质子交换膜燃料电池电极耐久性的研究
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摘要
质子交换膜燃料电池(PEMFC)具有能量效率、能量密度高;没有液体电解质腐蚀;可以低温快速启动和结构紧凑等特点。因此在电动汽车、地面发电站、水下潜艇和通讯电源等方面具有广泛的应用前景。目前影响燃料电池商业应用的主要问题是成本和寿命,特别是在汽车应用时负载随时随地变化,燃料电池寿命大幅度下降,目前最好的动态负载下燃料电池的寿命为2200h,距离燃料电池汽车商业化目标寿命5000h还有大的距离。因此,研究的燃料电池失效机理,寻找解决措施,对提高燃料电池使用寿命,推动燃料电池技术商业化,减少环境污染都具有重大意义。
前人已经就催化剂的耐久性进行了广泛的研究,得到了比较明确的结论。本文着重研究Nafion电解质的耐久性。Nafion作为电极催化剂的电解质,在不同的温度下具有不同的结晶度,而且在高温处理后才具有更好的稳定性。因此,本文采用改变电极后处理温度的方法来改变Nafion的结晶度,提高Nafion的稳定性,从而达到提高电极耐久性的目的。除此之外,本文对PEMFC催化剂载体的耐腐蚀性进行了研究。石墨纳米纤维(GNF)作为PEMFC载体的难点是GNF的颗粒达不到纳米级。前人已在常温下研究了GNF的耐腐蚀性。本文重点研究用高能球磨、湿磨的方法制备GNF;探讨在高温(80℃)环境下制备的GNF的耐久性,并对GNF作为PEMFC催化剂载体进行可行性研究。
本文通过对电极寿命测试的方法进行的研究得知,在酸性溶液环境下对电极做1000圈CV,电极性能可衰减57%,是一个快速的寿命测试方法。通过对电极后处理温度的研究,证明了在N2保护的条件下,恒温加热30min,且加热温度为180℃时,电极具有更好的电化学性能、单电池性能、电化学寿命以及耐腐蚀性;而且通过TEM可以看出,在这个条件下的电极,Pt颗粒的分布更均匀。
此外,本文还将废旧碳纸回收,经高温灼烧,得到石墨纤维纸的产率约为84%。采用高能球磨、湿磨的方法,制备GNF。通过TEM测试可以看出,制备的GNF具有高的石墨化程度,颗粒已经达到纳米级。通过交流阻抗分析可以看出,GNF的反应电阻和CNTs、XC-72相比,电阻最小。通过GNF、CNTs和XC-72的耐腐蚀性比较可以看出,GNF比CNTs、XC-72更难被氧化。这证实了GNF比CNTs、XC-72具有更好的耐腐蚀性。因此,采用高能球磨法制备的GNF具备了作为催化剂的载体的基本条件,且具有较好的抗电化学氧化性。
Proton exchange membrane fuel cells (PEMFCs) are promising in energy efficiency, high energy density, no liquid electrolyte corrosion, low temperature quick starting, compacting structure and so on. It has a wide application prospect in electric vehicles, ground stations, underwater submarine and communication power. The main issues are the cost and life, especially in automotive operation at any time when the load changes, the life drops significantly. Now, the best life of PEMFC is 2200h, there being a great distance from the life of 5000h. Therefore, studying failure mechanism of the fuel cell, finding solutions to improve the fuel cell life, promoting the commercialization of fuel cell and reducing environmental pollution is of great significance.
Catalyst durability had been studied by Predecessors and they had gained extensive conclusions. This article focuses on the durability of Nafion electrolyte. Nafion as electrodes’catalyst has different crystallinities at different temperatures. And it has a better stability after high temperature treatment. So change the degree of crystallinity of Nafion to enhance the stability of Nafion by changing electrode post-processing temperature, in order to achieve improving the purpose of the durability of the electrode. In addition, PEMFC catalyst support of the corrosion resistance has been studied. The difficulty of Graphite nanofibers (GNF) as a PEMFC’s support is not nano-scale particles. GNFs’corrosion resistance at room temperature had been studied. This article focuses on preparing GNF using method of high-energy ball milling; wet grinding, studying the durability of GNF at high-temperature (80℃), and conducting the feasibility of GNF as PEMFC catalyst support.
Electrode life testing is studied. The results show that scanning 1000 circle CV in acidic solution environment is an ideal testing method of life, because the electrode performance can be attenuated 57%. By studying post-processing temperature of the electrodes, the electrodes protecting in the N2 atmosphere, constant heating 30min, and heating in the temperature of 180℃have better electrochemical performance, single-battery performance, life expectancy, as well as electrochemical corrosion resistance; The TEM of this electrode shows that its Pt particles are more evenly distributed under these conditions.
The wasted carbon papers are recycled and production rate of 84%. GNF are prepared by the wet high-energy ball milling method. The TEM shows the prepared GNF have been reached nano-particles degree. The EIS shows that the resistance of GNF is the smallest. The comparison among GNF, CNTs and XC-72 shows that GNF have better corrosion resistance.
前人已经就催化剂的耐久性进行了广泛的研究,得到了比较明确的结论。本文着重研究Nafion电解质的耐久性。Nafion作为电极催化剂的电解质,在不同的温度下具有不同的结晶度,而且在高温处理后才具有更好的稳定性。因此,本文采用改变电极后处理温度的方法来改变Nafion的结晶度,提高Nafion的稳定性,从而达到提高电极耐久性的目的。除此之外,本文对PEMFC催化剂载体的耐腐蚀性进行了研究。石墨纳米纤维(GNF)作为PEMFC载体的难点是GNF的颗粒达不到纳米级。前人已在常温下研究了GNF的耐腐蚀性。本文重点研究用高能球磨、湿磨的方法制备GNF;探讨在高温(80℃)环境下制备的GNF的耐久性,并对GNF作为PEMFC催化剂载体进行可行性研究。
本文通过对电极寿命测试的方法进行的研究得知,在酸性溶液环境下对电极做1000圈CV,电极性能可衰减57%,是一个快速的寿命测试方法。通过对电极后处理温度的研究,证明了在N2保护的条件下,恒温加热30min,且加热温度为180℃时,电极具有更好的电化学性能、单电池性能、电化学寿命以及耐腐蚀性;而且通过TEM可以看出,在这个条件下的电极,Pt颗粒的分布更均匀。
此外,本文还将废旧碳纸回收,经高温灼烧,得到石墨纤维纸的产率约为84%。采用高能球磨、湿磨的方法,制备GNF。通过TEM测试可以看出,制备的GNF具有高的石墨化程度,颗粒已经达到纳米级。通过交流阻抗分析可以看出,GNF的反应电阻和CNTs、XC-72相比,电阻最小。通过GNF、CNTs和XC-72的耐腐蚀性比较可以看出,GNF比CNTs、XC-72更难被氧化。这证实了GNF比CNTs、XC-72具有更好的耐腐蚀性。因此,采用高能球磨法制备的GNF具备了作为催化剂的载体的基本条件,且具有较好的抗电化学氧化性。
Proton exchange membrane fuel cells (PEMFCs) are promising in energy efficiency, high energy density, no liquid electrolyte corrosion, low temperature quick starting, compacting structure and so on. It has a wide application prospect in electric vehicles, ground stations, underwater submarine and communication power. The main issues are the cost and life, especially in automotive operation at any time when the load changes, the life drops significantly. Now, the best life of PEMFC is 2200h, there being a great distance from the life of 5000h. Therefore, studying failure mechanism of the fuel cell, finding solutions to improve the fuel cell life, promoting the commercialization of fuel cell and reducing environmental pollution is of great significance.
Catalyst durability had been studied by Predecessors and they had gained extensive conclusions. This article focuses on the durability of Nafion electrolyte. Nafion as electrodes’catalyst has different crystallinities at different temperatures. And it has a better stability after high temperature treatment. So change the degree of crystallinity of Nafion to enhance the stability of Nafion by changing electrode post-processing temperature, in order to achieve improving the purpose of the durability of the electrode. In addition, PEMFC catalyst support of the corrosion resistance has been studied. The difficulty of Graphite nanofibers (GNF) as a PEMFC’s support is not nano-scale particles. GNFs’corrosion resistance at room temperature had been studied. This article focuses on preparing GNF using method of high-energy ball milling; wet grinding, studying the durability of GNF at high-temperature (80℃), and conducting the feasibility of GNF as PEMFC catalyst support.
Electrode life testing is studied. The results show that scanning 1000 circle CV in acidic solution environment is an ideal testing method of life, because the electrode performance can be attenuated 57%. By studying post-processing temperature of the electrodes, the electrodes protecting in the N2 atmosphere, constant heating 30min, and heating in the temperature of 180℃have better electrochemical performance, single-battery performance, life expectancy, as well as electrochemical corrosion resistance; The TEM of this electrode shows that its Pt particles are more evenly distributed under these conditions.
The wasted carbon papers are recycled and production rate of 84%. GNF are prepared by the wet high-energy ball milling method. The TEM shows the prepared GNF have been reached nano-particles degree. The EIS shows that the resistance of GNF is the smallest. The comparison among GNF, CNTs and XC-72 shows that GNF have better corrosion resistance.
引文
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