Hydrogen storage properties of amorphous and nanocrystalline (Mg24Ni10Cu2)100-xNdx (x = 0–20) alloys
Introduction
Hydrogen is deemed as one of the best fuels among all kinds of energy sources in the world for its convenient transportation, high efficiency, high safety coefficient and non-pollution [1]. For realizing the large-scale utilization of hydrogen, hydrogen storage technology becomes the key factor. For now, metal hydride systems are regarded as a good hydrogen storage method for its characters of high accurate, efficient and safe [2], [3], [4], [5], [6], [7], [8], [9]. Mg2Ni-type metal hydrides have many advantages, including high theoretical electrochemical capacity (about 1000 mAh/g) and gaseous hydrogen storage capacity of 3.6 wt% for Mg2NiH4 [10], [11], for which they are outstanding in the utilization in Ni-MH battery negative electrode and hydrogen fuel cell vehicle (HFCV) [12]. However, to realize the large-scale commercial application of hydrogen storage materials, there are still many obstacles need to be overcome, such as the high dehydriding temperature, tardy de-/hydriding kinetics and weak electrochemical cycle stability [13].
As a matter of fact, the chemical compositions and crystalline structures of hydride electrode materials show a lot of influence on their specific capacity and de-/hydriding kinetics [14]. It has been ascertained that comparing with crystalline Mg2Ni, the amorphous and nanocrystalline Mg and Mg-based alloys have larger hydrogen storage capacity and better de-/hydriding kinetics [2], [15]. Undoubtedly, high energy ball-milling is a common method for getting Mg or Mg-based alloys with an amorphous and nanocrystalline structure [12], [16]. However, the metastable structures generated during milling process are easily to be vanished after multiple electrochemical dis-/charging cycles, which results in the poor cycle stability of milled Mg or Mg-based alloys [17]. It is a great challenge for their large-scale application in batteries. As to melt spinning, it improves the Mg-based alloys not merely in overcoming the deficiencies mentioned above, but also in improving the electrochemical dis-/charging cycle stability [18]. In fact, Huang et al. [19] prepared an amorphous and nanocrystalline as-spun (Mg60Ni25)90Nd10 alloy which has a high discharge capacity of 580 mAh/g. Spassov et al. [20] found the rapid solidified Mg63Ni30Y7 alloy holds a maximal hydrogen storage capacity of about 3.0 wt%.
Form our previous work we found that replacing Ni by M (M = Cu, Co, Mn) or substituting Mg by La will dramatically improve the Mg2Ni-type alloys in both electrochemical and gaseous hydrogen storage properties [21], [22]. Thus, it can be anticipated that combing the addition of Cu and Nd elements with melt spinning process may significantly promote Mg2Ni-type alloys in hydrogen storage performances. For validating this judgment, we prepared the as-cast and spun (Mg24Ni10Cu2)100-xNdx (x = 0–20) alloys and performed a systematical research on the influence of adding Nd and Cu on their structures and electrochemical hydrogen storage performances.
Section snippets
Experimental
For convenience, we take Nd0, Nd5, Nd10, Nd15 and Nd20 to represent the (Mg24Ni10Cu2)100-xNdx (x = 0, 5, 10, 15 and 20) alloys with different Nd contents respectively in this experiment. The purities of the metallic materials of Mg, Ni, Cu, and Nd are at least 99.99%, which were all provided by CISRI Corporation. Under the protection of helium of 0.04 MPa, whose purity is 99.9% supplied by CISRI Corporation, the alloy ingots were prepared in a vacuum induction furnace. Partial alloy ingots were
Phase compositions and microstructures
Fig. 1 shows the XRD curves of the as-cast and spun (20 m/s) (Mg24Ni10Cu2)100-xNdx (x = 0–20) alloys. It can be found from Fig. 1 (a) that adding Nd changes the phase compositions of alloys. Obviously, each as-cast alloy holds a multiphase structure. Before adding Nd, the as-cast Nd0 alloy contains two phases of Mg2Ni (ICDD PDF 35-1225) as main phase and Mg6Ni (ICDD PDF 51-1179) as second phase. After adding Nd, there generate two new second phases of NdNi (ICDD PDF 19-0818) and Nd5Mg41 (ICDD
Conclusions
The as-cast and spun (Mg24Ni10Cu2)100-xNdx (x = 0–20) alloys were prepared in this work. We studied the alloys systematically in hydrogen storage properties and got the following primary conclusions:
- 1.
All as-cast alloys are multi-phased including the major phase Mg2Ni and some second phases. After adding Nd element, new phases of Nd5Mg41 and NdNi are generated and their proportions increase markedly with Nd content rising. Adding Nd improves the Mg2Ni-type alloy in glass formation, and increases
Acknowledgements
This work is financially supported by the National Natural Science Foundations of China (51761032 and 51471054) and Natural Science Foundation of Inner Mongolia, China (2015MS0558).
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