CN116706102A - 一种用于燃料电池的气体扩散层的制备方法和应用 - Google Patents
一种用于燃料电池的气体扩散层的制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种用于燃料电池的气体扩散层的制备方法和应用，至少包括以下步骤：S1、配制疏水浸渍液，S2、炭纸经过疏水浸渍液处理，并除去炭纸表面多余液体后，炭纸经过0.3~2 m的距离后进入烘箱后，使用气体吹拂炭纸，通过调整气体方向、气体流速、以及疏水浸渍液的粘度来控制疏水浸渍液向下流动的速度，通过调整走带速度、走带距离、气体温度来控制所述疏水浸渍液向下流动的时间；走带速度为0.1~1.5m/s、走带距离为所述烘箱的长度，所述烘箱长度为3~20 m、气流速度为0.3~16 m/s；S3、将浸渍完成并干燥后的炭纸经过烧结，涂布微孔层，之后再经过烧结后，得到所述气体扩散层。制备得到的GDB呈疏水性的阶梯式分布，使GDL具有更优越的水汽传输能力。
Description
技术领域
本发明涉及气体扩散层领域，特别涉及一种用于燃料电池的气体扩散层的制备方法和应用。
背景技术
气体扩散层（Gas diffusion layers），简称GDL，包括微孔层与支撑层（GDB）。支撑层的主要材料为炭纸，其主要作用为传导反应气体、排出多余的水、传导热量、传导电子以及为膜电极提供机械支撑；微孔层的作用类似，也是用于传导水、气、热及电子，并起着保护催化层的作用。因此，气体扩散层需要具有导电性高、孔结构佳、亲疏水性佳、导热性好、机械强度好，微孔层平整度高等特点。
目前，气体扩散层的制备步骤如下：丙烯腈经聚合后得到聚丙烯腈，再经过纺丝、烧结后得到碳纤维，再短切成10-15 mm长、直径为5-10 μm的短切碳纤维，将碳纤维经过表面处理后，抄纸得到原纸。将原纸经过填孔、烧结后得到炭纸；将炭纸浸渍PTFE并经过350-400℃烧结30-60 min后，再涂布微孔层、再经过350-400℃烧结30-60 min后得到气体扩散层。
质子交换膜燃料电池中GDL是水汽传输的重要途经，目前，虽然在GDL的微孔层中实现了阶梯化孔结构、阶梯化亲疏水结构，但是GDL中的微孔层只有10~50 μm，而GDB的厚度为100~400 μm，因此，更应该提高GDB侧的疏水性的阶梯式分布，使GDL具有更优越的水汽传输能力。
发明内容
针对现有技术的不足，本发明提供了一种用于燃料电池的气体扩散层的制备方法和应用，该制备方法可以制备出具有疏水性的阶梯式分布的GDB，从而提高GDL的水汽传输能力。
为解决上述技术问题，本发明的目的之一是提供一种用于燃料电池的气体扩散层的制备方法，至少包括以下步骤：
S1、配制疏水浸渍液，所述疏水浸渍液的原料包括0.5-10wt%疏水剂、0.5-10wt%增稠剂、以及溶剂；
S2、未经处理的炭纸经过所述疏水浸渍液浸渍处理，并除去炭纸表面多余液体后，所述炭纸经过0.3~2 m的距离后进入烘箱后，使用气体吹拂所述炭纸，通过调整气体方向、气体流速、以及所述疏水浸渍液的粘度来控制所述疏水浸渍液向下流动的速度，通过调整走带速度、走带距离、气体温度来控制所述疏水浸渍液向下流动的时间；其中，走带速度为0.1~1.5m/s、走带距离为所述烘箱的长度，所述烘箱长度为3~20 m、气流速度为0.3~16 m/s、所述疏水浸渍液的粘度为10~2000 mPa·s；
S3、将步骤2浸渍完成并干燥后的炭纸经过350~400℃烧结30 min~60min后，涂布微孔层，之后再经过350~400℃烧结30 min~60min后，得到所述气体扩散层。
进一步地，所述烘箱的温度沿着所述炭纸的走带方向由室温升高至360℃，高温保持一段时间后，再降低至室温。
进一步地，所述气体吹拂所述炭纸的范围为，烘箱前0.3~3 m的距离。
通过上述技术方案，炭纸经过疏水浸渍液浸渍处理后，需要经过一段距离进入烘箱，以及在烘箱前段距离中用气体吹炭纸（可于上方/下方吹），此时疏水浸渍液并没有完全干燥，在这段过程中疏水浸渍液不仅仅不会干燥，而且在重力、气体、流动阻力的作用下可以向下流动。本发明主要是通过调整疏水浸渍液的粘度、气体方向及流速来控制疏水浸渍液向下流动的速度，通过调整走带速度、走带距离、气体温度调整向下流动的时间，进而调整炭纸在y方向上的亲疏水性差异，继而实现GDB的疏水性阶梯化分布，并且本专利提供的方法可以实现连续化阶梯化，即PTFE含量梯度变化曲线更平滑。
如图5所示，图中，x是走带方向，y是炭纸厚度方向。在y方向上疏水浸渍液受到向下的重力G、气体推力FQ（图5中吹拂的气体为N2）、以及阻力Fμ，通过控制气体的流量、以及疏水浸渍液的粘度，因此在三种力的合力作用下，进而可以控制疏水浸渍液的流动方向和流动速度；同时通过调控走带速度、前端烘箱温度，疏水浸渍液在气体吹拂作用下会加速其干燥，从而达到控制干燥速度和时间的目的。
进一步地，所述气体垂直吹向所述炭纸的面。
进一步地，所述疏水剂为聚四氟乙烯溶液、偏聚四氟乙烯溶液、聚偏二氟乙烯溶液中的任意一种。
进一步地，所述增稠剂为羧甲基纤维素、丙二醇藻蛋白酸酯、甲基纤维素、淀粉磷酸钠、羧甲基纤维素钠、藻蛋白酸钠、酪蛋白、聚丙烯酸钠、聚氧乙烯、聚乙烯吡咯烷酮中的任意一种。
进一步地，所述溶剂为水、乙醇、N-甲基吡咯烷酮中的至少一种。
进一步地，所述气体为惰性气体。
本发明的目的之二是，本发明制备得到的一种气体扩散层在燃料电池中的应用。
发明的有益效果
本发明提供的制备方法简便、可操作性强，实现了GDB侧疏水剂含量阶梯化分布，制备出的GDL具备更优异的水汽传输能力。通过调控气体的方向、流速以及疏水浸渍液的粘度，可以实现GDB疏水性阶梯化分布。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，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示出的结构获得其他的附图。
图1为实施例1的电池性能曲线图。
图2为实施例2的电池性能曲线图。
图3为对比例1的电池性能曲线图。
图4为实施例1、实施例2和对比例1的接触角数据图。
图5为本申请中炭纸中浸渍液的受力分析图。
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
下述实施例中的实验方法，如无特殊说明，均为常规方法。下述实施例中所用的试验材料和试剂等，如无特殊说明，均可从商业途径获得。以下实施例中的定量试验，均设置三次重复实验，数据为三次重复实验的平均值或平均值±标准差。
另外，全文中的“和/或”包括三个方案，以A和/或B为例，包括A技术方案、B技术方案，以及A和B同时满足的技术方案；另外，各个实施例之间的技术方案可以相互结合，但是必须是以本领域普通技术人员能够实现为基础，当技术方案的结合出现相互矛盾或无法实现应当认为这种技术方案的结合不存在，也不在本发明要求的保护范围之内。
实施例1：
配制疏水浸渍液：分别取60%PTFE乳液166.7 g（2wt%）、羧甲基纤维素100 g（2wt%）、纯水4.9 kg，三者混合后，使用高速分散机对混合液进行分散，得到分散后的疏水浸渍液，并测其粘度为1000 mPa·s。其中，高速分散机的分散线速度为20m/s，分散时间为1h。
将疏水浸渍液置于浸渍托盘中对炭纸进行浸渍，炭纸浸渍后，经过1m的距离后进入烘箱，烘箱前1 m不工作，之后3.5 m梯度升温由室温升至360℃，之后的5 m保持360℃，之后3.5 m再由360℃将至室温。走带速度为0.5 m/min；在烘箱中前2 m不断由上至下吹氮气，风速为2 m/s使得疏水浸渍液可以更好地向下运动实现阶梯化分布；在此之后疏水浸渍液已经完全干燥，在烘箱中PTFE熔融形成疏水网络。分别测试处理好的炭纸2侧的接触角，测试结果如图4所示。
将浸渍完成的炭纸经过350℃烧结50min后，涂布微孔层，之后再经过400℃烧结30min后，得到所述气体扩散层。制备成气体扩散层并组装成燃料电池，测试结果如图1所示。
实施例2：
配制疏水浸渍液：分别取60%PTFE乳液166.7 g（2wt%）、羧甲基纤维素10 g（0.2wt%）、纯水4.9 kg，三者混合后，使用高速分散机对混合液进行分散，得到分散后的疏水浸渍液，并测其粘度为30 mPa·s。其中，高速分散机的分散线速度为20m/s，分散时间为1h。
将疏水浸渍液置于浸渍托盘中对炭纸进行浸渍，炭纸浸渍后，经过1m的距离后进入烘箱，烘箱前1m梯度升温由室温升至360℃，之后的5 m保持360℃，之后3.5 m再由360℃将至室温，最后3.5 m不工作。走带速度为0.5 m/min；在烘箱中前3 m不断由下至上吹氮气，风速为2 m/s使得疏水浸渍液可以更好地向下运动实现阶梯化分布；在此之后疏水浸渍液已经完全干燥，在烘箱中PTFE熔融形成疏水网络。分别测试处理好的炭纸2侧的接触角，测试结果如图4所示。
将浸渍完成的炭纸经过350℃烧结50min后，涂布微孔层，之后再经过400℃烧结30min后，得到所述气体扩散层。制备成气体扩散层并组装成燃料电池，测试结果如图2所示。
对比例1
配制疏水浸渍液：分别取60%PTFE乳液166.7 g（2wt%）、纯水4.8 kg，二者混合后，使用高速分散机对其进行分散，得到分散后的疏水浸渍液，并测其粘度为8mPa·s。其中，高速分散机的分散线速度为20m/s，分散时间为1h。
将疏水浸渍液置于浸渍托盘中对炭纸进行浸渍，炭纸浸渍后，烘箱前3.5 m梯度升温由室温升至360℃，之后的5 m保持360℃，之后3.5 m再由360℃到室温，烘箱最后1 m不工作。走带速度为0.5 m/min；在烘箱中前3.5m不吹氮气；在此之后疏水浸渍液已经完全干燥，在烘箱中PTFE熔融形成疏水网络。分别测试处理好的炭纸2侧接触角，测试结果如图4所示。
将浸渍完成的炭纸经过350℃烧结50min后，涂布微孔层，之后再经过400℃烧结30min后，得到所述气体扩散层。制备成气体扩散层并组装成燃料电池，测试结果如图3所示。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (9)
1.一种用于燃料电池的气体扩散层的制备方法，其特征在于，至少包括以下步骤：
S1、配制疏水浸渍液，所述疏水浸渍液的原料包括0.5-10wt%疏水剂、0.5-10wt%增稠剂、以及溶剂；
S2、未经处理的炭纸经过所述疏水浸渍液浸渍处理，并除去炭纸表面多余液体后，所述炭纸经过0.3~2 m的距离后进入烘箱后，使用气体吹拂所述炭纸，通过调整气体方向、气体流速、以及所述疏水浸渍液的粘度来控制所述疏水浸渍液向下流动的速度，通过调整走带速度、走带距离、气体温度来控制所述疏水浸渍液向下流动的时间；其中，走带速度为0.1~1.5m/s、走带距离为所述烘箱的长度，所述烘箱长度为3~20 m、气流速度为0.3~16 m/s、所述疏水浸渍液的粘度为10~2000 mPa·s；
S3、将步骤2浸渍完成并干燥后的炭纸经过350~400℃烧结30 min~60min后，涂布微孔层，之后再经过350~400℃烧结30 min~60min后，得到所述气体扩散层。
2.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述烘箱的温度沿着所述炭纸的走带方向由室温升高至360℃，高温保持一段时间后，再降低至室温。
3.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述气体吹拂所述炭纸的范围为，烘箱前0.3~3 m的距离。
4.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述气体垂直吹向所述炭纸的面。
5.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述疏水剂为聚四氟乙烯溶液、偏聚四氟乙烯溶液、聚偏二氟乙烯溶液中的任意一种。
6.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述增稠剂为羧甲基纤维素、丙二醇藻蛋白酸酯、甲基纤维素、淀粉磷酸钠、羧甲基纤维素钠、藻蛋白酸钠、酪蛋白、聚丙烯酸钠、聚氧乙烯、聚乙烯吡咯烷酮中的任意一种。
7.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述溶剂为水、乙醇、N-甲基吡咯烷酮中的至少一种。
8.根据权利要求1所述的一种用于燃料电池的气体扩散层的制备方法，其特征在于，所述气体为惰性气体。
9.一种如权利要求1所述的气体扩散层的制备方法所制备的所述气体扩散层在燃料电池中的应用。
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| CN101399347A (zh) * | 2007-09-27 | 2009-04-01 | 中国科学院大连化学物理研究所 | 用于质子交换膜燃料电池的气体扩散层及制法和应用 |
| JP2010086663A (ja) * | 2008-09-29 | 2010-04-15 | Toshiba Corp | 燃料電池 |
| JP2016136481A (ja) * | 2015-01-23 | 2016-07-28 | トヨタ自動車株式会社 | 燃料電池セル |
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| CN115377439A (zh) * | 2022-09-22 | 2022-11-22 | 深圳市通用氢能科技有限公司 | 一种增强水管理能力的气体扩散层的制备方法以及该气体扩散层在燃料电池中的应用 |
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| CN101399347A (zh) * | 2007-09-27 | 2009-04-01 | 中国科学院大连化学物理研究所 | 用于质子交换膜燃料电池的气体扩散层及制法和应用 |
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