Zr/Mn元素替代及退火处理对汽车电池用储氢合金电化学性能的影响

doi:10.19964/j.issn.1006-4990.2022-0503

Abstract

Abstract:

The（La，Mg）_1-_x Zr _x Ni_3.3-2_x Mn₂_x （x=0，0.1，0.2） hydrogen storage alloys were prepared by vacuum induction melting.The effect of Zr/Mn element substitution and annealing treatment on the phase structure，microstructure and electrochemical properties of the hydrogen storage alloys was studied.The results showed that a new phase of LaMgNi₄ appeared in the hydrogen storage alloy after Zr/Mn element substitution，and the contents of LaNi₅ phase and LaMgNi₄ phase were decreased after annealing，the contents of（La，Mg）₂Ni₇phase and（La，Mg）₅Ni₁₉ phase were increased.When the x value in the hydrogen storage alloy was increased from 0 to 0.2，the activation times N_a of the hydrogen storage alloy electrode was gradually decreased，the maximum discharge capacity C_max was gradually decreased，and the C_max of the annealed hydrogen storage alloy electrode was higher than that of the cast hydrogen storage alloy electrode at the same x value.The substitution of Zr/Mn could improve the charge retention rate of hydrogen storage alloy electrode in 24 h and reduce the capacity retention rate after 100 cycles，and both of them would be relatively improved after annealing.The high rate discharge performance of cast hydrogen storage alloy electrode was mainly determined by hydrogen diffusion coefficient D₀，while the high rate discharge performance of annealed hydrogen storage alloy electrode was mainly determined by exchange current density I₀.

Key words: La-Mg-Ni hydrogen storage alloy, Zr/Mn element, cast and annealed, phase structure, electrochemical properties

CLC Number:

TQ132.41

LI Zhiqiang, GUO Zhenghua, HE Yuru. Effect of Zr/Mn element substitution and annealing treatment on electrochemical properties of hydrogen storage alloys for automotive batteries[J]. Inorganic Chemicals Industry, 2023, 55(6): 78-84.

Figures/Tables 10

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Table 1

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Table 2

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Table 3

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Fig.7

References 21

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试样		相类型	w（相）/%	晶格常数		晶胞体积/ 10^-3 nm³
试样		相类型	w（相）/%	a/nm	c/nm	晶胞体积/ 10^-3 nm³
铸态	x=0	CaCu₅型LaNi₅	26.74	0.503 7	0.399 5	87.29
		Gd₂Co₇型（La，Mg）₂Ni₇	66.27	0.503 8	3.624 0	793.25
		Ce₅Co₁₉型（La，Mg）₅Ni₁₉	5.36	0.495 2	4.898 7	1 035.72
		Pr₅Co₁₉型（La，Mg）₅Ni₁₉	1.63	0.506 7	3.235 3	716.18
	x=0.10	CaCu₅型LaNi₅	31.72	0.503 5	0.399 9	87.31
		Gd₂Co₇型（La，Mg）₂Ni₇	50.77	0.503 4	3.630 0	793.08
		Ce₅Co₁₉型（La，Mg）₅Ni₁₉	3.97	0.494 8	4.894 4	1 033.35
		Pr₅Co₁₉型（La，Mg）₅Ni₁₉	—	0.505 1	3.236 8	712.10
		MgCu₄Zn	13.54	0.724 6	0.724 6	378.87
	x=0.20	CaCu₅型LaNi₅	35.56	0.503 8	0.400 5	87.54
		Gd₂Co₇型（La，Mg）₂Ni₇	45.61	0.504 1	3.633 9	796.22
		Ce₅Co₁₉型（La，Mg）₅Ni₁₉	3.55	0.495 4	4.898 0	1 036.64
		Pr₅Co₁₉型（La，Mg）₅Ni₁₉	—	0.506 0	3.244 4	716.32
		MgCu₄Zn	15.28	0.726 2	0.726 2	381.41
退火态	x=0	CaCu₅型LaNi₅	9.79	0.504 1	0.401 1	87.79
		Gd₂Co₇型（La，Mg）₂Ni₇	78.47	0.504 2	3.622 2	793.87
		Ce₅Co₁₉型（La，Mg）₅Ni₁₉	9.48	0.495 2	4.868 7	1 029.33
		Pr₅Co₁₉型（La，Mg）₅Ni₁₉	2.26	0.506 5	3.243 8	717.46
	x=0.10	CaCu₅型LaNi₅	12.19	0.504 5	0.404 4	88.44
		Gd₂Co₇型（La，Mg）₂Ni₇	70.64	0.504 7	3.624 1	795.90
		Ce₅Co₁₉型（La，Mg）₅Ni₁₉	9.14	0.494 3	4.874 7	1 027.04
		Pr₅Co₁₉型（La，Mg）₅Ni₁₉	3.37	0.507 1	3.246 1	719.78
		MgCu₄Zn	5.66	0.724 5	0.724 5	378.75
	x=0.20	CaCu₅型LaNi₅	15.17	0.505 5	0.404 1	88.93
		Gd₂Co₇型（La，Mg）₂Ni₇	64.85	0.505 7	3.630 1	800.48
		Ce₅Co₁₉型（La，Mg）₅Ni₁₉	8.10	0.495 1	4.874 1	1 030.19
		Pr₅Co₁₉型（La，Mg）₅Ni₁₉	3.23	0.505 4	3.226 5	710.68
		MgCu₄Zn	8.65	0.724 4	0.724 4	378.61

试样		24 h荷电保持率/%	循环100次容量保持率S₁₀₀/%
铸态	x=0.0	72.0	64.9
	x=0.1	74.6	60.3
	x=0.2	78.7	57.8
试样		24 h荷电保持率/%	循环100次容量保持率S₁₀₀/%
退火态	x=0.0	82.9	86.6
	x=0.1	86.5	79.7
	x=0.2	92.5	72.2

储氢合金试样		极化阻抗 R_p/mΩ	交换电流密度I₀/ （mA·g^-1）	腐蚀电流密度i/ （mA·cm^-2）	氢扩散系数D₀/ （10^-10cm²·s^-1）
铸态	x=0.0	63.25	407.01	341.98	0.74
	x=0.1	78.78	326.70	356.91	0.81
	x=0.2	92.30	278.79	364.24	0.82
退火态	x=0.0	67.68	380.31	118.51	0.78
	x=0.1	60.17	427.84	175.78	0.76
	x=0.2	49.30	522.42	233.38	0.68

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Effect of Zr/Mn element substitution and annealing treatment on electrochemical properties of hydrogen storage alloys for automotive batteries

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