CN115181210A - 一种高质子传导率的酸性水凝胶膜及其燃料电池应用 - Google Patents
一种高质子传导率的酸性水凝胶膜及其燃料电池应用 Download PDFInfo
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Abstract
本发明提供了一种具有高质子传导能力的酸性水凝胶膜制备方法以及其在燃料电池领域的应用，以提供一种新型柔性电解质的合成方法以及其实际应用的方案。酸性水凝胶膜的聚合母液由水溶性乙烯基单体、疏水性二乙烯基化合物交联剂、光引发剂以及强酸溶液组成，其中所述水溶性乙烯基单体含有酰胺基、羧酸、羟基等官能团或其组合，疏水性二乙烯基化合物含有苯环或直链烷烃。母液能够在紫外灯照射下迅速成胶，在模具中形成凝胶膜。该酸性水凝胶膜质子传导率高、力学性能稳定、热分解温度高，应用于氢氧燃料电池能获得较高功率密度。所述制备方法简单，材料价格低廉，为其规模生产应用提供了可能。
Description
技术领域
本发明涉及一种适用于氢氧燃料电池，具有高质子传导率，由酸性水溶液原位聚合制备的柔性凝胶膜材料。
背景技术
清洁能源对社会可持续发展具有重要意义，氢能作为一种清洁的二次能源收受到了广泛关注。氢氧燃料电池通过电化学反应将氢的化学能直接转化为电能，能量效率高且无二次污染，在移动能源具有广阔的应用前景，可为航空、汽车、游艇、便携式电子设备等提供电力来源。
质子交换膜燃料电池是一种利用氢能的典型电化学装置，其主要结构包括端板、双极板和膜电极等部件。膜电极是燃料电池的核心部件，主要由气体扩散层、催化剂和质子交换膜构成。质子交换膜是燃料电池的关键部件，直接影响到电池的性能和使用寿命。目前商业化的质子传导膜主要是含水的全氟磺酸膜，其具有力学性能好、稳定性强、传导率高等优点，表现出良好的电池适应性。但全氟磺酸膜制备的磺化与氟化工艺非常复杂，生产成本高且环境友好性差。
水凝胶是一种由网络支撑骨架和连续水相构成的复合材料，可以通过物理、化学交联方法简单获得，通过向水中加入溶质或电活性物质可用做电解质。目前酸性水凝胶在电化学领域主要用于超级电容器，主要通过聚乙烯醇共混和丙烯酰胺热聚合制备。由聚乙烯醇与酸性水溶液共混制备的水凝胶存在力学性能差和容易降解等问题，不适合制作氢氧燃料电池的质子传导膜。由丙烯酰胺单体和N,N’-亚甲基双丙烯酰胺交联剂在酸性水溶液中原位热聚合制备的水凝胶热稳定性差，不具备电解质器件化应用的条件。
现有的全氟磺酸膜存在生产工艺复杂、成本高等问题，而现有酸性水凝胶存在力学性能与稳定性不足的问题，开发一种低成本的稳定质子交换凝胶膜对于氢氧燃料电池的开发应用具有重要意义。
发明内容
本发明的目的在于提供一种高质子传导率的酸性水凝胶膜组成、制备方法及其燃料电池应用，具备配方简单、工艺简便、力学与热稳定性好等特点，旨在克服现有技术的不足。
本发明所述的酸性水凝胶膜配方包含酸性水溶液、水溶性乙烯基单体（质量分数15~30%）、疏水性交联剂（质量分数0.5~2%）和光引发剂（质量分数0.05~0.1%）。
本发明的酸性水凝胶膜制作方法是这样实现的：
（1）将一定量的水溶性乙烯基单体、疏水性交联剂溶于配置好的强酸水溶液中，持续搅拌24小时，使其分散均匀。
（2）再将一定量的引发剂溶于上述配置好的聚合液前体中，充分搅拌2小时得到聚合母液。
（3）将上述聚合母液注入膜状模具中，于紫外灯下照射一定时长，经脱模后即可得到具有质子传导能力的酸性水凝胶膜。
本发明的酸性水凝胶膜的燃料电池应用这样实现的：
将制备好的酸性水凝胶膜夹持在两片涂附铂碳催化剂（铂负载量0.5 mg cm−2）的气体扩散电极之间获得膜电极组件，再将膜电极装入两个石墨极板间组装成燃料电池。
本发明具有以下有益效果：
本发明的酸性凝胶膜制作方法简单，成本低廉，成型能力好，力学性能适宜，在氢氧燃料电池中具有良好性能。
本发明的酸性凝胶膜厚度可控，质子传导率在30 ℃下可达170 mS cm−1，满足燃料电池使用需求。
本发明的酸性凝胶膜拉伸断裂强度可达62.8 kPa，抗压强度12.1 MPa，压缩应变量可达99.9%，力学性能良好。
本发明的酸性凝胶膜热分解温度高于230 ℃，具有良好的热稳定性。
本发明的酸性凝胶膜组装成燃料电池后，输出峰值功率密度达到129 mW cm−2。
附图说明
图1是实施案例1-3制备的具有高传导能力的水凝胶电解质的传导率图。
图2是实施案例1-3在30 ℃下组装氢氧燃料电池上的电池极化曲线，其中氢气和氧气均经过加湿处理，通气量分别为120 mL min−1和60 mL min−1。
图3是实施案例1-3测试时所使用的氢氧燃料电池示意图。
图中：1、酸性水凝胶膜；2、气体扩散电极；3、硅胶垫片；4、石墨单极板。
具体实施方式
为了使本发明的目的、技术方案以及优点更加清晰明确，下面将本发明的技术方案进行详细的说明描述。以下所述的实施案例仅仅是本发明的一部分实施案例，不能理解为对本发明的可实施范围的限定。
实施案例1
首先将325 mg的丙烯酰胺和11 mg的二乙烯苯交联剂加入1 mL的4 mol L−1硫酸溶液之中，在加入1 mg的光引发剂1-羟基环己基苯基甲酮之后充分搅拌2小时得到聚合母液。将聚合母液倒入模具（18×16×0.2 mm）之中，在光照强度为6 mW cm−2、波长为365 nm紫外灯下照射0.5小时成胶。脱模后得到厚度为0.2 mm的酸性水凝胶膜，抗拉强度为62.8 kPa，抗压强度为6.5 MPa，对应压缩形变量为99%，30 ℃下传导率170.6 mS cm−1，初始热分解温度为232 ℃。
将酸性水凝胶膜1夹持在14×12 mm的气体扩散电极2间组装成膜电极，硅胶垫片3装在膜电极的两侧，将带有硅胶垫片3的膜电极装入石墨单极板4间组装成燃料电池。得到开路电压为0.934 V，短路电流463.8 mA cm−2，峰值功率密度达到71.9 mW cm−2。
实施案例2
首先将325 mg的丙烯酰胺和11 mg的二乙烯苯交联剂加入1 mL的2.5 mol L−1三氟甲磺酸溶液之中，在加入1 mg的光引发剂1-羟基环己基苯基甲酮之后充分搅拌2小时得到聚合母液。将聚合母液倒入模具（18×16×0.2 mm）之中，在光照强度为6 mW cm−2、波长为365 nm紫外灯下照射0.5小时成胶。脱模后得到厚度为0.2 mm的酸性水凝胶膜，抗拉强度为42.8 kPa，抗压强度为0.9 MPa，对应压缩形变量为97%，30 ℃下传导率133.5 mS cm−1，初始热分解温度为235 ℃。
将酸性水凝胶膜1夹持在14×12 mm的气体扩散电极2间组装成膜电极，硅胶垫片3装在膜电极的两侧，将带有硅胶垫片3的膜电极装入石墨单极板4间组装成燃料电池。得到开路电压为0.986 V，短路电流579.0 mA cm−2，峰值功率密度达到129.4 mW cm−2。
实施案例3
首先将325 mg的丙烯酰胺和11 mg的二乙烯苯交联剂加入1 mL的4 mol L−1三氟甲磺酸溶液之中，在加入1 mg的光引发剂1-羟基环己基苯基甲酮之后充分搅拌2小时得到聚合母液。将聚合母液倒入模具（18×16×0.2 mm）之中，在光照强度为6 mW cm−2、波长为365nm紫外灯下照射0.5小时成胶。脱模后得到厚度为0.2 mm的酸性水凝胶膜，抗拉强度为62.8kPa，抗压强度为12.1 MPa，对应压缩形变量为99.9%，30 ℃下传导率105.7 mS cm−1，初始热分解温度为231 ℃。
将酸性水凝胶膜1夹持在14×12 mm的气体扩散电极2间组装成膜电极，硅胶垫片3装在膜电极的两侧，将带有硅胶垫片3的膜电极装入石墨单极板4间组装成燃料电池。得到开路电压为0.974 V，短路电流493.5 mA cm−2，峰值功率密度达到101.5 mW cm−2。
图1为实施案例1-3中具有高传导能力的水凝胶电解质的传导率对比图，从图中可以看出，实施案例1中所得到的水凝胶电解质具有最高的传导率。每个实施案例中得到的水凝胶电解质的传导率均随着温度的上升而上升。
图2为实施案例1-3中具有高传导能力的水凝胶电解质在氢氧燃料电池上进行测试之后得到的电池极化曲线，实施案例1-3所得到的电池极化曲线相关数据见于表1。
图3为实施案例测试时所使用的氢氧燃料电池示意图。
表1．实施案例1-3在燃料电池上的开路电压、最大电流密度以及峰值功率密度
Claims (7)
1.一种高质子传导率的酸性水凝胶膜的制备方法，其特征在于：将水溶性乙烯基单体、疏水性交联剂和光引发剂引入强酸水溶液中，搅拌2~4小时得到聚合母液；然后将聚合母液注入膜状模具中，在波长为365nm、强度为4~8 mW cm−2 紫外光照射0.5~1小时，经脱模后得到质子传导水凝胶膜。
2.如权利要求1所述的一种高质子传导率的酸性水凝胶膜的制备方法，其特征在于：水溶性乙烯基单体含有酰胺基、羧酸、羟基等官能团或其组合，如丙烯酰胺、丙烯酸、2-羟基乙基甲基丙烯酸酯等，其质量分数为15~30%。
3.如权利要求1所述的一种高质子传导率的酸性水凝胶膜的制备方法，其特征在于：疏水性交联剂为含芳烃或长链烷烃疏水官能团的二乙烯基化合物，如二乙烯苯、1,9-双（丙烯酰氧基）壬烷等，其质量分数为0.5~2%。
4.如权利要求1所述的一种高质子传导率的酸性水凝胶膜的制备方法，其特征在于：聚合引发剂为烷基芳酮类、羟基酮类等水溶性光引发剂，如1-羟基环己基苯基丙酮、2-羟基-2-甲基-1-苯基丙酮等，其质量分数为0.05~0.1%。
5.如权利要求1所述的一种高质子传导率的酸性水凝胶膜的制备方法，其特征在于：酸性水溶液中的酸为三氟甲磺酸、硫酸等强酸或其组合，质量浓度为5~40%。
6.一种高质子传导率的酸性水凝胶膜，其特征在于：是由权利要求1所述的方法制备得到。
7.权利要求6所述的高质子传导率的酸性水凝胶膜在燃料电池中的应用。
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