质子交换膜燃料电池衰减机制及抗反极膜电极研究

质子交换膜燃料电池（PEMFCs）因其功率密度高、零污染以及加氢速度快等优点在近年来得到了广泛地研究、发展和应用。但由阳极缺氢引起的反极工况会拉高PEMFCs单电池（膜电极）的阳极电势，对阳极含碳材料造成不可逆的腐蚀破坏，从而严重削弱PEMFCs的放电功率、稳定性以及寿命，是其大规模商业化推广应用过程中的一大障碍。虽然反极工况可以通过监测电池电压以及尾气成分等手段及时发现并采取短接以及停机等被动措施来中断，但上述被动措施会增加控制系统复杂性和成本并且无法阻止反极对膜电极的破坏。在阳极催化层中加入具有高活性和高稳定性的氧析出反应（OER）催化剂（例如IrO_x, 0≤x≤2）能够通过延长OER电势平台来延缓阳极电势的进一步升高，从而延缓碳腐蚀速率的增大，提高膜电极的抗反极性能。然而上述OER电势平台经过一段时间反极后仍会突然结束，导致阳极电势急剧升高，膜电极失去抗反极能力。

针对上述OER电势平台突然结束的原因目前国际上提出了三种观点：（1）阳极催化层缺水导致OER催化剂缺少反应物，（2）OER催化剂因碳腐蚀导致与周围物质隔绝（物理失活），（3）OER催化剂本身失去催化OER活性（化学失活）。无明确证据支持阳极催化层缺水和OER催化剂化学失活导致OER电势平台失效。本文综述并分析了相关文献研究数据，认为OER催化剂的物理失活是导致OER电势平台突然结束的主要原因。更具体地，OER平台存在的碳腐蚀反应将OER催化剂逐渐与阳极催化层物理隔绝，导致OER催化剂不能有效地向阳极催化层传导OER所产生的电子和质子。因此，建立稳定的电子和质子通道有利于延长OER电势平台，提高膜电极的首次抗反极时间（FRT）。

本文制备了高金属含量的Ir-Pt(1:2)/C复合催化剂，其碳载体表面连续的贵金属纳米颗能够在阳极催化层中构建稳定的电子和质子传输通道，延缓OER催化剂（铱纳米颗粒）的物理失活。与低金属含量的Ir-Pt(1:2)/C相比，高金属含量的Ir-Pt(1:2)/C能够将膜电极的FRT提高至10倍，达到20小时。

常用的商业化OER催化剂（Com-IrO_x）因其团聚状态的微观结构更容易因碳腐蚀而发生物理失活，本文通过低比表面积的碳粉作为牺牲模板成功合成了具有强连接结构的OER催化剂（SC-IrO_x）。SC-IrO_x催化剂由相互连接的IrO_x纳米颗粒组成，同时具有良好的分散性，其在阳极催化层中形成的网状结构可以为OER催化剂提供稳定的电子和质子传输通道，延缓其自身物理失活。与Com-IrO_x催化剂相比，SC-IrO_x催化剂能够将膜电极的FRT延长至3.2倍，达到9.32小时。

由于阳极催化层中碳材料的电化学腐蚀能够引起OER催化剂的物理失活，本文通过低比表面积碳粉作为牺牲模板成功合成了具有树枝状结构的铂黑催化剂并将其与SC-IrO_x催化剂结合用于制备无碳抗反极阳极催化层。无碳阳极催化层能够最大程度地避免因碳腐蚀导致的OER催化剂物理失活。与商业化铂碳催化剂相比，使用铂黑催化剂的无碳阳极催化层能够将膜电极的FRT提高至4.8倍，达到44.5小时。

本文的研究结果表明高金属含量的Ir-Pt(1:2)/C复合催化剂、具有网状互连结构的强连接SC-IrO_x催化剂以及无碳抗反极阳极催化层能够为OER催化剂建立稳定的电子和质子传输通道，延缓OER催化剂因碳腐蚀导致的物理失活，为抗反极阳极催化剂以及催化层的设计和制备提供了新的思路。

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