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Hangyan Shi, Yingxian Zhang, Zhenglong Li, Fan Gao, Xinqiang Wang, Yaxiong Yang, Yanxia Liu, Xuezhang Xiao, Fang Fang, and Wen-Gang Cui, Unraveling the poisoning mechanism of impurity gases on TiFe hydrogen storage alloys, Int. J. Miner. Metall. Mater., (2025). https://doi.org/10.1007/s12613-025-3138-2
Hangyan Shi, Yingxian Zhang, Zhenglong Li, Fan Gao, Xinqiang Wang, Yaxiong Yang, Yanxia Liu, Xuezhang Xiao, Fang Fang, and Wen-Gang Cui, Unraveling the poisoning mechanism of impurity gases on TiFe hydrogen storage alloys, Int. J. Miner. Metall. Mater., (2025). https://doi.org/10.1007/s12613-025-3138-2
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揭示杂质气体对TiFe储氢合金的毒化机制

摘要: TiFe合金作为AB型固态储氢材料的典型代表,因其低成本、原料丰富、可在室温下进行吸放氢,成为了近年来固态储氢领域的研究热点。然而,杂质气体(如O2、CO、CO2和CH4)的存在对TiFe合金的储氢容量和动力学产生显著影响,极大限制了其在固态储氢领域的实际应用。因此,本文针对TiFe0.9合金在不同杂质气体(CH4、CO、CO2和O2)下的吸氢动力学及循环性能展开研究,并探究了合金在气体毒化过程中的微观结构变化规律。结合理论计算以及实验结果,清楚的阐明了CH4、CO、CO2和O2杂质气体对TiFe0.9储氢合金的毒化机制。研究结果表明,CH4虽不与合金发生化学反应,但通过物理覆盖作用影响合金的吸氢动力学;相反,CO和CO2占据H2活性位点,显著阻碍H2解离与吸附,减缓了合金的吸氢动力学。此外,O2直接与合金反应形成钝化层,阻碍氢气吸附,导致合金储氢容量降低。

 

Unraveling the poisoning mechanism of impurity gases on TiFe hydrogen storage alloys

Abstract: TiFe alloys are AB-based hydrogen storage materials with unique characteristics and a wide range of applications. However, the presence of impurity gases (such as O2, CO, CO2, and CH4) has a considerable impact on the hydrogen storage capacity and kinetics of TiFe alloys, drastically limiting their practical application in hydrogen storage. Consequently, in this study, we investigated the hydrogen absorption kinetics and cycling performance of the TiFe0.9 alloy in the presence of common impurity gases (including CH4, CO, CO2, and O2) and determined the corresponding poisoning mechanisms. Specifically, we found that CH4 did not react with the alloy but acted through physical coverage. In contrast, CO and CO2 occupy the active sites for H2, significantly impeding the dissociation and absorption of H2. In addition, O2 reacts directly with the alloy to form a passivating layer that prevents hydrogen absorption. These findings were further corroborated by in situ Fourier transform infrared spectrometry (FTIR) and density functional theory (DFT). The relationship between the adsorption energies of the impurity gases and hydrogen obtained through DFT calculations complements the experimental results. Understanding these poisoning behaviors is crucial for designing Ti-based high-entropy hydrogen storage alloy alloys with enhanced resistance to poisoning.

 

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