汽车用La0.79Mg0.21Ni3.95储氢合金的制备与电化学性能研究

doi:10.19964/j.issn.1006-4990.2020-0534

Abstract

Abstract:

In order to develop cathode materials for Ni-MH batteries with high energy density,La_0.79Mg_0.21Ni_3.95 hydrogen storage alloy was prepared by vacuum induction melting,and the phase composition,microstructure and electrochemical properties of as cast and annealed hydrogen storage alloys were compared and analyzed.The results showed that there were only LaNi₅ and（La,Mg）₂Ni₇ phases in as cast and 800 ℃/24 h annealed La_0.79Mg_0.21Ni_3.95 hydrogen storage alloys.When the tem-perature was raised to 900 ℃ or above,different contents of（La,Mg）₅Ni₁₉ phase and（La,Mg）₆Ni₂₄ phase were formed in the hydrogen storage alloy.The reversible hydrogen absorption and desorption performance of 900 ℃/24 h annealed hydrogen storage alloy was higher than that of 950 ℃/48 h annealed hydrogen storage alloy.The maximum discharge capacity of as cast and annealed hydrogen storage alloys reached the maximum in the first three cycles,and the hydrogen storage alloy annealed at 950 ℃/48 h mainly consisted of（La,Mg）₆Ni₂₄ phase,which had high cycle stability.As cast and annealed La_0.79Mg_0.21Ni_3.95 hy-drogen storage alloys had good electrochemical activation properties.The order of HRD₁₅₀₀ from high to low was: 950 ℃/48 h>950 ℃/24 h>900 ℃/24 h>800 ℃/24 h>as cast,the results showed that the HRD₁₅₀₀ of hydrogen storage alloy had the same trend with that of hydrogen diffusion rate（D） and exchange current density（I₀）.The maximum HRD₁₅₀₀ of hydrogen storage alloy annealed at 950 ℃/48 h was mainly due to the fact that the alloy electrode contained 61.8% of（La,Mg）₆Ni₂₄ phase and had higher D and I₀.

Key words: La_0.79Mg_0.21Ni_3.95 hydrogen storage alloy, annealing temperature, annealing time, microstructure, electrochemical property

CLC Number:

TM912
TB33

FAN Qingke,MENG Qinghua. Study on preparation and electrochemical properties of La_0.79Mg_0.21Ni_3.95 hydrogen storage alloy for vehicles[J]. Inorganic Chemicals Industry, 2022, 54(3): 71-76.

Figures/Tables 12

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References 16

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序号	退火温度/℃	退火时间/h	冷却方式
1	800、900	24	随炉冷却
2	950	24、48、60	随炉冷却
3	975	24	随炉冷却

试样	相组成	晶胞参数		w（相）/ %
试样	相组成	a/nm	b/nm	w（相）/ %
铸态	LaNi₅	0.503 4	0.399 5	50.9
铸态	（La,Mg）₂Ni₇	0.503 2	3.615 1	49.1
800 ℃/24 h	LaNi₅	0.503 7	0.400 6	45.1
800 ℃/24 h	（La,Mg）₂Ni₇	0.502 6	3.625 4	54.9
900 ℃/24 h	LaNi₅	0.504 1	0.400 0	35.2
900 ℃/24 h	（La,Mg）₅Ni₁₉	0.503 1	4.817 5	64.8
950 ℃/24 h	LaNi₅	0.503 0	0.4010	22.8
	（La,Mg）₅Ni₁₉	0.503 5	4.814 8	43.6
	（La,Mg）₆Ni₂₄	0.503 5	5.979 1	33.6
950 ℃/48 h	LaNi₅	0.502 2	0.400 3	20.1
	（La,Mg）₅Ni₁₉	0.503 6	4.814 6	18.1
	（La,Mg）₆Ni₂₄	0.496 4	6.108 8	61.8
950 ℃/60 h	LaNi₅	0.503 4	0.401 7	49.4
	（La,Mg）₂Ni₇	0.505 3	2.527 3	28.3
	（La,Mg）₆Ni₂₄	0.504 0	6.014 7	22.6
975 ℃/24 h	LaNi₅	0.499 6	0.402 8	68.1
	（La,Mg）₂Ni₇	0.499 8	2.528 3	22.1
	（La,Mg）₅Ni₁₉	0.512 1	3.207 0	10.1

试样	区域	相组成	质量分数/%			x（La）: x（Mg）:x（Ni）
试样	区域	相组成	La	Mg	Ni	x（La）: x（Mg）:x（Ni）
铸态	α	LaNi₅	33.74	—	66.26	1:0:4.73
铸态	β	（La,Mg）₂Ni₇	33.43	1.88	64.69	0.76:0.24:3.49
900 ℃/24 h	α	LaNi₅	33.68	—	66.32	1:0:4.69
900 ℃/24 h	γ	（La,Mg）₅Ni₁₉	33.49	1.26	65.25	0.81:0.17:3.80
950 ℃/24 h	α	LaNi₅	33.67	—	66.33	1:0:4.65
	γ	（La,Mg）₅Ni₁₉	33.35	1.20	65.45	0.81:0.18:3.79
	δ	（La,Mg）₆Ni₂₄	33.34	1.07	65.59	0.85:0.15:3.99
950 ℃/48 h	α	LaNi₅	33.64	—	66.36	1:0:4.76
	γ	（La,Mg）₅Ni₁₉	33.84	1.20	64.96	0.83:0.17:3.91
	δ	（La,Mg）₆Ni₂₄	33.65	0.80	65.55	0.87:0.13:4.13
950 ℃/60 h	α	LaNi₅	33.39	—	66.61	1:0:4.82
	δ	（La,Mg）₆Ni₂₄	33.21	0.89	65.90	0.86:0.12:4.12
	ε	（La,Mg）₂Ni₇	33.88	1.59	64.53	0.75:0.20:3.63
975 ℃/24 h	α	LaNi₅	32.64	—	67.36	1:0:4.90
	ε	（La,Mg）₂Ni₇	34.23	1.60	64.98	0.79:0.21:3.65
	η	（La,Mg）₅Ni₁₉	34.17	1.00	64.83	0.84:0.16:3.90

试样	C_max/ （mA·h·g^-1）	S₁₀₀/ %	HRD₁₅₀₀/ %	D/ （10^-11 cm²·s^-1）	I₀/ （mA·g^-1）
铸态	343	73.7	47.1	1.16	280.9
800 ℃/24 h	367	74.4	52.5	1.61	291.6
900 ℃/24 h	358	77.2	56.0	1.89	314.0
950 ℃/24 h	359	76.1	63.2	2.29	334.7
950 ℃/48 h	355	81.3	69.1	2.56	361.4

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Study on preparation and electrochemical properties of La_0.79Mg_0.21Ni_3.95 hydrogen storage alloy for vehicles

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Study on preparation and electrochemical properties of La0.79Mg0.21Ni3.95 hydrogen storage alloy for vehicles