Hydrogen Induced Phase Transition in TiZrNbHfV1-xTax High Entropy Alloys

Faye Greaves, Anis Bouzidi, Loïc Perrière, Gavin Vaughan, Vivian Nassif, Laetitia Laversenne, Andreas Borgschulte, Murillo Longo Martins, Yongqiang Cheng, Anibal Javier Ramirez-Cuesta, Petra Á Szilágyi, Patrick Cullen, Claudia Zlotea

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Abstract

Two extensively researched high-entropy alloys (HEAs) TiZrNbHfV and TiZrNbHfTa have been reported for their high hydrogen capacities yet have shown different behaviors with regard to hydrogen sorption properties. The first composition reacts with hydrogen within a one-step reaction mechanism associated with a phase transition from an initial body-centered cubic (BCC) lattice to body-centered tetragonal (BCT) dihydride phase while the latter alloy undergoes a two-step process from an initial BCC lattice to an intermediate BCT monohydride and finally to a face-centered cubic (FCC) dihydride. For deeper understanding of this change with the substitution of isoelectronic elements, the TiZrNbHfV1-xTax (where x = 0, 0.25, 0.5, 0.75, and 1) alloys have been investigated. The alloys were successfully synthesized using electric arc-melting, resulting in BCC lattices. Rapid hydrogen absorption kinetics were observed at 300 °C, achieving full capacity (2.0 H/M) in around 2 min under 55 bar. In situ neutron diffraction and thermal-desorption spectroscopy demonstrated a two-step phase transition during hydrogen desorption, transitioning from an FCC dihydride to an intermediate BCT monohydride, and finally to a BCC structure. The substitution of V by Ta was found to destabilize the FCC hydride phase, reducing the desorption onset temperature. These findings underscore the potential for tuning hydrogen storage properties through alloy composition, providing insights into the design of advanced HEAs for energy storage applications.

Original languageEnglish
Pages (from-to)2904-2912
Number of pages9
JournalJournal of Physical Chemistry C
Volume129
Issue number6
DOIs
StatePublished - Feb 13 2025

Funding

Fabrice Couturas, Valérie Lalanne, Olivier Rouleau, and Rémy Pires Brazuna from ICMPE Thiais, France, are acknowledged for their help with hydrogenation, arc-melting, XRD, and SEM-EDX experiments, respectively. F.G. and C.Z. thank Sofien Djellit from D1B-ILL (Institut Laue-Langevin, Grenoble, France) for help with neutron diffraction experiments at ILL. F.G., C.Z., P.A.S., and P.C. acknowledge the funding from the Agence de l’Innovation de Défense (AID, Convention No. 2022 65 0054). A.B., L.P., L.L., V.N., and C.Z. acknowledge the funding from the French ANR MASSHY project ANR-19-CE05-0029-01. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. The beam time was allocated to VISION on proposal number IPTS-29877.1.

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