CN116093345A - 一种基于静电纺丝的纳米纤维催化层膜和燃料电池膜电极及其制备方法 - Google Patents
一种基于静电纺丝的纳米纤维催化层膜和燃料电池膜电极及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种基于静电纺丝的纳米纤维催化层膜和燃料电池膜电极及其制备方法；催化层膜由催化剂纺丝浆料静电纺丝制得；所述催化剂纺丝浆料中包括树脂、催化剂、高分子载体和溶剂；所述高分子载体选自聚丙烯酸、聚氧化乙烯、聚四氟乙烯、聚偏氯乙烯、聚乙烯醇、聚醋酸乙烯、聚丙烯腈和聚甲基丙烯酸酯中的一种或多种。该催化层膜采用高分子载体作为原料之一，再结合静电纺丝编制而成，具有一定强度能单独成膜；利于其中间处理，以及与质子交换膜灵活匹配；与质子交换膜复合后的膜电极具有较高的极化性能。
Description
技术领域
本发明属于膜电极技术领域，尤其涉及一种基于静电纺丝的纳米纤维催化层膜和燃料电池膜电极及其制备方法。
背景技术
当今全世界由于气候的加速变化、能源资源的不断约束导致的能源结构深度调整的大环境下，氢能已经是公认的战略方向之一，备受关注。由于燃料电池不需要经过热机的卡诺循环而具有更高的效率，同时使用过程中不存在排放物而绿色环保，因此燃料电池是氢能重要应用方向之一。燃料电池正处在商业化应用的初期上升阶段，面临寿命不足、成本高等问题。而其核心部件-膜电极的制备工艺较为复杂，性能、生产效率、良品率等对燃料电池成本和寿命都至关重要。
目前膜电极连续生产工艺是基于喷涂、刮涂和丝网印刷等工艺直接将催化层制备到质子交换膜上形成膜电极，或将催化层制备到其他基底材料表面，然后通过热转印等工艺将催化层转印到质子交换膜上制备膜电极。
专利《一种生产膜电极的工艺方法》中，通过热转印工艺方法、热复合工艺方法、碳纸贴合工艺方法及热压工艺方法，该方法虽然可实现连续自动化生产，但是转印过程对于质子交换膜损伤较大，不利于膜电极耐久性。专利《一种燃料电池用膜-膜电极的集成化制备方法》提出的是从树脂溶液开始制备质子交换膜和膜电极，该方法具备工艺简单和易于实现规模化生产，但是在制备质子交换膜之后，不经过产品良率验证，直接进行膜电极制备，可能存在产品良率低的问题。
发明内容
有鉴于此，本发明的目的在于提供一种基于静电纺丝的纳米纤维催化层膜和燃料电池膜电极及其制备方法，该催化层膜能单独成卷；其具备通孔结构、沿纤维短传输路径等优势可实现高传质，制备的膜电极具备高性能。
本发明提供了一种基于静电纺丝的纳米纤维催化层膜，由催化剂纺丝浆料静电纺丝制得；
所述催化剂纺丝浆料中包括树脂、催化剂、高分子载体和溶剂；
所述高分子载体选自聚丙烯酸、聚氧化乙烯、聚四氟乙烯、聚偏氯乙烯、聚乙烯醇、聚醋酸乙烯、聚丙烯腈和聚甲基丙烯酸酯中的一种或多种。
现有技术中催化层直接做在质子交换膜上，或做在类似PTFE等材料上。由于质子交换膜或PTFE等材料连带着催化层，催化层进一步的高温处理的温度受限。本发明由于催化层可以独立成膜，因此不受后处理温度等条件限制。本发明提供的基于静电纺丝的纳米纤维催化层膜能够单独剥离成膜(见图1)；证明催化层膜与基底材料剥离可行性。
在本发明中，所述树脂选自长支链型全氟磺酸树脂、短支链型全氟磺酸树脂、磺化聚苯乙烯、磺化聚芳醚砜、磺化聚醚醚酮、聚偏氟乙烯、聚四氟乙烯和四氟乙烯-共聚-六氟乙烯中的一种或多种；
所述溶剂选自水、异丙醇、正丙醇、乙醇、甲醇、N,N-二甲基甲酰胺、二甲基亚砜和氯仿中的一种或多种；
所述催化剂选自铂碳催化剂、铂基合金催化剂和非贵金属催化剂中的一种或多种。
在本发明中，所述树脂、催化剂、高分子载体和溶剂的质量比为(0.1～5)：(0.1～5)：(0.01～2)：(1～60)。
在本发明中，所述催化剂纺丝浆料由树脂、催化剂、高分子载体和溶剂混合制得；
所述混合的方式选自超声、珠磨、搅拌和均质中的一种或多种。
在本发明中，所述催化剂纺丝浆料静电纺丝时的电压为0.1～100kv，喷头与接收基底的距离为1～20cm，温度为15～80℃，湿度为10％RH～80RH％；
针头选自针式喷头、无针式喷头或多微孔喷头。
在本发明中，所述接收基底选自离型纸、硅油纸或铝箔。
在本发明中，所述阴极纳米纤维催化层膜的载量为0.05～1mgPt/cm2；
所述阳极纳米纤维催化层膜的载量为0.05～1mgPt/cm2。
本发明纳米纤维催化层膜是通过静电纺丝在基底材料上制得；如图2所示，将基底材料放置料轴A上，通过辊压轴a进行牵引，基底材料按照设定速度前进，该速度主要根据催化层载量设定；纺丝设备在料轴B出进行纺丝，在辊压轴c处进行催化层膜和基底材料剥离，基底材料通过轴d收卷至料轴C；催化层膜经过轴e，再经过后处理工序收卷至料轴D，制备得到催化层膜。
所述催化层膜包括催化剂、树脂和高分子载体(PAA等)，通过纤维编制成催化层，因此具有一定强度可单独成卷，利于催化层的单独后处理。在本发明中，催化剂纺丝浆料静电纺丝后还包括后处理；
所述后处理包括热辊压、平板加热、红外加热或鼓风烘箱加热。
本发明提供了一种燃料电池膜电极，包括阴极纳米纤维催化层膜、质子交换膜和阳极纳米纤维催化层膜；
所述阴极纳米纤维催化层膜和阳极纳米纤维催化层膜均为上述技术方案所述纳米纤维催化层膜。
本发明提供了一种上述技术方案所述燃料电池膜电极的制备方法，包括以下步骤：
将阳极纳米纤维催化层膜、质子交换膜和阴极纳米纤维催化层膜复合，得到膜电极；
所述复合的压力为0.1～10MPa，复合的温度为10～140℃。
如图3所示，在一个具体实施例中，所述燃料电池膜电极的制备方法包括：将质子交换膜放置料轴E，将质子交换膜背膜剥离后收集至料轴F，质子交换膜通过辊压轴f牵引；阳极催化层膜和阴极催化层膜分别放置料轴G和料轴H，分别通过辊压轴h和辊压轴i牵引；质子交换膜、阳极纳米纤维催化层膜和阴极纳米纤维催化层膜通过辊压轴j和料轴k进行复合制备得到CCM产品，与背膜复合收集至料轴I；料轴j和料轴k处的复合工艺可控制压力、温度等参数。
参见图4：具体实施例中，所述燃料电池膜电极的制备方法具体包括S1:催化剂纺丝浆料的制备；S2：纳米纤维催化层膜制备工艺；S3：CCM制备-纳米纤维催化层膜与质子交换膜复合工艺。上述膜电极的生产过程灵活，质量可控，可实现降低CCM制备成本、提升良率的效果；与质子交换膜的复合过程较为温和，对其损伤较小，且在一定程度上缓解静电纺丝工艺的低效率问题。
本发明通过静电纺丝制备的纳米纤维催化层膜，具备通孔结构、沿纤维短传输路径等优势可实现高传质，膜电极具备高性能，如极化性能；其能单独成卷作为产品，利于催化层的中间处理，以及与质子交换膜的灵活匹配；实现催化层膜与质子交换膜的单独生产，加快催化剂涂覆膜(CCM)生产效率和灵活性。此外，催化层膜与质子交换膜温和复合工艺，可解决热转印工艺中对质子交换膜造成的损伤问题。
附图说明
图1为催化层膜单独剥离成膜的示意图；
图2为具体实施例中催化层膜的制备流程示意图；
图3为具体实施例中催化层膜与质子交换膜复合成膜电极的工艺过程；
图4为本发明具体实施例中基于静电纺丝的燃料电池膜电极的工艺过程；
图5为本发明实施例和对比例制备的膜电极的电化学活性面积(ECSA)比较；
图6为本发明实施例和对比例制备的膜电极的电池测试性能结果。
具体实施方式
为了进一步说明本发明，下面结合实施例对本发明提供的一种基于静电纺丝的纳米纤维催化层膜和燃料电池膜电极及其制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
对比例1
传统催化层制备
通过超声喷涂方法制备阴极载量0.15mgPt/cm2和阳极载量0.05mgPt/cm2的膜电极，所制备膜电极装入标准单池，80℃，100％ RH测试H2/Air下的极化性能。
实施例1
阴极催化层膜制备：称取阴极催化剂Pt/C(57wt％Pt)2.7g，加入9g水和9g异丙醇作为溶剂，在加入4.57g 20wt％全氟磺酸树脂，超声1h。再加入0.5g 45万分子量的PAA，搅拌48h；在质子交换膜的一侧，7×7cm区域上，通过静电纺丝(电压30kV，流速1mL/h，针头和接收器距离10cm)制备0.15mgPt/cm2阴极催化层膜；
阳极催化层膜制备：称取阳极催化剂Pt/C(50wt％Pt)2g，加入7g水和7g异丙醇作为溶剂，在加入4.5g 20wt％全氟磺酸树脂，超声1h。再加入0.5g45万分子量的PAA，搅拌48h；在质子交换膜的一侧，7×7cm区域上，通过静电纺丝(电压25kV，流速0.5mL/h，针头和接收器距离10cm)制备0.05mgPt/cm2阳极催化层膜；
所制备膜电极装入标准单池，80℃，100％ RH测试H2/Air下的极化性能。
实施例2
热处理的催化层膜制备：
阴极催化层膜制备：称取阴极催化剂Pt/C(57wt％Pt)2.7g，加入9g水和9g异丙醇作为溶剂，在加入4.57g20wt％全氟磺酸树脂，超声1h。再加入0.5g 45万分子量的PAA，搅拌48h；在7×7cm的离型纸上，通过静电纺丝(电压30kV,流速1mL/h,针头和接收器距离10cm)制备0.15mgPt/cm2阴极催化层膜，将催化层膜剥离，放置烘箱150℃热处理20min；
阳极催化层膜制备：称取阳极催化剂Pt/C(50wt％Pt)2g，加入7g水和7g异丙醇作为溶剂，在加入4.5g 20wt％全氟磺酸树脂，超声1h。再加入0.5g45万分子量的PAA，搅拌48h；在7×7cm的离型纸，通过静电纺丝(电压25kV,流速0.5mL/h,针头和接收器距离10cm)制备0.05mgPt/cm2阳极催化层膜，将催化层膜剥离，放置烘箱150℃热处理20min；
将阳极催化层膜、质子交换膜、阳极催化层膜按照图3所示工艺热压复合，得到膜电极；
将所制备的膜电极装入标准电池，80℃，100％RH测试H2/Air下的极化性能。
图5为本发明实施例和对比例制备的膜电极的电化学活性面积(ECSA)比较，实施例2>实施例1>对比例1，说明纳米纤维膜催化层内催化剂的利用率高于对比例1中的传统催化层，且热压工艺处理后催化剂利用率也明显提升，说明热压工艺促进纤维之间的结构重排，并且高温利于树脂在催化剂表面的均匀分布，可提升性能；
图6为本发明实施例和对比例制备的膜电极的电池性能极化曲线比较，实施例2制备的膜电极在2000mA/cm2下达到0.637V，实施例1制备的膜电极在2000mA/cm2下达到0.597V，而对比例1制备的膜电极在2000mA/cm2达到0.568V；可以看出，实施例2中的膜电极比传统膜电极在高电密区具备更优的传质能力，因此相同电流密度下体现更高的电压性能。
由以上实施例可知，本发明提供了一种基于静电纺丝的纳米纤维催化层膜，由催化剂纺丝浆料静电纺丝制得；所述催化剂纺丝浆料中包括树脂、催化剂、高分子载体和溶剂；所述高分子载体选自聚丙烯酸、聚氧化乙烯、聚四氟乙烯、聚偏氯乙烯、聚乙烯醇、聚醋酸乙烯、聚丙烯腈和聚甲基丙烯酸酯中的一种或多种。该催化层膜采用高分子载体作为原料之一，再结合静电纺丝编制而成，具有一定强度能单独成膜；利于其中间处理，以及与质子交换膜灵活匹配；与质子交换膜复合后的膜电极具有较高的极化性能。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种基于静电纺丝的纳米纤维催化层膜，由催化剂纺丝浆料静电纺丝制得；
所述催化剂纺丝浆料中包括树脂、催化剂、高分子载体和溶剂；
所述高分子载体选自聚丙烯酸、聚氧化乙烯、聚四氟乙烯、聚偏氯乙烯、聚乙烯醇、聚醋酸乙烯、聚丙烯腈和聚甲基丙烯酸酯中的一种或多种。
2.根据权利要求1所述的纳米纤维催化层膜，其特征在于，所述树脂选自长支链型全氟磺酸树脂、短支链型全氟磺酸树脂、磺化聚苯乙烯、磺化聚芳醚砜、磺化聚醚醚酮、聚偏氟乙烯、聚四氟乙烯和四氟乙烯-共聚-六氟乙烯中的一种或多种；
所述溶剂选自水、异丙醇、正丙醇、乙醇、甲醇、N,N-二甲基甲酰胺、二甲基亚砜和氯仿中的一种或多种；
所述催化剂选自铂碳催化剂、铂基合金催化剂和非贵金属催化剂中的一种或多种。
3.根据权利要求1所述的纳米纤维催化层膜，其特征在于，所述树脂、催化剂、高分子载体和溶剂的质量比为(0.1～5)：(0.1～5)：(0.01～2)：(1～60)。
4.根据权利要求1所述的基于静电纺丝的燃料电池膜电极，其特征在于，所述催化剂纺丝浆料由树脂、催化剂、高分子载体和溶剂混合制得；
所述混合的方式选自超声、珠磨、搅拌和均质中的一种或多种。
5.根据权利要求1所述的纳米纤维催化层膜，其特征在于，所述催化剂纺丝浆料静电纺丝时的电压为0.1～100kv，喷头与接收基底的距离为1～20cm，温度为15～80℃，湿度为10％RH～80RH％；
针头选自针式喷头、无针式喷头或多微孔喷头。
6.根据权利要求5所述的纳米纤维催化层膜，其特征在于，所述接收基底选自离型纸、硅油纸或铝箔。
7.根据权利要求1所述的纳米纤维催化层膜，其特征在于，所述阴极纳米纤维催化层膜的载量为0.05～1mgPt/cm2；
所述阳极纳米纤维催化层膜的载量为0.05～1mgPt/cm2。
8.根据权利要求1所述的纳米纤维催化层膜，其特征在于，催化剂纺丝浆料静电纺丝后还包括后处理；
所述后处理包括热辊压、平板加热、红外加热或鼓风烘箱加热。
9.一种燃料电池膜电极，其特征在于，包括阴极纳米纤维催化层膜、质子交换膜和阳极纳米纤维催化层膜；
所述阴极纳米纤维催化层膜和阳极纳米纤维催化层膜均为权利要求1所述纳米纤维催化层膜。
10.一种权利要求9所述燃料电池膜电极的制备方法，包括以下步骤：
将阳极纳米纤维催化层膜、质子交换膜和阴极纳米纤维催化层膜复合，得到膜电极；
所述复合的压力为0.1～10MPa，复合的温度为10～140℃。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010095826A (ja) * | 2008-10-17 | 2010-04-30 | Asahi Glass Co Ltd | 繊維の製造方法ならびに製造装置、触媒層の製造方法、導電性繊維および固体高分子形燃料電池用膜電極接合体 |
| CN105220267A (zh) * | 2015-10-28 | 2016-01-06 | 北京巨龙博方科学技术研究院 | 一种制备全氟磺酸催化纤维的方法 |
| CN110350150A (zh) * | 2019-07-16 | 2019-10-18 | 深圳市南科燃料电池有限公司 | 一种转印工艺和膜电极 |
| CN111952599A (zh) * | 2019-05-14 | 2020-11-17 | 中国科学院大连化学物理研究所 | 一种高稳定性质子交换膜燃料电池纳米纤维电极及其制备方法与应用 |
| CN113106629A (zh) * | 2021-04-07 | 2021-07-13 | 中国人民解放军国防科技大学 | 一种有序纳米纤维质子交换膜及其制备方法与应用 |
-
2023
- 2023-03-14 CN CN202310246660.7A patent/CN116093345A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010095826A (ja) * | 2008-10-17 | 2010-04-30 | Asahi Glass Co Ltd | 繊維の製造方法ならびに製造装置、触媒層の製造方法、導電性繊維および固体高分子形燃料電池用膜電極接合体 |
| CN105220267A (zh) * | 2015-10-28 | 2016-01-06 | 北京巨龙博方科学技术研究院 | 一种制备全氟磺酸催化纤维的方法 |
| CN111952599A (zh) * | 2019-05-14 | 2020-11-17 | 中国科学院大连化学物理研究所 | 一种高稳定性质子交换膜燃料电池纳米纤维电极及其制备方法与应用 |
| CN110350150A (zh) * | 2019-07-16 | 2019-10-18 | 深圳市南科燃料电池有限公司 | 一种转印工艺和膜电极 |
| CN113106629A (zh) * | 2021-04-07 | 2021-07-13 | 中国人民解放军国防科技大学 | 一种有序纳米纤维质子交换膜及其制备方法与应用 |
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