Degradation behaviors of La-Mg-Ni-based metal hydride alloys: structural stability and influence on hydrogen storage performances

doi:10.1007/s40195-018-0744-2

Abstract

Abstract:

The present work focuses on the structural stability upon hydrogenation of three typical La-Mg-Ni-based alloys: La₂MgNi₉, La₃MgNi₁₄ and La₄MgNi₁₉. Structural changes during gaseous and electrochemical cycles were characterized, and the influence of the structure distortion on the hydrogen storage properties was concerned. Hydrogen-induced amorphization (HIA) and disproportionation of the three alloys have occurred during both the gaseous and electrochemical cycles. Structural stability of the phase structures in the La-Mg-Ni system is found to follow the order: LaNi₅>(La,Mg)₅Ni₁₉>(La,Mg)₂Ni₇>(La,Mg)Ni₃>(La,Mg)Ni₂. HIA increases thermal stability of the metal hydrides and difficulty to dehydrogenation and leads to degradation of both the gaseous and electrochemical capacities. Interestingly, La₂MgNi₉ with poor stability presents elevated discharge capability even at 60 °C which can be attributed to increase in the hydrogen desorption capability and inhibition of the self-discharge induced by severe HIA at higher temperatures. In addition, HIA in the electrochemical reactions is obviously weaker than the extent during the gaseous cycles, which is mainly due to the slower hydrogenation speed. The development of HIA in the gaseous and electrochemical process is considered to follow the direct and gradual modes, respectively.

Key words: La-Mg-Ni-based alloys, Degradation behaviors, Hydrogen-induced amorphization, Electrochemical properties

Yi-Ming Li, Bao-Yu Duan, Zhuo-Cheng Liu, Yang-Huan Zhang, Hui-Ping Ren. Degradation behaviors of La-Mg-Ni-based metal hydride alloys: structural stability and influence on hydrogen storage performances[J]. Acta Metallurgica Sinica (English Letters), 2018, 31(9): 897-909.

Figures/Tables 15

Fig. 1 XRD patterns of three alloys after gaseous cycling by 10 times.

Fig. 2 TEM analysis of gaseously cycled La2MgNi9 alloy: a bright-field image of hydrogen-induced amorphization phase; b corresponding SAED pattern of a; c bright-field image of crystal LaNi5; d SAED pattern of crystal LaNi5.

Fig. 3 HRTEM images of gaseously cycled La2MgNi9 alloy in region 1 a and region 2 b.

Fig. 4 STEM a and EDS-mapping of Ni b, La c and Mg d in gaseously cycled La2MgNi9 alloy.

Fig. 5 Bright-field image (inset is SAED) a, dark-field image b and HRTEM images at low c and high d magnification of region where amorphous and crystal structure coexisting in gaseously cycled La2MgNi9 alloy.

Fig. 6 Hydrogen absorption content of three alloys during gaseous cycling.

Fig. 7 DSC a and TG b curves of three alloys after gaseous cycling.

Table 1 Discharge capacities (mAh g-1) of three alloys under various conditions

Alloy	DC (30 °C)	DC (Gaseous phase activated)	DC (40 °C)	DC (60 °C)
La₂MgNi₉	350.8	299.1	365.9	370.8
La₃MgNi₁₄	366.3	341.8	376.6	324.5
La₄MgNi₁₉	332.1	340.6	336.4	282.4

Fig. 8 P-C-T curves of La2MgNi9 a and La4MgNi19 b alloys under different temperatures (Abs and Des are abbreviations for absorption and desorption, respectively) .

Fig. 9 Structural evolution of La2MgNi9 alloy under various hydrogenation processes.

Fig. 10 TEM characterization of La2MgNi9 alloy after 100th electrochemical cycling: a bright-field image; b bright-field image of selected region for SAED; c SAED pattern; d bright-field image of diffraction spot in c.

Fig. 11 HRTEM image of La2MgNi9 alloy after 100th electrochemical cycling a and corresponding fast Fourier transformation of area 1 b, area 5 c, area 6 d, area 7 e and area 10 f.

Fig. 12 Hydrogen absorption plateau of La2MgNi9 alloy by slow charge.

Fig. 13 Discharge capacities of La2MgNi9 alloy at different charging rates.

Fig. 14 Schematic illustration of degradation characters of AB3-, A2B7- and A5B19-type La-Mg-Ni-based alloys.

References

[1]	S. Yasuoka, Y. Magari, T. Murata, T. Tadayoshi, J. Ishida, H. Nakamura, T. Nohma, K. Masaru, J.Power Sources 156, 662 (2006)
[2]	Y.F. Liu, Y.H. Cao, L. Huang, M.X. Gao, H.G. Pan, J. Alloys Compd. 509, 675(2011)
[3]	J.J. Liu, S.M. Han, Y. Li, L. Zhang, Y.M. Zhao, S.Q. Yang, B.Z. Liu, Int. J. Hydrog. Energy 41, 20261 (2016)
[4]	B. Liao, Y.Q. Lei, G.L. Lu, L.X. Chen, H.G. Pan, Q.D. Wang, J. Alloys Compd. 356-357, 746 (2003)
[5]	J.J. Liu, S.M. Han, Y. Li, S.Q. Yang, W.Z. Shen, L. Zhang, Y. Zhou, J. Alloys Compd. 552, 119(2013)
[6]	X. Cai, F.S. Wei, F.N. Wei, H.H. Lu, Acta Metall. Sin. (Engl. Lett.) 29, 614(2017)
[7]	Y. Zhang, F.S. Wei, J.N. Xiao, X. Cai, Acta Metall. Sin. (Engl. Lett.) 30, 1033(2017)
[8]	B. Liao, Y.Q. Lei, L.X. Chen, G.L. Lu, H.G. Pan, Q.D. Wang, J.Power Sources 129, 358 (2004)
[9]	F.L. Zhang, Y.C. Luo, J.P. Chen, R.X. Yan, J.H. Chen, J. Alloys Compd. 430, 302(2007)
[10]	F. Li, K. Young, T. Ouchi, M.A. Fetcenko, J. Alloys Compd. 471, 371(2009)
[11]	W.K. Hu, R.V. Denys, C.C. Nwakwuo, T. Holm, J.P. Maehlen, J.K. Solberg, V.A. Yartys, Electrochim. Acta 96, 27 (2013)
[12]	T. Sakai, K. Oguro, H. Miyamura, N. Kuriyama, A. Kato, H. Ishikawa, J.Power Sources 161, 193(1990)
[13]	D. Chartouni, F. Meli, A. Züttel, K. Gross, L. Schlapbach, J. Alloys Compd. 241, 160(1996)
[14]	Y.F. Liu, H.G. Pan, Y.J. Yue, X.F. Wu, N. Chen, Y.Q. Lei, J. Alloys Compd. 395, 291(2005)
[15]	X.Z. Sun, H.G. Pan, M.X. Gao, R. Li, Y. Lin, S. Ma, Trans. Nonferrous Met. Soc. China 16, 8 (2006)
[16]	Y.H. Zhang, D.L. Zhao, B.W. Li, H.P. Ren, X.P. Dong, X.L. Wang, Trans. Nonferrous Met. Soc. China 17, 816 (2007)
[17]	R.C. Bowman, C.H. Luo, C.C. Ahn, C.K. Witham, B. Fultz, J. Alloys Compd. 217, 185(1995)
[18]	Y.M. Li, H.W. Zhang, Y.H. Zhang, H.P. Ren, Rare Met. 36, 101(2017)
[19]	J. Chen, H.T. Takeshita, H. Tanaka, N. Kuriyama, T. Sakai, I. Uehara, M. Haruta, J. Alloys Compd. 302, 304(2000)
[20]	R.V. Denys, B. Riabov, V.A. Yartys, R.G. Delaplane, M. Sato, J. Alloys Compd. 446-447, 166 (2007)
[21]	R.V. Denys, V.A. Yartys, M. Sato, A.B. Riabov, R.G. Delaplane, J.Power Sources 180, 2566(2007)
[22]	R.V. Denys, A.B. Riabov, V.A. Yartys, M. Sato, R.G. Delaplane, J.Power Sources 181, 812(2008)
[23]	W. Wang, Y.G. Chen, C.L. Wu, Rare Met. Mater. Eng. 40, 2080 (2011)
[24]	A. Férey, F. Cuevas, M. Latroche, B. Knosp, P. Bernar, Electrochim. Acta 54, 1710 (2009)
[25]	R.V. Denys, V.A. Yartys, J. Alloys Compd. 509s, S540(2011)
[26]	L. Zhang, S.M. Han, D. Han, Y. Li, X. Zhao, J.J. Liu, J. Alloys Compd. 268, 575(2014)
[27]	Y.M. Li, H.P. Ren, Y.H. Zhang, Z.C. Liu, H.W. Zhang, Int. J.Hydrogen Energy 40, 7093 (2015)
[28]	Y.M. Li, Y.H. Zhang, H.P. Ren, Acta Metall. Sin. (Engl. Lett.) (2018).
[29]	J.J. Liu, Y. Li, D. Han, S.Q. Yang, X.C. Chen, L. Zhang, S.M. Han, J.Power Sources 300, 77 (2015)
[30]	J. Nakamura, K. Iwase, H. Hayakawa, Y. Nakamura, E. Akiba, J. Phys. Chem.C 113, 5853 (2009)
[31]	T.T. Zhai, T. Yang, Z.M. Yuan, S. Xu, W.G. Bu, Y. Qi, Y.H. Zhang, J. Alloys Compd. 639, 15(2015)
[32]	K. Young, T. Ouchi, H. Shen, L.A. Bendersky, Int. J. Hydrog. Energy 40, 8941 (2015)
[33]	M. Balogun, Z.M. Wang, H.G. Zhang, Q.R. Yao, J.Q. Deng, H.Y. Zhou, J. Alloys Compd. 579, 438(2013)
[34]	Q.R. Yao, H.Y. Zhou, Z.M. Wang, S.K. Pan, G.H. Rao, J. Alloys Compd. 606, 81(2014)
[35]	J. Lin, Y. Cheng, F. Liang, L.S. Sun, D.M. Yin, Y.M. Wu, L.M. Wang, Int. J. Hydrog. Energy 39, 13231 (2014)
[36]	X.Q. Shen, Y.G. Chen, M.D. Tao, C.L. Wu, G. Deng, Z.Z. Kang, Int. J. Hydrog. Energy 34, 3395 (2009)
[37]	Z.R. Jia, L. Zhang, Y.M. Zhao, J. Cao, Y. Li, Z.T. Dong, W.F. Wang, S.M. Han, J.Power Sources 188, 371 (2017)
[38]	E. Axinte, Mater. Des. 35, 518(2012)
[39]	Y.G. Kim, J.Y. Lee, J. Alloys Compd. 187, 1(1992)
[40]	K. Aoki, T. Masumoto, J. Alloys Compd. 231, 20(1995)
[41]	K. Aoki, Mater. Sci. Eng. A 304-306, 45(2001)
[42]	K. Young, T. Ouchi, J. Nei, J.M. Koch, Y.L. Lien, Batteries 3, 34 (2017)
[43]	H.Z. Yan, W. Xiong, L. Wang, B.Q. Li, J. Li, X. Zhao, Int. J. Hydrog. Energy 42, 2257 (2017)
[44]	L.Z. Ouyang, J.L. Huang, H. Wang, J.W. Liu, M. Zhu, Mater. Chem. Phys. 200, 164(2017)
[45]	Z.J. Cao, L.Z. Ouyang, L.L. Li, Y.S. Lu, H. Wang, J.W. Liu, D. Min, Y.W. Chen, F.M. Xiao, T. Sun, R.H. Tang, M. Zhu, Int. J. Hydrog. Energy 40, 451 (2015)
[46]	L.Z. Ouyang, T.H. Yang, M. Zhu, D. Min, T.Z. Luo, H. Wang, F.M. Xiao, R.H. Tang, J. Alloys Compd. 735, 98(2018)
[47]	Z.J. Cao, L.Z. Ouyang, H. Wang, J.W. Liu, D.L. Sun, Q.A. Zhang, M. Zhu, J. Alloys Compd. 608, 14(2014)
[48]	Y.M. Zhao, L. Zhang, Y.Q. Ding, J. Cao, Z.R. Jia, C.P. Ma, Y. Li, S.M. Han, J. Alloys Compd. 649, 1089(2017)
[49]	W. Xiong, H.Z. Yan, L. Wang, V. Verbetsky, X. Zhao, S. Mitrokhin, B.Q. Li, J. Li, Y. Wang, Int.J. Hydrogen Energy 42, 10131 (2017)
[50]	J.J. Liu, Y.K. Yan, H.H. Cheng, S.M. Han, Y.F. Lv, K. Li, C. Lu, J.Power Sources 351, 26 (2017)
[51]	F.L. Zhang, Y.C. Luo, J.P. Chen, R.X. Yan, L. Kang, J.H. Chen, J.Power Sources 150, 247 (2005)
[52]	J.J. Liu, S.M. Han, Y. Li, J.L. Zhang, Y.M. Zhao, L.D. Che, Int. J. Hydrog. Energy 38, 14903 (2013)
[53]	J.J. Liu, S.M. Han, D. Han, Y. Li, S.Q. Yang, L. Zhang, Y.M. Zhao, J.Power Sources 287, 237 (2015)
[54]	C.J. Xue, L. Zhang, Y.P. Fan, G.X. Fan, B.Z. Liu, S.M. Han, Int. J. Hydrog. Energy 42, 6051 (2017)
[55]	J.J. Liu, S.M. Han, Y. Li, X. Zhao, S.Q. Yang, Y.M. Zhao, Int. J. Hydrog. Energy 40, 1116 (2015)
[56]	Y.H. Zhang, X.P. Dong, S.H. Guo, G.Q. Wang, J.Y. Ren, X.L. Wang, Int. J. Hydrog. Energy 31, 63 (2006)
[57]	H.P. Ren, Y.H. Zhang, B.W. Li, X.P. Dong, X.L. Zhao, X.L. Wang, Mater. Charact. 58, 289(2007)
[58]	Y.H. Zhang, B.W. Li, H.P. Ren, Y. Cai, X.P. Dong, X.L. Wang, Int. J. Hydrog. Energy 32, 4627 (2007)
[59]	Y.H. Zhang, Y. Cai, C. Zhao, T.T. Zhai, G.G. Zhang, D.L. Zhao, Int. J. Hydrog. Energy 37, 14590 (2012)
[60]	Y.M. Li, Y.H. Zhang, H.P. Ren, Z.C. Liu, H. Sun, Int. J. Hydrog. Energy 41, 18571 (2016)