Key Takeaways & Executive Findings
- •• Co-modification with Ce doping and cold rolling enables room-temperature activation of V70Ti10Cr20 alloy without incubation, achieving 4 wt% hydrogen capacity within 12 minutes. • CeO2 particles act as active sites that facilitate hydrogen penetration through the surface oxide layer, while cold rolling introduces dislocations that create rapid diffusion pathways. • The synergistic effect of Ce alloying and cold rolling significantly outperforms either method alone, reducing activation temperature and time dramatically. • This work provides a practical engineering strategy for improving the activation performance of vanadium-based hydrogen storage alloys, advancing their industrial application.
Abstract
The study investigated the influence of Ce alloying and cold rolling on the activation behavior of V70Ti10Cr20-based alloys. The activation conditions of single cold rolled (V70Ti10Cr20-0.3) and single Ce replaced (V70Ti10Cr20Ce1) samples were reduced from the original two heat treatments to one heat treatment, and the incubation time was about 105 min. Unexpectedly, the two modification methods produce excellent synergistic effects that the co-modified sample (V70Ti10Cr20Ce1-0.5) was activated at room temperature (25°C) without incubation period, and reached saturation capacity (4wt%) within 12 min. Further studies show that CeO2 formed through Ce doping, serves as an active site for hydrogen absorption, facilitating the passage of hydrogen atoms through the dense oxide layer on the surface of vanadium-based alloys. Upon the foundation of Ce doping, cold rolling leads to the aggregation of dislocations around CeO2 sites, thereby further establishing a hydrogen diffusion pathway from the surface into the bulk phase, thus significantly improving the activation performance of the alloy. This work establishes a robust basis for the practical engineering use of vanadium-based hydrogen storage alloys.
1. Introduction
Hydrogen is generally considered to be a zero-carbon energy source today [1–4]. Hydrogen storage alloys with low cost and high hydrogen storage efficiency will undoubtedly become one of the important directions for hydrogen storage in the future [5–9]. In recent years, significant progress has been made in the research of hydrogen storage materials, with the emergence of advanced materials such as high-entropy alloys, magnesium-based (Mg-based) hydrogen storage alloys, and vanadium-based (V-based) hydrogen storage alloys. High-entropy alloys, due to their multi-principal element composition and unique microstructure, exhibit excellent hydrogen storage properties, including high hydrogen storage capacity and good cycling stability [10]. Mg-based hydrogen storage materials have become a research hotspot because of their high theoretical hydrogen storage capacity (7.6wt%) and relatively low cost [11]. In addition, V-based alloys, as an important type of hydrogen storage material, possess distinct physical and chemical characteristics that give them significant advantages in the field of hydrogen storage.
Hydrogen storage alloys based on V have been the subject of extensive research due to their superior characteristics in hydrogen storage, such as high theoretical capacity of 3.8wt%, operation close to room temperature (25°C) and atmospheric pressure. However, V-based alloys with high V content often have poor activation properties. It usually requires preconditioning at a high temperature above 400°C and a long incubation and hydriding time to the completely activation [12]. It is well known that V-based alloys with high V content has good cycle stability and high reversible hydrogen storage capacity, so improving its activation performance is helpful to advancing the practical implementation of V-based hydrogen storage alloys in industry [13–16]. The main reasons for the poor activation performance of V-based hydrogen storage alloys can be attributed to the easy formation of a layer of low activity oxide film on the surface. In order to improve the activation properties, there are two common modification methods: alloying and processing. The doping of Zr and Nb elements produces the secondary phase of C14 Laves structure, which can easily to absorb hydrogen and break the particle to expose fresh surface [17–18]. This idea is generally to enhance the activation performance by reducing the penetration time for hydrogen to break the oxide film, but this optimization method has certain limitations, that is, with the increase of Laves phase, other hydrogen storage capacity are likely to deteriorate. The mechanism of action of rare earth elements such as La and Ce has generally been considered to form a “new hydrogen absorption channel” [19–20]. Taking Ce as an example, the principle of this mechanism is due to its high 4f electron energy level, low electronegativity, and high chemical reactivity. These properties make it easy for Ce to form a second phase of Ce oxide, thereby creating high-activity sites on the alloy surface [21–22]. Mechanical processing methods such as cold rolling, high-pressure torsion (HPT) and mechanical ball milling have signifi
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Zhenguang Huang, Qiang Shen, Shiting Yang, Peimei Dong, Chunju Lv, Meiqiang Fan, Yongfu Cui, Leichao Meng, Chao Li, Zhendong Yao (2025). Impact of Ce doping and cold rolling on the activation performance of V70Ti10Cr20 alloy. Int. Journal of Minerals, Metallurgy and Materials (矿物冶金与材料学报). https://doi.org/10.1007/s12613-025-3175-x
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Frequently Asked Questions
What is the main finding of this study on V70Ti10Cr20 alloy?
The study demonstrates that co-modification with Ce doping and cold rolling enables room-temperature activation of V70Ti10Cr20 alloy without an incubation period, achieving a saturation capacity of 4 wt% within 12 minutes.
How does Ce doping improve the activation performance of vanadium-based alloys?
Ce doping leads to the formation of CeO2 particles on the alloy surface, which act as active sites for hydrogen absorption, facilitating the passage of hydrogen atoms through the dense oxide layer.
What role does cold rolling play in the activation process?
Cold rolling introduces dislocations that aggregate around CeO2 sites, creating a hydrogen diffusion pathway from the surface into the bulk phase, thereby significantly enhancing activation performance.
What are the practical implications of this research?
The findings provide a robust basis for the practical engineering use of vanadium-based hydrogen storage alloys by offering a cost-effective and efficient method to improve their activation performance, which is critical for industrial applications.
What is the significance of the synergistic effect between Ce doping and cold rolling?
The synergistic effect is significant because it reduces the activation temperature from over 400°C to room temperature and eliminates the incubation period, which is a major breakthrough for the practical use of these alloys.
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