一种质子交换膜氢燃料电池用炭纸的制备方法，其特征在于，所述步骤6中炭化处理的温度为1400～2200℃，时间为5秒～20分钟。
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