稀土元素替代对汽车电池负极用储氢合金相结构和电化学性能的影响

doi:10.19964/j.issn.1006-4990.2025-0012

摘要/Abstract

摘要：

为提升汽车电池负极用储氢合金的电化学性能，对比分析真空感应熔炼法制备的不同稀土元素R（R为La、Pr、Nd和Gd）替代制备的La_0.65R_0.15Mg_0.2Ni₃储氢合金的相结构和电化学性能。结果表明，不同稀土元素替代制备的La_0.65R_0.15Mg_0.2Ni₃储氢合金均主要含LaNi₅、LaMgNi₄、（La，Mg）Ni₃、（La，Mg）₂Ni₇和（La，Mg）₅Ni₁₉相，R原子半径的减小会使（La，Mg）₂Ni₇-2H相向（La，Mg）₂Ni₇-3R相转变，晶胞体积逐渐减小而晶胞参数c/a变化不大。4种稀土元素替代制备的La_0.65R_0.15Mg_0.2Ni₃储氢合金的活化次数均为1，且随着R原子半径减小，La_0.65R_0.15Mg_0.2Ni₃储氢合金的最大放电容量C_max逐渐增大，当R分别为La、Pr、Nd和Gd时，La_0.65R_0.15Mg_0.2Ni₃储氢合金循环100次时的容量保持率S₁₀₀分别为50.6%、53.7%、53.6%和43.7%，储氢合金的高倍率放电性能HRD₁₅₀₀从高至低的顺序为Nd、Pr、La、Gd；其中La_0.65Nd_0.15Mg_0.2Ni₃储氢合金具有良好的活化性能、循环稳定性和高倍率放电性能。La_0.65R_0.15Mg_0.2Ni₃储氢合金的交换电流密度I₀和氢扩散系数D₀与HRD₁₅₀₀变化趋势保持一致，同时证明La_0.65R_0.15Mg_0.2Ni₃储氢合金的高倍率放电性能由I₀和D₀共同决定。

关键词: 汽车电池负极, 储氢合金, 稀土元素替代, 相结构, 电化学性能

Abstract:

In order to improve the electrochemical performance of hydrogen storage alloys for automotive battery cathodes，the phase structure and electrochemical performance of La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloys prepared by vacuum induction melting method with different rare earth elements（R was La，Pr，Nd，and Gd） as substitutes were compared and analyzed.The results showed that when different rare earth elements were substituted，La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloys mainly contained LaNi₅，LaMgNi₄，（La，Mg）Ni₃，（La，Mg）₂Ni₇，and（La，Mg）₅Ni₁₉ phases.The decrease in R atomic radius would cause the（La，Mg）₂Ni₇-2H phase to transition to the（La，Mg）₂Ni₇-3R phase，and the unit cell volume was gradually decreased while the unit cell parameters c/a changed little.The activation times of La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloy replaced by four rare earth elements were all 1，and as the radius of the R atom decreased，the C_max of La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloy was gradually increased.When R=La，Pr，Nd，and Gd，the S₁₀₀ of La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloy was 50.6%，53.7%，53.6%，and 43.7%，respectively.The high rate discharge performance HRD₁₅₀₀ of hydrogen storage alloy from high to low was as follows：Nd，Pr，La，Gd.The La_0.65Nd_0.15Mg_0.2Ni₃ hydrogen storage alloy exhibited excellent activation performance，cycling stability，and high rate discharge performance.The exchange current density I₀ and hydrogen diffusion coefficient D₀ of La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloy showed a consistent trend with HRD₁₅₀₀，indicating that the high rate discharge performance of La_0.65R_0.15Mg_0.2Ni₃ hydrogen storage alloy was determined by both I₀ and D₀.

Key words: cathode of automotive battery, hydrogen storage alloy, substitution of rare earth elements, phase structure, electrochemical performance

中图分类号:

TQ138.13

何玉汝, 李志强, 刘力, 周曦, 孟冉浩. 稀土元素替代对汽车电池负极用储氢合金相结构和电化学性能的影响[J]. 无机盐工业, 2026, 58(3): 58-64.

HE Yuru, LI Zhiqiang, LIU Li, ZHOU Xi, MENG Ranhao. Effect of rare earth element substitution on phase structure and electrochemical properties of hydrogen storage alloys for automotive battery cathodes[J]. Inorganic Chemicals Industry, 2026, 58(3): 58-64.

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替代元素	相组成	相丰度/%	晶胞参数
替代元素	相组成	相丰度/%	a/nm	c/nm	V/nm³	c/a
La	（La，Mg）Ni₃	27.12	0.506 1	2.456 5	54.227 6	4.853 8
	（La，Mg）₂Ni₇-2H	25.74	0.505 2	2.433 0	53.529 6	4.815 9
	（La，Mg）₂Ni₇-3R	7.86	0.506 5	3.640 4	80.507 2	7.187 4
	（La，Mg）₅Ni₁₉-3R	7.74	0.506 0	4.834 9	106.701 9	9.555 1
	LaNi₅	25.64	0.503 6	0.399 6	8.716 7	0.793 5
	LaMgNi₄	5.90	0.719 5
Pr	（La，Mg）Ni₃	34.01	0.505 6	2.445 1	53.889 3	4.836 0
	（La，Mg）₂Ni₇-2H	33.23	0.504 5	2.426 8	53.245 8	4.810 3
	（La，Mg）₂Ni₇-3R	13.95	0.504 0	3.634 6	79.596 5	7.211 5
	（La，Mg）₅Ni₁₉-3R	7.65	0.502 9	4.823 0	105.165 8	9.590 4
	LaNi₅	6.10	0.502 3	0.399 5	8.672 5	0.795 3
	LaMgNi₄	5.06	0.718 5
Nd	（La，Mg）Ni₃	36.68	0.505 5	2.443 2	53.814 0	4.833 2
	（La，Mg）₂Ni₇-2H	25.46	0.504 5	2.425 0	53.204 9	4.806 7
	（La，Mg）₂Ni₇-3R	16.18	0.503 6	3.631 2	79.382 6	7.210 5
	（La，Mg）₅Ni₁₉-3R	8.85	0.502 4	4.822 7	104.947 5	9.599 3
	LaNi₅	9.73	0.501 7	0.399 1	8.641 4	0.795 5
	LaMgNi₄	3.10	0.714 5
Gd	（La，Mg）Ni₃	35.06	0.504 9	2.443 0	53.695 9	4.838 6
	（La，Mg）₂Ni₇-2H	10.01	0.503 9	2.421 5	53.007 8	4.805 5
	（La，Mg）₂Ni₇-3R	30.04	0.503 4	3.630 0	79.294 8	7.211 0
	（La，Mg）₅Ni₁₉-3R	14.35	0.502 3	4.818 7	104.824 7	9.593 3
	LaNi₅	10.54	0.500 9	0.399 2	8.616 0	0.797 0

替代元素	区域	La原子数分数/%	R原子数分数/%	Mg原子数分数/%	Ni原子数分数/%
La	α	40.32		1.18	56.96
	β	37.16		1.56	60.19
	γ	36.52		1.39	61.07
	ε	33.11		0.18	65.62
Pr	α	32.09	7.63	3.08	56.04
	β	33.93	6.30	1.16	57.44
	γ	25.89	8.48	0.85	63.64
	ε	26.09	7.17	0.21	65.41
Nd	α	33.39	7.62	3.22	54.70
	β	36.39	4.35	1.21	56.83
	γ	28.62	8.17	1.28	60.83
	ε	25.94	7.38	0.38	65.26
Gd	α	33.11	5.23	1.69	58.69
	β	25.98	8.92	0.72	63.17
	γ	24.63	9.24	0.28	64.81
	ε	24.53	9.21	0.23	64.85

替代元素	极限电流密度/ （mA·g^-1）	电荷转移电阻/ Ω	高倍率放电性能HRD₁₅₀₀/%	交换电流密度（I₀）/（mA·g^-1）	氢扩散系数（D₀）/（× 10^-11cm²·s^-1）
La	3.410	0.241	73.88	342.35	2.81
Pr	3.755	0.232	81.25	367.53	3.24
Nd	3.883	0.204	86.94	388.33	3.31
Gd	3.181	0.292	69.09	315.02	2.41

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