CN102751512B - 新型直接硼氢化钠燃料电池用Fe/N/C阴极生产技术 - Google Patents
新型直接硼氢化钠燃料电池用Fe/N/C阴极生产技术 Download PDFInfo
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Abstract
本发明提供一种制备Fe/N/C阴极的工业生产技术，该阴极可直接用于直接硼氢化钠燃料电池。该技术包括多孔石墨烯网络的制备、纳米铁的负载和氮掺杂的原位处理、阴极和膜组件的制备等过程。使用本发明提供的技术可以实现Fe/N/C中石墨烯片层的可控生长和阴极的连续生产。且避免传统工艺的憎水处理环节，显著简化了燃料电池阴极的制作流程，对促进燃料电池实用化具有重要意义。
Description
技术领域
本技术涉及电极制备领域，特别涉及直接硼氢化钠燃料电池阴极制备领域。
背景技术
燃料电池是一种直接将储存在燃料中的化学能转化为电能的发电技术，由于其具有能量转换效率高、低排放、无污染和无噪音等优点，被认为是继火力、水力、核能之外的第四种发电方法。开发非贵金属催化剂一直是降低燃料电池成本，推动燃料电池技术实用化的关键问题之一[Michel Lefèvre, Eric Proietti, Frédéric Jaouen, Jean-Pol Dodelet, Science, 2009, 324:71-74]。
Co/N/C催化剂被认为是最有潜力取代昂贵的Pt/C作为燃料电池阴极催化剂之一。Co/N/C催化剂包含金属钴或者钴的化合物，N元素以及碳载体。已有研究表明将碳载体在高温通以氮气或者氨气能使部分氮原子掺杂到碳载体中，然后用这种掺杂了氮的碳载体与钴或其化合物混合所得的复合物具有较好的对氧气还原反应的催化活性。可以把该复合物粉末与憎水乳液（如聚四氟乙烯等）混合调浆涂抹到碳纸晾干烧结制得直接硼氢化钠燃料电池所用的阴极，进而与阳极、质子交换膜、极板等一起装配为完整的电池。憎水处理对于阴极的电化学活性有很大的影响，憎水物质的用量较少将使阴极憎水性质不佳进而导致电池工作时出现水淹情况阻碍氧气扩散，而提高憎水物质的用量虽能改善憎水性质但将伴随出现导电性下降的结果。因此憎水物质的用量存在一个中间最优值。这增加了阴极制备质量稳定性控制的难度，同时使阴极制备流程繁琐复杂化，不利于直接硼氢化钠燃料电池的规模化工业制造。
石墨烯是碳原子以sp2混成轨域呈蜂巢晶格排列构成的单层二维晶体材料，它具有独特的物理化学性质，如高理论比表面积（约2630 m2 g-1）、高化学稳定性、高电导率（106S cm-1）和易功能化等[Dongsheng Geng, Songlan Yang, Yong Zhang, et al., Applied Surface Science, 2011, 257:9193– 9198]，具有重要的科学研究意义和广泛的应用前景。最近氮掺杂石墨烯的合成及其电化学特性的研究受到广泛关注[Dongsheng Geng, Songlan Yang, Yong Zhang, et al., Applied Surface Science, 2011, 257:9193–9198; Yuyan Shao, Sheng Zhang, Mark H. et al., Journal of Materials Chemistry, 2010, 20:7491–7496; Liangti Qu, Yong Liu, Jong-Beom Baek, et al., Nano, 2010, 4:1321–1326 ]。研究表明，氮掺杂石墨烯后可以有效提高石墨烯的电导率和耐腐蚀性；[Dongsheng Geng, Songlan Yang, Yong Zhang, et al., Applied Surface Science, 2011, 257:9193– 9198]；而Shao等人研究表明，由于氮功能团和表面结构缺陷的引入，氮掺杂石墨烯对氧气和双氧水还原反应的催化活性明显高于纯石墨烯[Yuyan Shao, Sheng Zhang, Mark H. et al., Journal of Materials Chemistry, 2010, 20:7491–7496]；由此可见，氮掺杂石墨烯是一种非常有潜力应用到燃料电池非贵金属阴极催化剂的新型材料。石墨烯的物理化学性能与石墨烯的层数密切相关，理论上而言单原子层的石墨烯具有最佳的物理化学性能。研究发现在金属镍表面容易生长多层石墨烯，且在生长过程中难以通过控制反应组元、温度等参数简单调控石墨烯的层数。
发明内容
为了同时解决电极憎水处理和开发新型高催化活性的阴极，本发明公开了一种具有自憎水性能的新型Fe/N/C催化剂阴极，并提供了一种制备该阴极的规模化工业生产技术。
本发明基于以下思路：利用石墨烯本身具有良好的憎水性免除常规阴极的憎水处理，利用石墨烯良好的导电性和多孔透气性充当气体扩散层和导电层，同时以石墨烯作为特殊碳载体进行氮掺杂和担载铁化合物成为自憎水Fe/N/C催化剂阴极。
本发明的具体实施过程如下：在密闭的可抽真空和通气氛的安装有电动收卷放卷装置的反应器中，将泡沫镍和碳布双层卷放在左侧转轴，抽出泡沫镍和碳布一头穿过中间反应区固定于右侧收卷机构。将反应器抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将中间反应区温度升至1050 oC，开始通入甲烷和氮气混合气体，同时开动右侧传动收卷机构使泡沫镍和碳布连续通过中间反应区，使泡沫镍表面生长有石墨烯。当泡沫镍和碳布完全收卷于右侧后停止加热和通气，使反应器内温度降低至100 oC以下后打开反应器取出泡沫镍和碳布双层卷。然后利用去除泡沫镍并吸附硫酸亚铁的连续收卷装置，将该双层卷连续通过FeCl3/HCl腐蚀液槽和铁盐液槽并保持泡沫镍层在碳布层上方，使得泡沫镍溶解且石墨烯网络中间吸附铁盐。将所收得的碳布卷在60 oC烘干后再次装入反应器，抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将反应区温度升至900~1050 oC，开始通入氨气和氮气混合气体，同时开动收卷机构使碳布卷以一定的速度连续通过中间反应区，从而得到包含纳米铁氧化物的氮掺杂石墨烯碳布卷，将反应器内温度降低至100 oC以下后打开反应器取出卷。根据燃料电池流场面积，从卷中裁剪适当尺寸的碳布，与质子交换膜和阳极直接组装成MEA，之后与流场极板装配为直接硼氢化钠燃料电池。
本发明的有益效果：实现了氮掺杂石墨烯载铁催化剂原位一体地应用于直接硼氢化钠燃料电池阴极并使电池获得高的发电性能；避免使用Pt贵重金属和Co等战略金属；免去难控制的憎水工序，极大地简化了电池阴极的制备技术；实现阴极大批次规模化工业生产，提高电池生产率并降低生产成本。
附图说明
图1原位反应器示意图
图2去除泡沫镍并吸附铁盐的连续收卷机构示意图
图3氮掺杂石墨烯载铁碳布卷的结构示意图
图4 MEA结构图
具体实施方式
实施例1：
在如图1所示的反应器中，将泡沫镍和碳布双层卷放在左侧转轴，抽出泡沫镍和碳布一头穿过中间反应区固定于右侧收卷机构。将反应器抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将中间反应区温度升至1050 oC，开始通入甲烷和氮气混合气体（甲烷体积分数为40%，氮气体积分数为60%），同时开动右侧传动收卷机构使泡沫镍和碳布以0.5 mm/min的速度连续通过中间反应区，使泡沫镍表面生长有石墨烯。当泡沫镍和碳布完全收卷于右侧后停止加热和通气，使反应器内温度降低至100 oC以下后打开反应器取出泡沫镍和碳布双层卷。然后利用去除泡沫镍并吸附硫酸亚铁的连续收卷装置，将该双层卷以1 mm/min的速度连续通过FeCl3/HCl腐蚀液槽和Fe(SO4)2液槽(Fe(SO4)2浓度为1 mol/L)并保持泡沫镍层在碳布层上方，使得泡沫镍溶解且石墨烯网络中间吸附Fe(SO4)2。将所收得的碳布卷在60 oC烘干后再次装入图1的反应器，抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将反应区温度升至900 oC，开始通入氨气和氮气混合气体（氨气体积分数为10%，氮气体积分数为90%），同时开动收卷机构使碳布卷以0.5 mm/min的速度连续通过中间反应区，从而得到包含纳米铁氧化物的氮掺杂石墨烯碳布卷，将反应器内温度降低至100 oC以下后打开反应器取出卷。根据燃料电池流场面积，从卷中裁剪适当尺寸的碳布，与质子交换膜和阳极直接按图4结构组装成MEA，之后与流场极板装配为直接硼氢化钠燃料电池。该电池以10wt.%NaOH-5wt.%NaBH4为燃料在80 oC的最大输出功率密度可达到310 mW/cm2。
实施例2：
在如图1所示的反应器中，将泡沫镍和碳布双层卷放在左侧转轴，抽出泡沫镍和碳布一头穿过中间反应区固定于右侧收卷机构。将反应器抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将中间反应区温度升至1050 oC，开始通入甲烷和氮气混合气体（甲烷体积分数为20%，氮气体积分数为80%），同时开动右侧传动收卷机构使泡沫镍和碳布以5 mm/min的速度连续通过中间反应区，使泡沫镍表面生长有石墨烯。当泡沫镍和碳布完全收卷于右侧后停止加热和通气，使反应器内温度降低至100 oC以下后打开反应器取出泡沫镍和碳布双层卷。然后利用去除泡沫镍并吸附铁盐的连续收卷装置，将该双层卷以5 mm/min的速度连续通过FeCl3/HCl腐蚀液槽和FeCl2液槽(FeCl2浓度为5 mol/L)并保持泡沫镍层在碳布层上方，使得泡沫镍溶解且石墨烯网络中间吸附FeCl2。将所收得的碳布卷在60 oC烘干后再次装入图1的反应器，抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将反应区温度升至1000 oC，开始通入氨气和氮气混合气体（氨气体积分数为40%，氮气体积分数为60%），同时开动收卷机构使碳布卷以5 mm/min的速度连续通过中间反应区，从而得到包含纳米铁氧化物的氮掺杂石墨烯碳布卷，将反应器内温度降低至100 oC以下后打开反应器取出卷。根据燃料电池流场面积，从卷中裁剪适当尺寸的碳布，与质子交换膜和阳极直接按图4结构组装成MEA，之后与流场极板装配为直接硼氢化钠燃料电池。该电池以10wt.%NaOH-5wt.%NaBH4为燃料在80 oC的最大输出功率密度可达到380 mW/cm2。
实施例3：
在如图1所示的反应器中，将泡沫镍和碳布双层卷放在左侧转轴，抽出泡沫镍和碳布一头穿过中间反应区固定于右侧收卷机构。将反应器抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将中间反应区温度升至1050 oC，开始通入甲烷和氮气混合气体（甲烷体积分数为40%，氮气体积分数为60%），同时开动右侧传动收卷机构使泡沫镍和碳布以50 mm/min的速度连续通过中间反应区，使泡沫镍表面生长有石墨烯。当泡沫镍和碳布完全收卷于右侧后停止加热和通气，使反应器内温度降低至100 oC以下后打开反应器取出泡沫镍和碳布双层卷。然后利用去除泡沫镍并吸附硫酸亚铁的连续收卷装置，将该双层卷以10 mm/min的速度连续通过FeCl3/HCl腐蚀液槽和Fe(CH3COO)2液槽(Fe(CH3COO)2浓度为20 mol/L)并保持泡沫镍层在碳布层上方，使得泡沫镍溶解且石墨烯网络中间吸附Fe(CH3COO)2。将所收得的碳布卷在60 oC烘干后再次装入图1的反应器，抽真空至10-2 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于10-4 Pa。将反应区温度升至1050 oC，开始通入氨气和氮气混合气体（氨气体积分数为80%，氮气体积分数为20%），同时开动收卷机构使碳布卷以50 mm/min的速度连续通过中间反应区，从而得到包含纳米铁氧化物的氮掺杂石墨烯碳布卷，将反应器内温度降低至100 oC以下后打开反应器取出卷。根据燃料电池流场面积，从卷中裁剪适当尺寸的碳布，与质子交换膜和阳极直接按图4结构组装成MEA，之后与流场极板装配为直接硼氢化钠燃料电池。该电池以10wt.%NaOH-5wt.%NaBH4为燃料在80 oC的最大输出功率密度可达到360 mW/cm2。
不脱离本发明的范围和原理，本发明的不同改变和变化对于本领域普通技术人员是显而易见的，应当理解本发明不限于在上文提出的示例性实施方式。
Claims (4)
1.一种Fe/N/C 阴极的工业生产方法，包括如下步骤：
1) 在密闭的可抽真空和通气氛的安装有电动收卷放卷装置的容器中， 将泡沫镍和碳布双层卷放在左侧转轴， 抽出泡沫镍和碳布一头穿过中间反应区固定于右侧收卷机构 ；将反应装置抽真空至 Pa 并充氮气再抽真空，反复数次使反应器内氧气残余量小于 Pa；将中间反应区温度升至 1050 ℃，开始通入甲烷和氮气混合气体，甲烷与氮气混合气体中甲烷体积比例为 10%~40%，氮气体积比例为 60%~90%，同时开动右侧传动收卷机构使泡沫镍和碳布连续通过中间反应区，所述的泡沫镍和碳布双层卷的收卷速度为 0.5~50 mm/min，使泡沫镍表面生长有石墨烯；当泡沫镍和碳布完全收卷于右侧后停止加热和通气， 使反应器内温度降低至100℃以下后打开反应器取出泡沫镍和碳布双层卷；
2) 将步骤1)所获得的双层卷连续通过FeCl3/HCl腐蚀液槽和铁盐溶液槽并保持泡沫镍层在碳布层上方，使得泡沫镍溶解且石墨烯网络中间吸附铁盐；双层卷的收放卷速度为 1~10 mm/min；
3) 将步骤2)所获得的碳布卷在60 ℃烘干后再次装入步骤1)所述的反应器，抽真空至 Pa并充氮气再抽真空，反复数次使反应器内氧气残余量小于 Pa；将反应区温度升至 900~1050℃，开始通入氨气和氮气混合气体，氨气与氮气的混合气体中氨气体积比例为 10%~80% ；氮气体积比例为 20%~90%，同时开动收卷机构使碳布卷连续通过中间反应区，所述的碳布卷收卷速度为 5~50 mm/min，当反应器内温度降低至 100℃以下后打开反应器取出碳布卷；
4) 将步骤 3) 所获得的碳布卷裁剪为合适尺寸作为阴极，与阳极、电解质膜制作成膜组件。
2.如权利要求1所述的一种Fe/N/C阴极的工业生产方法，其特征在于：步骤2)所述的铁盐液槽中盛有硝酸铁、硫酸铁、盐酸铁、草酸铁或醋酸铁的一种或多种混合，且溶液中Fe离子的总浓度为 1~20 mol/L。
3.如权利要求1所述的一种Fe/N/C阴极的工业生产方法， 其特征在于所制备的Fe/N/C 中Fe以纯铁或者铁的氧化物纳米颗粒嵌在多孔状的石墨烯网络中。
4.一种质子交换膜燃料电池，其特征是：其具备使用权利要求 1~3中任一项所述的Fe/N/C阴极的工业生产方法得到的阴极。
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