Rare Metals

, 30:464 | Cite as

Effects of annealing treatment on the microstructure and electrochemical properties of low-Co hydrogen storage alloys containing Cu and Fe

  • Suxia Yang
  • Zhiping Liu
  • Shumin Han
  • Wei Zhang
  • Jianzheng Song
Article

Abstract

The effects of annealing treatment on the microstructure and electrochemical properties of low-Co LaNi3.55Mn0.35Co0.20Al0.20Cu0.75Fe0.10 hydrogen storage alloys were investigated. X-ray diffraction (XRD) analysis indicated that annealing treatment remarkably reduced the lattice strain and defects, and increased the unit-cell volume. The optical microscope analysis showed that the as-cast alloy had a crass dendrite microstructure with noticeable composition segregation, which gradually disappeared with increasing annealing temperature, and the microstructure changed to an equiaxed structure after annealing the alloy at 1233 K. The electrochemical tests indicated that the annealed alloys demonstrated much better cycling stability compared with the as-cast one. The capacity retention at the 100th cycle increased from 90.0% (as-cast) to 94.7% (1273 K). The annealing treatment also improved the discharge capacity. However, the high rate dischargeability (HRD) value of the annealed alloy slightly dropped, which was believed to be ascribed to the decreased exchange current density and the hydrogen diffusion coefficient in alloy bulk.

Keywords

hydrogen storage alloys annealing phase structure microstructure electrochemical properties 

References

  1. [1]
    Ruiz F.C., Castro E.B., Real S.G., Peretti H.A., Visintin A., and Triaca WE., Electrochemical characterization of AB2 alloys used for negative electrodes in Ni/MH batteries, Int. J. Hydrogen Energy, 2008, 33: 3576.CrossRefGoogle Scholar
  2. [2]
    Ding H.L., Han S.M., Liu Y., Hao J.S., Li. Y., and Zhang J.W., Electrochemical performance studies on cobalt and nickel electroplated La-Mg-Ni-based hydrogen storage alloys, Int. J. Hydrogen Energy, 2009, 34: 9403.Google Scholar
  3. [3]
    Ma J.X., Pan H.G., Chen C.P., and Wang Q.D., The electrochemical properties of Co-free AB5 type MlNi(4.45−x)Mn0.40Al0.15Snx hydride electrode alloys, J. Alloys Compd., 2002, 343: 164.CrossRefGoogle Scholar
  4. [4]
    Li P., Wang X.L., Zhang Y.H., Wu J.M., Li R, and Qu X.H., Research of low-Co AB5 type rare-earth-based hydrogen storage alloy electrodes, J. Alloys Compd., 2003, 354: 310.CrossRefGoogle Scholar
  5. [5]
    Wang Z.X., Li X.H., Chen Q.Y., Guo B.K., Peng W.J., and Guo H.J., Structure of Sn doped AB5 non-stoichiometric hydrogen-absorbing alloys, J. Rare Earths, 2000, 18: 226.Google Scholar
  6. [6]
    Yang S.X., Li Y., Liu Z.P., Han S.M., and Yang S.Q., Rare earth-based AB5 type electrode hydrogen storage alloy with low content cobalt, Acta Phys. Chim. Sin., 2003, 21: 61.Google Scholar
  7. [7]
    Wei X.D., Liu S.S., Dong H., Zhang P., Liu Y.N., Zhu J.W., and Yu G., Microstructures and electrochemical properties of Co-free AB5-type hydrogen storage alloys through substitution of Ni by Fe, Electrochim. Acta, 2007, 52: 2423.CrossRefGoogle Scholar
  8. [8]
    Li P, Zhang Y.H., Wang X.L., Lin Y.F., and Qu X.H., Research of Mm(NiMnAlCu)4.9Co0.2 hydrogen storage alloys prepared by cast and rapidly quenched, J. Power Sources, 2003, 124: 285.CrossRefGoogle Scholar
  9. [9]
    Hu W.K., Kim D.M., Jang K.J., and Lee J.Y., Studies on co-free rare-earth-based hydrogen storage alloys, J. Alloy Compd., 1998, 269: 254.CrossRefGoogle Scholar
  10. [10]
    Zhang Y.H., Wang G.Q., Dong X.P., Guo S.H., Ren J.Y., and Wang X.L., Effect of substituting Co with Fe on the cycle stabilities of the as-cast and quenched AB5-type hydrogen storage alloys, J. Power Sources, 2005, 148: 105.CrossRefGoogle Scholar
  11. [11]
    Li C.J., Wang X.L., Wu J.M., and Wang C.Y., Effect of annealing on the hydrogen-storage properties of rapidly quenched AB5-type alloys, J. Power Sources, 1998, 70: 106.CrossRefGoogle Scholar
  12. [12]
    Li C.J., Wang X.L., Wu J.M., and Wang C.Y., Investigations on ML(NiCoMnTi)5 alloys prepared with different solidification rates, J. Alloys Compd., 1998, 266: 300.CrossRefGoogle Scholar
  13. [13]
    Chuan H.J., Huang S.S., Ma C.Y., and Chan S.L.I., Effect of annealing heat treatment on an atomized AB2 hydrogen storage, J. Alloys Compd., 1999, 285: 284.CrossRefGoogle Scholar
  14. [14]
    Li P., Wang X.L., Lin Y.F., Li R., and Wu J.M., Rare earth-based AB5 type electrode hydrogen storage alloy with low content cobalt, J. Chin. Rare Earth Soc., 2003, 21: 61.Google Scholar
  15. [15]
    Zhang Y.H., Wang G.Q., Dong X.P., Guo S.H., and Wang X.L., Effects of rapid quenching on the electrochemical performances and microstructures of the Mm(NiMnSiAl)4.3Co0.6−xFex (x = 0−0.6) electrode alloys, J. Power Sources, 2004, 137: 309.CrossRefGoogle Scholar
  16. [16]
    Yu L.M., Jiang W.Q., and Fu Z.Z., Properties analysis of Fe-bearing low cobalt AB5 type hydrogen storage alloys, Rare Met., 2005, 29: 856.Google Scholar
  17. [17]
    Li Y., Han D., Han S.M., Zhu X.L., Hu L., Zhang Z., and Liu Y.W., Effect of rare earth elements on electrochemical properties of La-Mg-Ni-based hydrogen storage alloys, Int. J. Hydrogen Energy, 2009, 34: 1399.CrossRefGoogle Scholar
  18. [18]
    Pan H.G., Liu Y.F., Gao M.X., Zhu Y.F., Lei Y.Q., and Wang Q.D., A study on the effect of annealing treatment on the electrochemical properties of La0.67Mg0.33Ni2.5Co0.5 alloy electrodes, Int. J. Hydrogen Energy, 2003, 28: 113.CrossRefGoogle Scholar
  19. [19]
    Ye H., Zhang H., Cheng J.X., and Huang T.S., Effect of Ni content on the structure, thermodynamic and electrochemical properties of the non-stoichiometric hydrogen storage alloys, J. Alloys Compd., 2000, 308: 163.CrossRefGoogle Scholar
  20. [20]
    Wang J.J., Hou Y, and Liu J., Study on AB5−x type hydrogen storage alloys, J. Power Sources, 2003, 27: 85.Google Scholar
  21. [21]
    Iwakura C., Oura T., Inoue H., and Matsuoka M., Effects of substitution with foreign metals on the crystallographic, thermodynamic and electrochemical properties of AB5-type hydrogen storage alloys, Electrochim. Acta, 1996, 41: 117.CrossRefGoogle Scholar
  22. [22]
    Zhang Y.H., Chen M.Y., Wang X.L., Wang G.Q., Dong X.P., and Qi Y., Microstructure and electrochemical characteristics of Mm(Ni,Co,Mn,Al)5Bx (x = 0−0.4) hydrogen storage alloys prepared by cast and rapid quenching and electrochemical characteristics of Mm(Ni,Co,Mn,Al)5Bx (x = 0−0.4) hydrogen storage alloys prepared by cast and rapid quenching, Electrochim. Acta, 2004, 49: 1161.CrossRefGoogle Scholar
  23. [23]
    Zhang Y.H., Wang G.Q., Dong X.P., Guo S.H., Wu J.M., and Wang X.L., Investigation on the microstructure and electrochemical performances of La2Mg(Ni0.85Co0.15)9Bx (x = 0−0.2) hydrogen storage electrode alloys prepared by casting and rapid quenching, J. Alloys Compd., 2004, 379: 298.CrossRefGoogle Scholar

Copyright information

© The Nonferrous Metals Society of China and Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  • Suxia Yang
    • 1
    • 2
  • Zhiping Liu
    • 1
  • Shumin Han
    • 1
    • 2
  • Wei Zhang
    • 2
  • Jianzheng Song
    • 2
  1. 1.State Key Laboratory of Metastable Materials Science and TechnologyYanshan UniversityQinhuangdaoChina
  2. 2.College of Environmental and Chemical EngineeringYanshan UniversityQinhuangdaoChina

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