Improved hydrogen ab-/desorption performance of Ti–Cr based alloys via dual-effect of oxide reduction and element substitution by minor Al additive

• Published in: International journal of hydrogen energy 2024-01, Vol.53, p.1123-1136
• Main Authors: Cao, Ziming, Zhou, Panpan, Xiao, Xuezhang, Zhang, Haikuo, Jia, Yuxiao, Zhan, Liujun, Piao, Mingyuan, Li, Zhinian, Jiang, Lijun, Chen, Lixin
• Format: Article
• Language: English
• Subjects: Al additive; Aluminothermic reduction; Hydrogen storage performance; Hysteresis amelioration; Substitution; Ti-Cr based alloys
• ISSN: 0360-3199
• DOI: 10.1016/j.ijhydene.2023.11.334

Hysteresis of hydrogen storage alloys essentially hinders the compressibility and operation efficiency of metal hydride hydrogen compressors. In this work, minor Al additive was added into Ti–Cr based hydrogen compression alloys through induction levitation melting, and the apparent hysteresis was successfully ameliorated. The XRD and SEM results indicate homogeneous element distribution of a main C14 Laves phase of Ti0.96Zr0.06Cr1.0Mn0.6Fe0.4Alx (x = 0, 0.01, 0.02, 0.04, 0.08) alloys, and vanishing of a minor oxide phase in case the Al additive is introduced. As Al stoichiometry increases in the alloys, the hydrogenation plateau decreases obviously but the dehydrogenation plateau hardly changes. Meanwhile, the hydrogen capacity ascends initially but descends slightly. Additionally, no severe performance degradation is induced. The mechanism for overall performance improvement can be concluded as dual functions of Al additive: one can be oxide reduction of other elements during melting determined by XPS and ICP, and the other can be partial Al substitution for the B-side elements, leading to relieved deformation energy surrounding the vacant Al-containing interstitials. As to hydrogenation kinetics, the alloys exhibit accelerated hydrogenation rate with increased Al stoichiometry due to decreased activation energy and hydrogenation plateau. Furthermore, the first-principles calculation results indicate random Al substitution for the B-side atoms, and anisotropic expansion of the unit cell can be attributed to Al substitution at 6h sites. This work reveals a simple and effective way to enhance hydrogen storage performance of Ti–Cr based alloys. [Display omitted] •Influence of minor Al additive in Ti–Zr–Cr–Mn–Fe based alloys is investigated.•Hysteresis is remarkably modified by Al additive with overall enhanced performance.•Reduction and substitution dual-effect of Al is key mechanism for modification.•Results of first-principles calculation indicate random Al substitution at B-sites.•Optimum stoichiometry of Al additive should be 0.01–0.04 in the studied alloys.