质子交换膜燃料电池中铱基催化剂抗反极研究

质子交换膜燃料电池（PEMFC）具有功率密度高、无电解质泄露风险、可于室温下快速启停、清洁和无二氧化碳排放等优点，已成为潜力巨大、被广泛关注的新型车载动力电源。然而，PEMFC的高成本和低耐久性阻碍了其大规模商业化应用，阳极燃料不足引起的电池反极是PEMFC性能衰减的主要因素。因此，通过克服PEMFC中的反极问题来解决阳极材料耐久性差的问题，是促进其大规模商业应用的关键。在这项研究中，我们研究了一种氧化铱（IrO_X）基水电解催化剂，并将其添加到膜电极（MEA）中，以提高PEMFC的抗反极性能。本论文主要研究了三种提高PEMFC耐久性的IrO_X基阳极催化剂。

（1）负载型IrO_X类催化剂。无机金属氧化物，尤其是二氧化钛或掺杂二氧化钛，由于其在恶劣环境中的高稳定性，有希望成为IrO_X纳米颗粒（NPs）的载体。然而二氧化钛的电导率相对较低。基于此，开展基于IrO_X NPs均匀分散在Nb掺杂的TiO₂上，作为阳极高电位条件下的耐腐蚀载体。评估了所制备催化剂的物理化学性质，并通过半电池和全电池测试研究了其电化学活性。在常规三电极体系中，所制备的20 wt.% IrO_X/Nb_0.1Ti_0.9O₂-700在电流密度10 mA cm^-2下析出氧气的过电位是330 mV。与此同时，在模拟缺氢条件下MEA进行抗反极测试。以IrO_X/Nb_0.1Ti_0.9O₂-700作为抗反极阳极（RTA）的MEA表现出最长的抗反极时间（29.1 min）。该研究为优化Ir表面电子结构、提高Ir催化活性稳定性提出了一种新方法。在燃料电池中应用该催化剂，可降低80%的Ir载量，从而降低燃料电池的成本。

（2）研究质子交换膜燃料电池阳极添加剂铱氧化物（IrO_X）的晶体结构和抗反极性能的关系。反极可以通过在阳极催化剂层添加基于析氧电催化剂铱氧化物（IrO_X）来克服。阳极材料的晶体结构和抗反极性能研究较少。基于此，开展并探讨非晶态的IrO_X在热处理下晶体结构的转变，以研究其在PEMFCs中的抗反极性能。研究发现，热处理导致催化剂颗粒变大，从而降低了析氧反应（OER）活性，然而它表现出更好的抗反极性能（132.2 min）。这表明在PEMFCs的抗反极性能中，活性和稳定性之间的均衡是至关重要的。物理表征说明稳定性和抗反极能力的提高归因于IrO_X晶体的结晶度和择优取向，以及非晶态和晶态IrO_X的共存。本工作提出了在抗反极阳极催化剂中尝试使用混合相IrO_X，并强调了相应的颗粒大小和稳定性对PEMFC长期耐久性的作用。

（3）IrO_X中空纳米球与间质C作为质子交换膜燃料电池的抗反极阳极电催化剂。我们证明了通过引入间质碳（C-IrO₂-IrSe）可以同时提高IrO₂的稳定性和活性。通过Se的蒸发和C的燃烧制备了C-IrO₂-IrSe催化剂。将C载IrSe₂空心纳米球（IrSe₂ HNSs）在400℃空气气氛下加热20 h，生成C-IrO₂-IrSe-20。优化后的IrO₂-IrSe-20表现出增强的OER活性，显著高于商用IrO₂。更重要的是，IrO₂-IrSe-20表现出了更好的稳定性，在0.5 M H₂SO₄中，在电流密度为10 mA cm^-2的条件下可以持续23.4 h，是文献报道的最稳定的酸性OER电催化剂之一。与此同时，在模拟缺氢条件下MEA进行抗反极测试。以IrO₂-IrSe-20作为抗反极阳极（RTA）的MEA在所有MEA中表现出最长的抗反极时间（206.8 min）。通过引入间质C可以稳定IrO₂，从而可以作为一种强酸性OER和抗反极双功能电催化剂。

Proton exchange membrane fuel cells (PEMFCs) are a promising renewable energy source for automotive applications due to their high power density, lack of electrolyte leakage risk, quick start and stop at room temperature, as well as clean and zero carbon dioxide emissions. However, the widespread use of PEMFCs is hindered by their high cost and low durability. The primary factor for performance attenuation in PEMFCs is the cell voltage reversal caused by fuel starvation at the anode. Therefore, overcoming the voltage reversal problem in PEMFCs to enhance their durability is critical for promoting their large-scale commercial application. In this study, we investigated the potential of an iridium oxide (IrOx)-based water electrolysis catalyst incorporated into membrane electrode assemblies (MEAs) to improve the voltage reversal tolerance performance of PEMFC. The thesis comprises three studies on IrOx-based anode catalysts aimed at enhancing the durability of PEMFCs.

Inorganic metal oxides, especially titanium dioxide or doped titanium dioxide, are promising candidates to support IrO₂ nanoparticles (NPs) due to their high stability in harsh environments. However, the conductivity of TiO₂ is relatively low. Herein, we have fabricated IrO_X NPs dispersed on Nb-doped TiO₂, a corrosion resistant support under anodic high potential conditions. The physicochemical properties of as-prepared catalysts were evaluated using various spectroscopic techniques and the electrochemical activity was investigated by half-cell and full cell tests. The as-prepared IrO_X/Nb_0.1Ti_0.9O₂-700 required an initial overpotential of 330 mV to catalyze water oxidation at 10 mA cm^-2 in a conventional three-electrode cell. Meanwhile, the reversal tolerance was analyzed in a MEA setup under simulated hydrogen starvation conditions. The MEA with IrO_X/Nb_0.1Ti_0.9O₂-700 as the reversal tolerant anodes (RTAs) exhibited an extended reversal tolerance time of 29.1 minutes among the various MEAs. This study proposed a new method for optimizing the electronic structure of the Ir surface and enhancing the stability of Ir catalytic activity. Furthermore, the application of the catalyst in fuel cells can reduce the Ir loading by 80%, thus decreasing the cost of fuel cells.

Similarly, in another work on voltage reversal tolerance in PEMFCs, we have incorporated IrO_X-based electrocatalysts for oxygen evolution reaction (OER) into the anode catalyst layer. The crystal structure and antireversal properties of anode materials have received little attention in previous studies. An amorphous IrO_X was prepared and its crystal structure transformation was analyzed under heat treatment to investigate its antireversal performance in PEMFCs. It is found that heat treatment results in larger catalyst particles which consequently lowers OER activity; however, it shows better voltage reverse tolerance (132.2 min). These investigations demonstrate that a balance between activity and durability is crucial for antireversal properties in PEMFCs. Physical characterizations revealed that improved stability and reversal tolerance are attributed to crystallinity and preferred orientation of IrO_X crystals as well as the existence of amorphous and crystalline IrO_X. This work proposes an attempt to use the mixed phase IrO_X in the antireversal anode catalyst and highlights the role of corresponding particle size and durability characteristics for the long-term durability of PEMFCs.

Finally, we have demonstrated high activity and stability of IrO₂ simultaneously by introducing interstitial carbon (C-IrO₂-IrSe). The C-IrO₂-IrSe catalyst was prepared through the combined evaporation of Se and combustion of C. Specifically, the C-supported IrSe₂ hollow nanospheres (IrSe₂ HNSs) were heated for 20 h at 400 ℃ in air atmosphere to generate C-IrO₂-IrSe-20. The optimized C-IrO₂-IrSe-20 exhibits substantially higher OER activity than that of commercial IrO₂. More importantly, C-IrO₂-IrSe-20 shows improved stability, which can endure up to 23.4 h at current densities of 10 mA cm^-2 in 0.5 M H₂SO₄, representing one of the most stable acidic OER electrocatalysts reported in the literature. Meanwhile, reversal tolerance was analyzed in a membrane electrode assembly (MEA) setup under a simulated hydrogen starvation condition. The MEA with the C-IrO₂-IrSe-20 as the reversal tolerant anodes exhibited the longest reversal tolerance time (206.8 min) compared to all the other MEAs tested. Therefore, experimental results demonstrate that IrO₂ can be stabilized by introducing interstitial C and thus can be used as a robust acidic OER and reversal tolerant bifunctional electrocatalyst.

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