CN102544542B - 具低穿透率的有机无机混成的复合质子交换膜 - Google Patents
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Abstract
本发明公开了一种具低穿透率的有机无机混成的复合质子交换膜，其为通过将修饰过的石墨烯与具质子传导性的高分子混掺使之形成而作为燃料组绝材料的复合质子交换膜。所述复合质子交换膜，包括0.001wt％～10wt％无机材料以及99.999wt％～90wt％有机材料。无机材料为具二维结构的石墨烯衍生物。有机材料包括具磺酸根的高分子材料。本发明将质子交换树脂中混掺具二维结构的石墨烯衍生物，能利用其明显的片状结构来阻绝甲醇穿透的问题。
Description
技术领域
本发明涉及一种质子交换膜，尤其涉及一种具有低穿透率(permeability)的有机无机混成（organic-inorganic hybrid）的复合质子交换膜。
背景技术
燃料电池(Fuel Cell,FC)是一种利用化学能直接转换为电能的发电装置，与传统发电方式比较之下，燃料电池具有低污染、低噪音、高能量密度以及较高的能量转换效率等优点，是极具未来前瞻性的干净能源，可应用的范围包括携带式电子产品、家用发电系统、运输工具、军用设备、太空工业以及小型发电系统等各种领域。
各类燃料电池依其运作原理及操作环境之不同而有不同的应用市场，在可移动式能源上的应用主要是以氢气质子交换膜燃料电池(Proton ExchangeMembrane fuel Cell,PEMFC)及直接甲醇燃料电池(Direct Methanol Fuel Cell，DMFC)为主，两者都属于使用质子交换膜进行质子传导机制之低温启动型燃料电池。
直接甲醇燃料电池的操作原理，为甲醇与水在阳极触媒层进行氧化反应，产生氢离子(H+)、二氧化碳(CO2)以及电子(e-)，其中氢离子可以经由质子传导膜传递至阴极，而电子则经由外部电路传输至负载作功之后再传递至阴极，此时供给阴极端的氧气会与氢离子及电子于阴极触媒层进行还原反应并产生水。此类质子交换膜燃料电池的性能决定于触媒三相反应效率，牵涉电子传导、离子传导及燃料传输效率，在燃料电池设计中三者同等重要，任何一条传导路径遭到阻碍，燃料电池的性能即受到影响。其中主导离子传导速率者为质子交换膜。
然而，直接甲醇燃料电池的膜电极组(membrane electrode assembly，MEA)因为甲醇穿透(methanol crossover)现象，因而使其面临电池寿命短、发电效率衰退等问题。在现有燃料电池中，阳极结构存在着液态、胶态、固态、或气态的有机燃料(如甲醇等醇类、醛类、或酸类)穿透的问题，如部份燃料与水经过阳极未与触媒产生反应，而直接穿越质子交换膜到达阴极，导致阴极催化反应能力降低。此外，燃料在阴极触媒进行氧化反应，与其周围氧气的还原反应共同形成混合电位(mixed potential)现象，使得燃料电池输出电压下降。这不但使燃料电池的输出功率降低，也使得燃料使用效率降低。此外，穿透的燃料也会导致质子交换膜与阴极的电极粘着剂膨润而加速阴极结构老化。
有鉴于甲醇穿透的问题是造成阴极触媒毒化而影响电池的耐久性(durability)，与发生混合电位(mixed potential)使得输出功率下降的主要因素。因此亟需一种可以降低甲醇穿透的质子交换膜。此外如质子交换膜具有低膨润(swelling)的行为也将大幅降低因质子交换膜与电极粘着剂膨润所造成之剥离(peeling)脱落的情形。
发明内容
本发明提供一种有机无机混成的复合质子交换膜，可以降低甲醇穿透。
本发明提出一种有机无机混成的复合质子交换膜，包括0.001wt%～10wt%无机材料以及99.999wt%～90wt%有机材料。无机材料为具二维结构的石墨烯衍生物。有机材料包括具磺酸根的高分子材料。
在本发明的一实施例中，所述石墨烯衍生物是选自由氧化石墨烯、硫化石墨烯、氢氧化石墨烯、碳酸化石墨烯、氮化石墨烯与磺酸化石墨烯所组成的族群。
在本发明的一实施例中，所述有机材料包括磺酸化聚氟共聚高分子(PTFE-PFSA copolymer)或磺酸化碳氢型高分子。
在本发明的一实施例中，所述磺酸化碳氢型高分子包括磺化聚醚醚酮(sulfonated poly(ether ether ketone)，s-PEEK)、磺化聚亚酰胺(sulfonatedpolyimides，s-PI)、磺化聚氧化二甲苯(sulfonated poly(phenylene oxide)，s-PPO)、磺化聚芳醚砜(sulfonated poly(arylene ether sulfone)，s-PES)、或磺化聚(4-苯氧基1,4苯基芐基酯)(sulfonated poly(4-phenoxybenzoyl-1,4-phenylene)，s-PPBP)。
在本发明的一实施例中，所述石墨烯衍生物是氧化石墨烯时，其添加量例如0.001wt%～5wt%。
在本发明的一实施例中，所述石墨烯衍生物是硫化石墨烯时，其添加量例如0.001wt%～5wt%。
在本发明的一实施例中，所述石墨烯衍生物是磺酸化石墨烯时，其添加量例如0.001wt%～5wt%。
基于上述，本发明是将质子交换树脂中混掺具二维结构的石墨烯衍生物，所以能利用其明显的片状结构来阻绝甲醇穿透的问题。
附图说明
图1是实验四的质子交换膜对于时间以及甲醇浓度之间的关系图。
具体实施方式
本实施例所提出的质子交换膜，是由有机材料与无机材料混成的一种有机无机混成的复合质子交换膜，其中包括约0.001wt%～10wt%的二维结构的石墨烯衍生物作为无机材料、以及99.999wt%～90wt%的具磺酸根的高分子材料作为有机材料。本文中的石墨烯衍生物是选自由氧化石墨烯、硫化石墨烯、氢氧化石墨烯、碳酸化石墨烯、氮化石墨烯与磺酸化石墨烯所组成的族群。而有机材料例如磺酸化聚氟共聚高分子(PTFE-PFSA copolymer)或如s-PEEK、s-PPO、s-PI、s-PES或s-PPBP之类的磺酸化碳氢型高分子。
在本发明的一实施例中，上述有机无机混成的质子交换膜中的磺酸化石墨烯的含量为0.005wt%，有机材料的含量为99.995wt%。在另一实施例中，上述有机无机混成的质子交换膜中磺酸化石墨烯的含量为0.05wt%，有机材料的含量为99.95wt%。在又一实施例中，上述有机无机混成的质子交换膜中磺酸化石墨烯的含量为0.5wt%，有机材料的含量为99.5wt%。在又一实施例中，上述有机无机混成的质子交换膜中氧化石墨烯的含量为1wt%，有机材料的含量为99wt%。在又一实施例中，上述有机无机混成的质子交换膜中氧化石墨烯的含量为2wt%，有机材料的含量为98wt%在又一实施例中，上述有机无机混成的质子交换膜中氧化石墨烯的含量为5wt%，有机材料的含量为95wt%。
以下列举几个实验例来验证本发明的效果。
首先，在以下实验一至实验三中针对混掺不同石墨烯衍生物的质子交换膜之甲醇穿透率进行量测。
实验一
氧化石墨的合成：
氧化石墨的合成方式是将石墨放置在浓硫酸下利用过锰酸钾(KMnO4)与硝酸钠(NaNO3)来进行氧化。此氧化反应是将10克石墨分散在250毫升的浓硫酸当中接着再将5克的硝酸钠(NaNO3)缓慢的加入溶液当中,随后通过冰浴将该液体冷却至0℃左右，随后在5个小时内缓慢的加入30克的过锰酸钾(KMnO4)，当添加完毕，移除冰浴，使该溶液回到室温再进行5个小时的反应。反应后将该溶液再度放置于冰浴中并通过加入5%过氧化氢(H2O2)的水溶液来去除过量过锰酸钾(KMnO4)的活性，随后将该溶液过滤而得到氧化石墨并利用盐酸水溶液与纯水多次清洗至中性，而所得氧化石墨的固体将其放置于真空下干燥。
实验二
氧化石墨烯(exfoliated graphite oxide):
将100毫克的氧化石墨分散在100毫升的纯水中并且将该溶液通过数小时的超音波震荡，震荡到整体溶液澄清为止，即可得到氧化石墨烯(graphene oxide，简称GO)的分散溶液。
实验三
磺酸化氧化石墨烯:
将1克干燥的氧化石墨烯粉末放置于30毫升的发烟硫酸中，将该溶液搅拌混合并维持在50℃下反应3天，反应结束后，将该溶液冷却过滤并用纯水洗涤，洗至该粉末呈中性，该粉末使用前仍需通过一小时的超音波震荡来将之分散于水中，即可得到磺酸化氧化石墨烯(简称GO-SO3H)的分散溶液。
实验四
利用烷基磺酸盐来修饰氧化石墨烯:
将50毫克的氧化石墨烯加入到0.06M的对氨基苯磺酸溶液并加热到70℃，在持续搅拌中缓慢逐滴的加入2毫升6x10-3M的亚硝酸钠(NaNO2)溶液，并在持续在70℃下反应12小时。反应结束后，将该溶液冷却过滤并用纯水洗涤，洗至该粉末呈中性，即可得到苯磺酸化氧化石墨烯(简称GO-Ph-SO3H)的分散溶液。
实验五
将95wt%(以固态的重量计)的NAF(由杜邦公司制造的DE2020CS商品)分散而二甲基乙胺(DMAc)中，再将5wt%(以固态的重量计)的氧化石墨烯分散于溶液中，以形成一浆料(ink)，通过超音波震荡与搅拌，经过12小时熟化之后，将所得的浆料涂布在玻璃基材上并将溶剂挥发，随后取下即可得到一质子交换膜。
实验六、七
以相同于实验五的方法制膜，但氧化石墨烯的含量分别改变为2wt%，1wt%。
实验八～十
以相同于实验五的方法制膜，但所添加的无机物改为苯磺酸化氧化石墨烯而其含量分别改变为0.5wt%、0.05wt%以及0.5wt%。
实验十一、十二
以相同于实验五的方法制膜，但将NAF(由杜邦公司制造的DE2020CS商品)改成磺化聚醚醚酮(sulfonated poly(ether ether ketone)，并将添加的无机物改为苯磺酸化氧化石墨烯而其含量为0.05wt%
甲醇穿透率的量测方式
甲醇穿透率的测量方式是利用两对称的玻璃连通管状槽体，而两连通管体接缝处夹有质子交换膜（一端装有纯水而另一端装有20%的甲醇水溶液），在恒温25℃之下随着实验的进行，甲醇将会由甲醇水溶液的槽体经由质子交换膜穿透到装有纯水的槽体，通过时间与纯水槽体内的甲醇浓度变化，公式P=[CB(t)TVB]/[(t-t0)ACA]利用进而求得该质子交换膜的甲醇穿透率。而P即为甲醇穿透率，而CA与CB则分别为甲醇水溶液槽体内的甲醇浓度与纯水槽体内的甲醇浓度，T为质子交换膜的厚度，而A为质子交换膜的测试面积。VB是纯水槽体的体积，t、t0是时间。
表一
其中，
是杜邦质子交换膜，商品名称Nafion，型号是N-117。
从表一可知，实验五到十的例子中可以归纳出有混掺有氧化石墨烯或苯磺酸化氧化石墨烯的质子交换膜能有效阻绝甲醇穿透的问题，尤其是仅需少量(约0.01%以上)即有明显的效果。
在图1所表示的是针对各种添加量的复合质子交换膜做甲醇（MeOH）穿透率的实验数据，由图1可以得知当有添加适量的无机材料进入质子交换膜里，在较薄的厚度即可得到与N-117相当的甲醇穿透率。
在以下表二中则是针对有无混掺氧化氧化石墨烯及其衍生物的质子交换膜(实验五～实验十)在对两种不同浓度的甲醇水溶液中的膨胀比(swelling ratio)。本组实验的做法上是将不同的复合质子交换膜剪裁成5公分平方的面积后再将之放于不同浓度、摄氏四十度的甲醇水溶液浸泡一小时后，随后取出测量其面积即可得到面积上的膨润百分比。
实验结果显示于表二。
表二
从表二可知，实验五到实验十中有混掺氧化石墨烯及其衍生物的质子交换膜无论在较低浓度(20vol%)或较高浓度(50vol%)的甲醇溶液中，都能大幅降低膨胀比，因此可借以减少电池的结构变形。
在以下表三则针对有无混掺氧化石墨烯的质子交换膜在吸水率以及甲醇吸取率上的观察。而这系列相关实验方式为:将不同的复合质子交换膜置于不同浓度摄氏四十度的甲醇水溶液，经过一小时的平衡，随随后将之取出秤量出所谓的湿重，随后再将之加热彻底除干可得干重，当湿重减干重即可得该质子交换膜的溶液含量，将溶液含量除以湿膜重即可得得到溶液吸取率。
表三
从表三可知，混掺氧化石墨烯及其衍生物的质子交换膜其仍维持一定的吸溶液的比水率较低，与该系列的质子交换膜的面积膨润率较低的现象有相互支持的结果。
在表四则针对有混掺氧化石墨烯及其衍生物的复合质子交换膜的导电度变化。由表中的数据可发现除了添加量大到5wt%时会导致质子导电度大幅下降以外，其余较低添加量则是在质子导电度上没有太大的差异。
表四
从表四可知，混掺氧化石墨烯及其衍生物的复合质子交换膜在低无机物添加量时(小于2wt%)仍维持一定的导电率。
表五
| 质子交换膜材料 | 甲醇穿透率(10-8cm2s-1) |
| s-PEEK | 1.0 |
| s-PEEK+0.05%GO-Ph-SO3H | 0.5 |
从表五可知，混掺磺化石墨烯于磺化聚醚醚酮的质子交换膜能有效阻绝甲醇穿透的问题，仅需少量磺化石墨烯(约0.05wt%)即有明显的效果。
从实验结果证实，本发明实施例的复合质子交换膜在降低甲醇穿透率，减少膨润，有显著的改进。
当然，本发明还可有其它多种实施例，在不背离本发明精神及其实质的情况下，熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形，但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (3)
1.一种有机无机混成的复合质子交换膜，其特征在于，包括：
0.001wt%～0.5wt%无机材料，该无机材料为具二维结构的石墨烯衍生物，该石墨烯衍生物选自磺酸化石墨烯,该磺酸化石墨烯选自磺酸化氧化石墨烯；以及
99.999wt%～99.5wt%有机材料，该有机材料包括具磺酸根的高分子材料。
2.根据权利要求1所述的有机无机混成的复合质子交换膜，其特征在于，该有机材料包括磺酸化聚氟共聚高分子或磺酸化碳氢型高分子。
3.根据权利要求2所述的有机无机混成的复合质子交换膜，其特征在于，该磺酸化碳氢型高分子包括磺化聚醚醚酮、磺化聚亚酰胺、磺化聚氧化二甲苯、磺化聚芳醚砜或磺化聚(4-苯氧基1,4苯基芐基酯)。
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| 麻琪.氧化石墨烯纳米复合膜研究.《中国优秀硕士学位论文全文数据库（工程科技I辑）》.2009,(第8期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI525881B (zh) | 2016-03-11 |
| US20120172461A1 (en) | 2012-07-05 |
| TW201228072A (en) | 2012-07-01 |
| CN102544542A (zh) | 2012-07-04 |
| US8552075B2 (en) | 2013-10-08 |
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