Electrochemical charge-discharge characteristics of composites based on Mg2Ni/Mg and transition metals

Keywords

magnesium, nickel, composite materials, electrochemical properties, nickel-metal hydride batteries.

Cite as

Verbovytskyy Yu. V., Zavaliy I. Yu., and Zasadnyy T. M. Electrochemical charge-discharge characteristics of composites based on Mg₂Ni/Mg and transition metals. Physicochemical Mechanics of Materials. 2025. 61(5), 005-011.

https://doi.org/10.15407/pcmm2025.05.005

Abstract

Mechanical ball milling of Mg₂Ni/Mg alloys with transition metal (Ni, Co, Cu) powders resulted in the formation of nanostructured or amorphous materials. Negative electrodes based on these synthesized composites exhibited improved electrochemical charge-discharge properties. Specifically, the electrode containing the Mg₂Ni + Ni composite achieved a high initial discharge capacity of 810 mAh/g. While the composites with cobalt and copper showed lower capacity than with the nickel composite, their cyclic stability was somewhat better. The electrodes remained amorphous during cycling. However, after a certain time of operation, they began to show signs of degradation, particularly the formation of magnesium hydroxide.

References

1. G. Liang, J. Huot, S. Boily, A. Van Neste, and R. Schulz, “Catalytic effect of transition metals on hydrogen sorption in nanocrystalline ball milled MgH2-Tm (Tm=Ti, V, Mn, Fe and Ni) systems,” J. Alloys Compd., 292, 247-252 (1999). https://doi.org/10.1016/S0925-8388(99)00442-9
2. C. X. Shang, M. Bououdina, and Z. X. Guo, “Structural stability of mechanically alloyed (Mg+10Nb) and (MgH2+10Nb) powder mixtures,” J. Alloys Compd., 349, 217-223 (2003). https://doi.org/10.1016/S0925-8388(02)00920-9
3. S. Rivoirard, P. de Rango, D. Fruchart, “Catalytic effect of additives on the hydrogen absorption properties of nano-crystalline MgH2(X) composites,” J. Alloys Compd, 356-357, 622-625 (2003). https://doi.org/10.1016/S0925-8388(03)00145-2
4. J. Charbonnier, P. de Rango, D. Fruchart, S. Miraglia, L. Pontonnier, S. Rivoirard, N. Skryabina, and P. Vulliet, “Hydrogenation of transition element additives (Ti, V) during ball milling of magnesium hydride,” J. Alloys Compd, 383, 205-208 (2004). https://doi.org/10.1016/j.jallcom.2004.04.059
5. W. Oelerich, T. Klassen, and R. Bormann, “Metal oxides as catalysts for improved hydrogen sorption in nanocrystalline Mg-based materials,” J. Alloys Compd., 325, 237-242 (2001). https://doi.org/10.1016/S0925-8388(00)01284-6
6. C. X. Shang, M. Bououdina, Y. Song, and Z. X. Guo, “Mechanical alloying and electronic simulations of (MgH2+M) systems (M=Al, Ti, Fe, Ni, Cu and Nb) for hydrogen storage,” Int. J. Hydrogen Energy, 29, 73-80 (2004). https://doi.org/10.1016/S0360-3199(03)00045-4
7. H. Blomqvist, Magnesium Ions Stabilizing Solid-State Transition Metal Hydrides. Dissertation. Institutionen for Fysikalisk kemi, Organisk kemi och Strukturkemi Stockholms Universitet, Stockholm, 2003.
8. W. H. Liu, Y. Q. Lei, D. L. Sun, J. Wu, and Q. D. Wang, “A study of the degradation of the electrochemical capacity of amorphous Mg50Ni50 alloy,” J. Power Sources, 58, 243-247 (1996). https://doi.org/10.1016/S0378-7753(96)02394-4
9. N. Cui, B. Luan, H. K. Liu, and S. X. Dou, “Discharge behaviour of Mg2Ni-type hydrogen-storage alloy electrodes in 6 M KOH solution by electrochemical impedance spectroscopy,” J. Power Sources, 63, 209-214 (1996). https://doi.org/10.1016/S0378-7753(96)02473-1
10. H. T. Yuan, Q. D. Li, H. N. Song, Y. J. Wang, and J. W. Liu, “Electrochemical characteristics of Mg2Ni-type alloys prepared by mechanical alloying,” J. Alloys Compd., 353, 322-326 (2003). https://doi.org/10.1016/S0925-8388(02)01325-7
11. M. Anik, “Electrochemical hydrogen storage capacities of Mg2Ni and MgNi alloys synthesized by mechanical alloying,” J. Alloys Compd., 491, 565-570 (2010). https://doi.org/10.1016/j.jallcom.2009.11.004
12. Y. Q. Lei, Y. M. Wu, Q. M. Yang, J. Wu, and Q. D. Wang, “Electrochemical behavior of some mechanically alloyed Mg – Ni-based amorphous hydrogen storage alloys,” Z. Phys. Chem., 183, 379-384 (1994). https://doi.org/10.1524/zpch.1994.183.Part_1_2.379
13. Y. Zhang, Z. Yuan, T. Yang, T. Zhai, Z. Liu, and S. Guo, “Highly improved electrochemical performances of the nanocrystalline and amorphous Mg2Ni-type alloys by substituting Ni with M (M = Cu, Co, Mn),” J. Wuhan Univ. Technol.-Mat. Sci. Edit., 32, 685-694 (2017). https://doi.org/10.1007/s11595-017-1653-3
14. K. Tatsuoki, and K. Motoya, “Effect of partial substitution on hydrogen storage properties of Mg2Ni alloy,” J. Electrochem. Soc., 144, 2384-2388 (1997). https://doi.org/10.1149/1.1837823
15. S. Noharaa, N. Fujitab, S.G. Zhanga, H. Inouea, and C. Iwakuraa, “Electrochemical characteristics of a homogeneous amorphous alloy prepared by ball-milling Mg2Ni with Ni,” J. Alloys Compd., 267, 76-78 (1998). https://doi.org/10.1016/S0925-8388(97)00491-X
16. M. Li, Yu. Zhu, C. Yang, J. Zhang, W. Chen, and L. Li, “Enhanced electrochemical hydrogen storage properties of Mg2NiH4 by coating with nano-nickel,” Int. J. Hydrogen Energy, 40, 13949-13956 (2015). https://doi.org/10.1016/j.ijhydene.2015.08.076
17. S. Huaiyu, and L. Xingguo, “Effect of nanostructure and partial substitution on gas absorption and electrochemical properties in Mg2Ni-based alloys,” J. Alloys Compd., 667, 191-197 (2016). https://doi.org/10.1016/j.jallcom.2016.01.180
18. Yu. V. Verbovytskyy, N. Y. Zhurina, I. Yu. Zavaliy, and T. M. Zasadnyy, “Magnesium composite materials for nickel-metal hydride batteries,” Powder Metall. Met. Ceram., 57, 679-686 (2019). https://doi.org/10.1007/s11106-019-00031-w
19. Yu. V. Verbovytskyy, V. V Oprysk, V. V. Shtender, and I. Yu. Zavaliy, “Hydrogen sorption properties of materials based on alloys and components with a high content of magnesium,” Mater. Sci., 57, Is. 3, 366-376 (2021). https://doi.org/10.1007/s11003-021-00551-0
20. W. Kraus, and G. Nolze, PowderCell for Windows, Federal Institute for Materials Research and Testing, Berlin (1999).
21. J. Rodriguez-Carvajal, and T. Roisnel, “FullProf.98 and WinPLOTR: New Windows 95/NT applications for diffraction commission for powder diffraction.” International Union for Crystallography, Newsletter Is.°20 (May-August) Summer (1998).
22. Kh. I. Vlad, Yu. V. Verbovytskyy, V. M. Bogatyrov, and I. Yu. Zavaliy, “Structure and electrochemical charge-discharge properties of Ni-Co-C nanocomposites,” Mater. Sci., 58, No. 6, 788-794 (2023). https://doi.org/10.1007/s11003-023-00731-0
23. I. Y. Marchuk, T. M. Zasadnyy, and I. Y. Zavaliy, “Hydrogenation of nickel and Ni-based materials (a review),” Mater. Sci., 60, No. 6, 675-683 (2025). https://doi.org/10.1007/s11003-025-00936-5
24. M. Abdellaoui, S. Mokbli, F. Cuevas, M. Latroche, A. Percheron-Guégan, and H. Zarrouk, “Structural and electrochemical properties of amorphous-rich MgxNi100-x nanomaterial obtained by mechanical alloying,” J. Alloys Compd., 356-357, 557-561 (2003). https://doi.org/10.1016/S0925-8388(03)00119-1
25. M. Anik, G. Özdemir, N. Küçükdeveci, and B. Baksan, “Effect of Al, B, Ti and Zr additive elements on the electrochemical hydrogen storage perfor¬mance of MgNi alloy,” Int. J. Hydrogen Energy, 36, 1568-1577 (2011). https://doi.org/10.1016/j.ijhydene.2010.10.087
26. S. F. Santos, J. F. R de Castro, and E. A. Ticianelli, “Microstructures and electrode performances of Mg50Ni(50-x)Pdx alloys,” Cent. Eur. J. Chem., 11, 485-491 (2013). https://doi.org/10.2478/s11532-012-0182-3
27. A. Etiemble, S. Rousselot, W. Guo, H. Idrissi, and L. Roué, “Influence of Pd addition on the electrochemical performance of Mg-Ni-Ti-Al-based metal hydride for Ni-MH batteries,” Int. J. Hydrogen Energy, 38, 7169-7177 (2013). https://doi.org/10.1016/j.ijhydene.2013.03.080