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Development of Ti–V–Cr–Mn–Mo–Ce high-entropy alloys for high-density hydrogen storage in water bath environments

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Abstract

The V-based body-centered cubic (BCC)-type hydrogen storage alloys have attracted significant attention due to their high theoretical hydrogen storage capacity of 3.80 wt%. However, their practical application faces challenges related to low dehydriding capacity and poor activation performance. To overcome these challenges, a BCC-type Ti–V–Cr–Mn–Mo–Ce high-entropy alloy (HEA) with an effectively dehydriding capacity of 2.5 wt% above 0.1 MPa was prepared. By introduction of Mo and conducting heat treatment, the precipitation of Ti-rich phase in HEA was successfully suppressed, resulting in improved compositional uniformity and dehydriding capacity. Consequently, the effective dehydriding capacity increased significantly from 0.60 wt% to 2.50 wt% at 65 °C, surpassing that of other types of hydrogen storage alloys under the same conditions. Moreover, the addition of 1 wt% Ce enabled initial hydrogen absorption at 25 °C without the need for activation at 400 °C. Furthermore, Ce do** reduced the dehydriding activation energy of the Ti–V–Cr–Mn–Mo–Ce HEA from 52.71 to 42.82 kJ·mol−1. Additionally, the enthalpy value of dehydrogenation decreased from 46.89 to 17.96 kJ·mol−1, attributed to a decrease in the hysteresis factor from 0.68 to 0.52. These findings provide valuable insights for optimizing the hydrogen storage property of HEA.

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摘要

钒基体心立方(BCC)型储氢合金因其高达3.80 wt%的理论储氢容量而备受关注。然而, 在实际应用存在着脱氢率低和活化困难等难题。为此, 制备了一种BCC型TiVCrMnMoCe高熵合金(HEA), 该合金在0.1 MPa以上的有效脱氢量达到2.5 wt%。通过引入Mo和热处理, 成功抑制了HEA中富Ti相的析出, 改善了HEA成分均匀性和脱氢能力。在65°C时, HEA有效脱氢量由0.60 wt%提高到2.50 wt%, 在相同条件下优于其他类型储氢合金的有效脱氢量。此外, 添加1 wt%的Ce可以使得HEA无需在400°C下进行活化, 而在25°C下能直接吸氢。Ce的掺杂使得HEA的脱氢活化能从52.71降低到42.82 kJ·mol−1。脱氢焓值从46.89降低到17.96 kJ·mol−1, 这是由于滞后系数从0.68降低到0.52。研究结果为优化HEA的储氢性能提供了指导.

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Acknowledgements

This work was supported by National Key R&D Program of China (No. 2022YFB3504700), the National Natural Science Foundation of China (No. 92061125), and Jiangxi Natural Science Foundation (No. 20212ACB213009).

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  1. Key Laboratory of Rare Earths, Chinese Academy of Sciences, Jiangxi Institute of Rare Earths, Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou, 341000, China

    Hua-Zhou Hu, Hou-Qun **ao, **n-Cong He, Wen-Hao Zhou, **ao-Xuan Zhang, Rui-Zhu Tang, Jie Li, Chuan-Ming Ma & Qing-Jun Chen

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Hu, HZ., **ao, HQ., He, XC. et al. Development of Ti–V–Cr–Mn–Mo–Ce high-entropy alloys for high-density hydrogen storage in water bath environments. Rare Met. (2024). https://doi.org/10.1007/s12598-024-02618-8

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