The role of magnesium on properties of La3-xMgxNi9 (x=0, 0.5, 1.0, 1.5, 2.0) hydrogen storage alloys from first-principles calculations

• Published in: International journal of hydrogen energy Vol. 47; no. 86; pp. 36408 - 36417
• Main Authors: Chen, Yujie, Mo, Xiaohua, Huang, Yong, Hu, Chunyan, Zuo, Xiaoli, Wei, Qi, Zhou, Rui, Li, Xiangyu, Jiang, Weiqing
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 22.10.2022
• Subjects: Electronic structure; First-principles calculation; Hydrogen storage performance; La-Mg-Ni alloy; Hydrogen storage performance; La-Mg-Ni alloy; Electronic structure; First-principles calculation
• ISSN: 0360-3199; 1879-3487
• DOI: 10.1016/j.ijhydene.2022.08.242

The present work gives the electronic structures of La3-xMgxNi9 (x = 0.0–2.0) alloys by first-principles calculations using the generalized gradient approximation of Perdew-Wang 91 (GGA-PW91) method within Cambridge Serial Total Energy Package (CASTEP), aiming at gaining insight into the hydrogen storage mechanism of La3-xMgxNi9 alloys modified by Mg. The results show that the La3-xMgxNi9 alloys consist predominantly of interactions between La-Ni, Ni-Ni or/and Mg-Ni. Among them, La-Ni interaction is the major factor controlling the structural stability of the alloys. Mg substitution increases the La-Ni bonding interactions to achieve stable Mg-containing metal matrices for reversible hydrogen absorption-desorption. This is particularly obvious at high Mg composition, as the La-Ni interactions gradually increase with Mg content. The increase of La-Ni interactions coupled with the decrease of Mg-Ni and Ni-Ni interactions will relieve the hydrogen-induced amorphization and disproportionation, and subsequently enhance the cyclic stability of La3-xMgxNi9 alloys at high Mg content. However, Mg substitution for La leads to a subsequent contraction in cell volume, dramatically reducing the reversible H capacity at high Mg composition such as LaMg2Ni9. Suitable Mg content in La-Mg-Ni systems, such as an approximately range x = 1.0–1.4 in La3-xMgxNi9 alloys, is required in trade-off between hydrogen storage capacity and cycle life. •La3-xMgxNi9 (x = 0–2) alloys with defined La and Mg atoms are introduced for calculation.•Mg substitution leads to a gradual contraction in cell volume for less H-capacity.•La-Ni interaction is dominant in the structural stability of La3-xMgxNi9 alloys.•Increased La-Ni and decreased Mg/Ni-Ni interactions favor for cycle stability.