Leveraging Atomic Disorder to Modulate Hydrogen Storage Thermodynamics in Intermetallics

Abstract

Hydrogen storage in metal hydrides holds great promise for advancing a low-carbon energy future. Yet, fine-tuning the thermodynamics of hydrogen absorption remains challenging with traditional microalloying approaches. Here, we report a strategy inspired by compositionally complex alloy design to introduce atomic disorder into the prototypical TiFe intermetallic system. By progressively substituting Fe with Co, Ni, Cu, and Mn in equal proportions, we synthesize a series of near-single-phase B2-structured compositionally complex intermetallics, that is, Ti₅₀(FeCo)₅₀, Ti₅₀(FeCoNi)₅₀, Ti₅₀(FeCoNiCu)₅₀, and Ti₅₀(FeCoNiCuMn)₅₀ (at.%). These materials exhibit hydrogen storage capacities (measured by pressure-composition isotherm, PCI) of 1.39, 1.42, 1.31, and 1.14 wt.% under 100 bar of H₂ at 50°C, respectively. Notably, Ti₅₀(FeCo)₅₀ demonstrates rapid hydrogen uptake kinetics, achieving 90% of its full capacity within 77 s under 50 bar of hydrogen pressure at 50°C. Hydrogen storage thermodynamic analyses reveal that increasing atomic disorder stabilizes the hydride phase, with thermodynamic stability following the order: Ti₅₀(FeCoNiCuMn)₅₀ > Ti₅₀(FeCoNi)₅₀ > Ti₅₀(FeCoNiCu)₅₀ > Ti₅₀(FeCo)₅₀. Our findings establish atomic disorder as a versatile thermodynamic tuning knob for intermetallic hydrides, offering a rational framework for the design of advanced hydrogen storage materials.

Keywords

compositionally complex intermetallics / density functional theory calculations / functional properties / hydrogen storage materials

References

[1] E. Tzimas, C. Filiou, S. D. Peteves, and J. B. Veyret, “Hydrogen Storage: State-of-the-Art and Future Perspective,” EU Commission, JRC Petten, EUR 20995EN. 2003.

[2] P. Chen and M. Zhu, “Recent Progress in Hydrogen Storage,” Materials Today 11 (2008): 36–43.

[3] A. Schneemann, J. L. White, S. Kang, et al., “Nanostructured Metal Hydrides for Hydrogen Storage,” Chemical Reviews 118 (2018): 10775–10839.

[4] Y. Wang, Y. Xue, and A. Züttel, “Nanoscale Engineering of Solid-State Materials for Boosting Hydrogen Storage,” Chemical Society Reviews 53 (2024): 972–1003.

[5] Y. Cho, A. J. E. Rowberg, S. Chatterjee, et al., “Chemical Redox Agent-Driven Noncorrosive Formation of Nanoporous Mg Structures for Advanced Hydrogen Storage,” ACS Nano 19 (2025): 5649–5658.

[6] X. Y. Wang, P. Peng, M. D. Witman, V. Stavila, M. D. Allendorf, and H. M. Breunig, “Technoeconomic Insights Into Metal Hydrides for Stationary Hydrogen Storage,” Advancement of Science 12 (2025): 2415736.

[7] Y. Zhang, C. Li, Z. Yuan, Y. Qi, S. Guo, and D. Zhao, “Research Progress of TiFe-Based Hydrogen Storage Alloys,” Journal of Iron and Steel Research International 29 (2022): 537–551.

[8] Y. Shang, S. Liu, Z. Liang, et al., “Developing Sustainable FeTi Alloys for Hydrogen Storage by Recycling,” Communications Materials 3 (2022): 101.

[9] V. Y. Zadorozhnyy, S. N. Klyamkin, M. Y. Zadorozhnyy, O. V. Bermesheva, and S. D. Kaloshkin, “Mechanical Alloying of Nanocrystalline Intermetallic Compound TiFe Doped by Aluminum and Chromium,” Journal of Alloys and Compounds 586 (2014): S56–S60.

[10] Y. Li, H. Shang, Y. Zhang, P. Li, Y. Qi, and D. Zhao, “Investigations on Gaseous Hydrogen Storage Performances and Reactivation Ability of As-Cast TiFe_1−xNi_x (x = 0, 0.1, 0.2 and 0.4) Alloys,” International Journal of Hydrogen Energy 44 (2019): 4240–4252.

[11] E. M. Dematteis, N. Berti, F. Cuevas, M. Latroche, and M. Baricco, “Substitutional Effects in TiFe for Hydrogen Storage: A Comprehensive Review,” Materials Advances 2 (2021): 2524–2560.

[12] E. M. Dematteis, D. M. Dreistadt, G. Capurso, J. Jepsen, F. Cuevas, and M. Latroche, “Fundamental Hydrogen Storage Properties of TiFe-Alloy With Partial Substitution of Fe by Ti and Mn,” Journal of Alloys and Compounds 874 (2021): 159925.

[13] H. Emami, K. Edalati, J. Matsuda, E. Akiba, and Z. Horita, “Hydrogen Storage Performance of TiFe After Processing by Ball Milling,” Acta Materialia 88 (2015): 190–195.

[14] T. Suda, M. Ohkawa, S. Sawada, S. Watanabe, S. Ohnuki, and S. Nagata, “Effect of Surface Modification by Ion Implantation on Hydrogenation Property of TiFe Alloy,” Materials Transactions 43 (2002): 2703–2705.

[15] L. E. R. Vega, D. R. Leiva, R. M. Leal Neto, et al., “Mechanical Activation of TiFe for Hydrogen Storage by Cold Rolling Under Inert Atmosphere,” International Journal of Hydrogen Energy 43 (2018): 2913–2918.

[16] Z. Yuan, Y. Sui, Q. Yuan, et al., “Effects of Ball Milling Time on the Microstructure and Hydrogen Storage Performances of Ti_21.7Y_0.3Fe₁₆Mn₃Cr Alloy,” International Journal of Hydrogen Energy 48 (2023): 11340–11351.

[17] J. W. Yeh, S. K. Chen, S. J. Lin, et al., “Nanostructured High-Entropy Alloys With Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes,” Advanced Engineering Materials 6 (2004): 299–303.

[18] B. Cantor, I. T. H. Chang, P. Knight, and A. J. B. Vincent, “Microstructural Development in Equiatomic Multicomponent Alloys,” Materials Science and Engineering: A 375–377 (2004): 213–218.

[19] E. P. George, D. Raabe, and R. O. Ritchie, “High-Entropy Alloys,” Nature Reviews Materials 4 (2019): 515–534.

[20] J. T. Ren, L. Chen, H. Y. Wang, and Z. Y. Yuan, “High-Entropy Alloys in Electrocatalysis: From Fundamentals to Applications,” Chemical Society Reviews 52 (2023): 8319–8373.

[21] S. Schweidler, M. Botros, F. Strauss, et al., “High-Entropy Materials for Energy and Electronic Applications,” Nature Reviews Materials 9 (2024): 266–281.

[22] Z. Li, R. Wu, D. Duan, et al., “Empowering Multicomponent Alloys With Unique Nanostructure for Exceptional Oxygen Evolution Performance Through Self-Replenishment,” Joule 8 (2024): 2920–2937.

[23] Z. W. Chen, J. Li, P. Ou, et al., “Unusual Sabatier Principle on High Entropy Alloy Catalysts for Hydrogen Evolution Reactions,” Nature Communications 15 (2024): 359.

[24] L. He, M. Li, L. Qiu, et al., “Single-Atom Mo-Tailored High-Entropy-Alloy Ultrathin Nanosheets With Intrinsic Tensile Strain Enhance Electrocatalysis,” Nature Communications 15 (2024): 2290.

[25] H. Luo, Z. Pan, T. Yang, et al., “A High-Entropy Alloy for Superior Resistance to Biogenic Sulfuric Acid Corrosion and Hydrogen Embrittlement,” Matter 8 (2025): 101944.

[26] S. Dangwal and K. Edalati, “High-Entropy Alloy TiV₂ZrCrMnFeNi for Hydrogen Storage at Room Temperature With Full Reversibility and Good Activation,” Scripta Materialia 238 (2024): 115774.

[27] S. Dangwal, Y. Ikeda, B. Grabowski, and K. Edalati, “Machine Learning to Explore High-Entropy Alloys With Desired Enthalpy for Room-Temperature Hydrogen Storage: Prediction of Density Functional Theory and Experimental Data,” Chemical Engineering Journal 493 (2024): 152606.

[28] C. Guan, X. Yue, and Q. Xiang, “The Role of Lattice Distortion in Catalysis: Functionality and Distinctions From Strain,” Advanced Materials 37 (2025): 2501209.

[29] R. Kirchheim, “Diffusion of Hydrogen and Other Interstitials in Disordred and Amorphous Materials,” Defect and Diffusion Forum 143 (1997): 911–926.

[30] Z. Ding, Y. Li, H. Jiang, et al., “The Integral Role of High-Entropy Alloys in Advancing Solid-State Hydrogen Storage,” Interdisciplinary Materials 4 (2025): 75–108.

[31] H. Kim, S. Kang, J. Y. Lee, et al., “A New Perspective on the Initial Hydrogenation of TiFe_0.9M_0.1 (M = V, Cr, Fe, Co, Ni) Alloys Gained From Surface Oxide Analyses and Nucleation Energetics,” Applied Surface Science 610 (2023): 155443.

[32] G. K. Sujan, Z. Pan, H. Li, D. Liang, and N. Alam, “An Overview on Tife Intermetallic for Solid-State Hydrogen Storage: Microstructure, Hydrogenation and Fabrication Processes,” Critical Reviews in Solid State and Materials Sciences 45 (2020): 410–427.

[33] A. Santhosh, S. Kang, N. Keilbart, et al., “Influence of Near-Surface Oxide Layers on TiFe Hydrogenation: Mechanistic Insights and Implications for Hydrogen Storage Applications,” Journal of Materials Chemistry A 11 (2023): 18776–18789.

[34] A. Khawam and D. R. Flanagan, “Solid-State Kinetic Models: Basics and Mathematical Fundamentals,” Journal of Physical Chemistry B 110 (2006): 17315–17328.

[35] K. Edalati, J. Matsuda, A. Yanagida, E. Akiba, and Z. Horita, “Activation of TiFe for Hydrogen Storage by Plastic Deformation Using Groove Rolling and High-Pressure Torsion: Similarities and Differences,” International Journal of Hydrogen Energy 39 (2014): 15589–15594.

[36] K. Edalati, M. Matsuo, H. Emami, et al., “Impact of Severe Plastic Deformation on Microstructure and Hydrogen Storage of Titanium-Iron-Manganese Intermetallics,” Scripta Materialia 124 (2016): 108–111.

[37] C. E. Lundin, F. E. Lynch, and C. B. Magee, “A Correlation Between the Interstitial Hole Sizes in Intermetallic Compounds and the Thermodynamic Properties of the Hydrides Formed From Those Compounds,” Journal of the Less Common Metals 56 (1977): 19–37.

[38] D. Kuroda, M. Niinomi, M. Morinaga, Y. Kato, and T. Yashiro, “Design and Mechanical Properties of New β Type Titanium Alloys for Implant Materials,” Materials Science and Engineering: A 243 (1998): 244–249.

[39] F. Kong, X. Liu, Y. Song, et al., “Selectively Coupling Ru Single Atoms to PtNi Concavities for High-Performance Methanol Oxidation via d-Band Center Regulation,” Angewandte Chemie International Edition 61 (2022): e202207524.

[40] A. P. Hammersley, “FIT2D: An Introduction and Overview,” European Synchrotron Radiation Facility Internal Report ESRF97HA02T 68 (1997): 58.

[41] J. B. Nelson and D. P. Riley, “An Experimental Investigation of Extrapolation Methods in the Derivation of Accurate Unit-Cell Dimensions of Crystals,” Proceedings of the Physical Society 57 (1945): 160–177.

[42] L. Lutterotti, S. Matthies, and H. R. Wenk, “MAUD: A Friendly Java Program for Material Analysis Using Diffraction,” IUCr: Newsletter of the CPD 21 (1999): 14–15.

[43] G. Ashiotis, A. Deschildre, Z. Nawaz, et al., “The Fast Azimuthal Integration Python Library,” Journal of Applied Crystallography 48 (2015): 510–519.

[44] G. Kresse and J. Furthmüller, “Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set,” Computational Materials Science 6 (1996): 15–50.

[45] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54 (1996): 11169–11186.

[46] J. P. Perdew, A. Ruzsinszky, G. I. Csonka, et al., “Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces,” Physical Review Letters 100 (2008): 136406.

[47] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77 (1996): 3865–3868.

[48] A. van de Walle, P. Tiwary, M. de Jong, et al., “Efficient Stochastic Generation of Special Quasirandom Structures,” Calphad 42 (2013): 13–18.

[49] G. Henkelman, A. Arnaldsson, and H. Jónsson, “A Fast and Robust Algorithm for Bader Decomposition of Charge Density,” Computational Materials Science 36 (2006): 354–360.

[50] V. Wang, N. Xu, J. C. Liu, G. Tang, and W. T. Geng, “VASPKIT: A User-Friendly Interface Facilitating High-Throughput Computing and Analysis Using VASP Code,” Computer Physics Communications 267 (2021): 108033.

RIGHTS & PERMISSIONS

2026 The Author(s). Interdisciplinary Materials published by Wuhan University of Technology and John Wiley & Sons Australia, Ltd.