离子交换树脂对Pt/C催化剂耐久性的影响

Influence of ionomer on the durability of Pt/C catalyst

  • 摘要: 离子交换树脂(Ionomer)是质子交换膜燃料电池催化层的重要组成部分,它在催化层中的主要作用是作为质子传导相传导质子。本文采用旋转圆盘电极法(RDE),在模拟燃料电池真实的运行环境(模式一)和模拟燃料电池启停环境(模式二)两种模式下,研究了Ionomer对铂碳催化剂电压循环耐久性的影响。通过相同位置透射电镜分析法(IL-TEM),分析了铂碳催化剂经历模式二耐久性测试后的结构变化。研究发现Ionomer的存在可以提高铂碳催化剂的耐久性。在模式一的测试中:添加Ionomer后,其氧还原半波电位下降值∆E从23 mV下降至11 mV;没有发生碳的腐蚀,Pt颗粒的长大是催化剂性能下降的主要原因;Ionomer的存在延缓了Pt电化学比表面积(ECSA)的降低从而有利于保持Pt的活性。在模式二的测试中:添加Ionomer后,其氧还原半波电位下降值∆E从25 mV下降至5 mV,除了铂颗粒长大外还发生了载体碳的腐蚀;Ionomer的存在同样可以保持Pt的活性;IL-TEM分析可以看到明显的铂颗粒长大和碳腐蚀,碳载体的腐蚀造成铂的严重流失和团聚。含Nafion的催化剂中铂颗粒平均粒径从2.7 nm增加到了3.76 nm,不含Nafion的催化剂中的铂颗粒平均粒径从2.44 nm增加到了4.19 nm。

     

    Abstract: Ionomer is an important part of the catalytic layer in proton exchange membrane fuel cell. Its main role is to conduct protons. We investigated the effect of ionomer on the durability of Pt/C catalyst using rotating disk electrode (RDE) under two modes: the real operating conditions (mode 1) and startup/shutdown conditions (mode 2). The structural changes of Pt/C catalyst after the durability test were analyzed by identical location transmission electron microscopy (IL-TEM). Results show that the addition of ionomer improved the durability of Pt/C catalysts. After the durability test of mode 1, the addition of ionomer reduced the change of half-wave potential (∆E1/2) of oxygen reduction reaction from 23 to 11 mV, which is attributed to the growth of Pt particles rather than carbon corrosion. Ionomer delayed the decrease of electrochemical specific surface area (ECSA) of Pt/C catalyst, which is beneficial to the maintenance of Pt activity. After the durability test of mode 2, in addition to the growth of platinum particles, carbon corrosion occurred in the catalyst layer, and the growth of platinum particles was mainly due to carbon corrosion. The addition of ionomer reduced the ∆E1/2 of oxygen reduction reaction from 25 to 5 mV. Furthermore, the growth of platinum particles and carbon corrosion can be clearly seen by IL-TEM, and the corrosion of the carbon support resulted in the loss and agglomeration of platinum. The average particle size of platinum in Nafion-containing catalyst increased from 2.7 to 3.76 nm, while that of Nafion-free catalyst increased from 2.44 nm to 4.19 nm.

     

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