International Journal of Hydrogen Energy, Vol.42, No.9, 6051-6064, 2017
Phase transformation and electrochemical hydrogen storage performances of La3RMgNi19 (R = La, Pr, Nd, Sm, Gd and Y) alloys
Adjusting the rare earth (RE) compositions in the RE Mg Ni alloys can effectively improve the electrochemical hydrogen storage performances of the alloy electrodes. Herein, A(5)B(19) type hydrogen storage alloys with the elemental composition of La3RMgNi19 (R = La, Pr, Nd, Sm, Gd and Y) were prepared by induction melting and subsequent annealing. The phase transformation and electrochemical hydrogen storage performances of La3RMgNi19 alloys were investigated in detail. X-ray diffraction analysis shows that La3RMgNi19 alloys contains AB(5), A(2)B(7) (Ce2Ni7 and Gd2Co7) and A(5)B(19) (Pr5Co19 and Ce5Co19) phases, and the increase of annealing temperature obviously reduces the phase abundance of LaNi5 phase. Sm, Gd and Y contribute to the formation of A(5)B(29) phase, especially Ce5Co19, and Pr and Nd promote the formation of A(2)B(7) phase for La3RMgNi19 alloys. With increasing annealing temperature, the maximum discharge capacity (C-max) of La3RMgNi19 alloy electrodes first increases and then decreases, and the highest value of C-max is achieved as the annealing temperature is 1223 K. This evolution trend of the C-max is inversely proportional to that of LaNi5 phase abundance. The substation of La by Pr, Nd, Sm, Gd or Y causes the decrease of C-max, which is mainly ascribed to the decrease of cell volume. Due to the decrement of LaNi5 phase, the cycling stability increases at first when the annealing temperature is below 1223 K. However, when annealing temperate further increases to 1273 K, the cycling stability decreases, which is caused by the increment of LaNi5 phase. It is worth noting that the phase composition (LaNi5 phase abundance) plays more important role than other factor. The slight decrement of high-rate dischargeability resulted from the substitution of La by Pr, Nd, Sm, Gd or Y should be attributed to the combined effect of advantageous and disadvantageous factors. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keywords:A(5)B(19)-type La-Mg-Ni alloys;Rare earth substitution;Phase transformation;Electrochemical hydrogen storage performance