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

Abstract

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

CLC Number:

TQ138.13

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.

Figures/Tables 12

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Table 1

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Table 3

Fig.9

References 22

[1]	张凤霞，谈诚.先进镍氢电池负极材料的研究进展［J］.材料导报，2023，37（S2）：18-26.
	ZHANG Fengxia， TAN Cheng.Research progress of advanced cathode electrode materials for Nickel-Metal hydride battery［J］.Materials Reports，2023，37（S2）：18-26.
[2]	袁芳雪，杨智勇.La-Y-Ni体系储氢合金的电化学性能的研究［J］.山东化工，2024，53（6）：38-41.
	YUAN Fangxue， YANG Zhiyong.Study of electrochemical properties of La-Y-Ni system hydrogen storage alloys［J］.Shandong Chemical Industry，2024，53（6）：38-41.
[3]	李志强，郭正华，何玉汝.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［J］.无机盐工业，2023，55（6）：78-84.
	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.
[4]	胡文娟，申小中，王汝佳，等.退火处理对汽车电池用储氢合金相结构与电化学性能的影响［J］.无机盐工业，2024，56（11）：51-58.
	HU Wenjuan， SHEN Xiaozhong， WANG Rujia，et al.Effect of annealing temperature on phase structure and electrochemical performance of hydrogen storage alloys for automotive batteries［J］.Inorganic Chemicals Industry，2024，56（11）：51-58.
[5]	GUO Yanan， WANG Wenfeng， SU Huanhuan，et al.Insights into the effect of Y substitution on superlattice structure and electrochemical performance of A₅B₁₉-type La-Mg-Ni-based hydrogen storage alloy for nickel metal hydride battery［J］.Journal of Materials Science & Technology，2025，207：60-69.
[6]	王飞，李丽君，梅琼珍，等.汽车电池用La-Mg-Ni基储氢合金的元素替代及电化学性能［J］.矿冶工程，2024，44（4）：90-94.
	WANG Fei， LI Lijun， MEI Qiongzhen，et al.Element substitution and electrochemical performance of La-Mg-Ni based hydrogen storage alloys for automotive batteries［J］.Mining and Metallurgical Engineering，2024，44（4）：90-94.
[7]	贺祥云，王辉，徐杰，等.AB₄型La₂YNi_12- _x Mn _x （x=0.5，1.0，1.5）合金的结构和电化学储氢性能［J］.稀土，2024，45（6）：27-38.
	HE Xiangyun， WANG Hui， XU Jie，et al.Structural and electrochemical hydrogen storage properties of AB₄-type La₂YNi_12- _x Mn _x （x=0.5，1.0，1.5） alloys［J］.Chinese Rare Earths，2024，45（6）：27-38.
[8]	齐颖，李宏鑫，万初斌.元素替代在La-Mg-Ni系储氢合金中应用的研究进展［J］.稀土，2023，44（5）：117-126.
	QI Ying， LI Hongxin， WAN Chubin.Research progress of element substitution applied in La-Mg-Ni hydrogen storage alloy［J］.Chinese Rare Earths，2023，44（5）：117-126.
[9]	JIA Qiuyue， PAN Xiangyu， WANG Wenfeng，et al.Enhanced long cycling durability of Ce₂Ni₇-type single-phase Sm-Mg-Ni-based hydrogen storage alloys for nickel metal hydride batteries［J］.Journal of Power Sources，2024，624：235573.
[10]	杨天辉，刘力，周曦，等.汽车电池用无镁储氢合金的合金化与电化学性能［J］.实验室研究与探索，2022，41（12）：57-62.
	YANG Tianhui， LIU Li， ZHOU Xi，et al.Alloying and electrochemical properties of magnesium free hydrogen storage alloys for automotive batteries［J］.Research and Exploration in Laboratory，2022，41（12）：57-62.
[11]	杨振，宋佳音，汪洋青.新能源汽车电池用无镁储氢合金的制备与性能研究［J］.时代汽车，2022（17）：112-114.
	YANG Zhen， SONG Jiayin， WANG Yangqing.Preparation and properties of magnesium-free hydrogen storage alloys for new energy vehicle batteries［J］.Auto Time，2022（17）：112-114.
[12]	ZHANG Yongxi， WU Guanjiu， GU Jing，et al.A2B7-type La-Mg-Ni alloys prepared by Mg thermal diffusion for improved hydrogen storage performance［J］.Rare Metals，2024，43（7）：3260-3272.
[13]	FENG Dianchen， ZHENG Chunling， ZHAO Zhiyuan，et al.Effect of graphene addition on activation and kinetic properties of La-Mg-Ni-based hydrogen storage alloys［J］.Journal of Iron and Steel Research International，2025，32（1）：227-238.
[14]	彭卫锋，施卫.Co替代Ni对汽车电池用La_0.8Mg_0.2Ni 3.8-xCox储氢合金电化学性能的影响［J］.无机盐工业，2024，56（11）：65-71.
	PENG Weifeng， SHI Wei.Effect of Co replacing Ni on electrochemical performance of La_0.8Mg_0.2Ni_3.8- _x Co _x hydrogen storage alloy for automotive batteries［J］.Inorganic Chemicals Industry，2024，56（11）：65-71.
[15]	宋捷，李琦峰.添加剂对汽车电池用Mg₂Ni合金性能的影响［J］.电池，2022，52（5）：559-563.
	SONG Jie， LI Qifeng.Effect of additives on performance of Mg₂Ni alloy for automotive battery［J］.Battery Bimonthly，2022，52（5）：559-563.
[16]	WANG Yingjie， LI Hao， ZHANG Jianshe，et al.Effect of Y content on the microstructure and hydrogen storage properties of annealed La_1- _x Y _x MgNi_3.8Al_0.2（x=0，0.1，0.2，0.3，0.4） hydrogen storage alloys［J］.Journal of Alloys and Compounds，2024，1005：175868.
[17]	佘翔，刘冬梅，李雪，等.车用金属氢化物-镍电池负极材料的性能［J］.电池，2022，52（1）：38-42.
	SHE Xiang， LIU Dongmei， LI Xue，et al.Performance of anode material of metal hydride-nickel battery for automobile［J］.Battery Bimonthly，2022，52（1）：38-42.
[18]	ZHANG Rui， ZHAO Jianxun， LIU Wanqiang，et al.Enhanced electrochemical hydrogen storage performance of Co_0.9Cu_0.1Si alloy achieved through the synergistic effects of PANI，NiO NPs，and GO［J］.Journal of Electroanalytical Chemistry，2025，978：118890.
[19]	肖冬玲，郭飞，李强.NiCo比对La_0.8Mg_0.2（Ni，Co）_3.8储氢合金性能的影响［J］.电池，2023，53（2）：191-195.
	XIAO Dongling， GUO Fei， LI Qiang.Effect of ratio between Ni and Co on the performance of La_0.8Mg_0.2（Ni，Co）_3.8 hydrogen storage alloys［J］.Battery Bimonthly，2023，53（2）：191-195.
[20]	WU Guanjiu， XIE Yichao， LI Yuan，et al.Effect of Y，Al co-doping on hydrogen storage properties of La-Mg-Ni-based alloys［J］.Acta Metallurgica Sinica（English Letters），2024，37（8）：1399-1410.
[21]	ZHANG Junling， HAN Shumin， LI Yuan，et al.Effects of PuNi₃- and Ce₂Ni₇-type phase abundance on electrochemical characteristics of La-Mg-Ni-based alloys［J］.Journal of Alloys and Compounds，2013，581：693-698.
[22]	CHEN Yujie， MO Xiaohua， HUANG Yong，et al.The role of magnesium on properties of La_3- _x Mg _x Ni₉（x=0，0.5，1.0，1.5，2.0） hydrogen storage alloys from first-principles calculations［J］.International Journal of Hydrogen Energy，2022，47（86）：36408-36417.

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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Inorganic Acid-Base-Salt Committee of CIESC

Effect of rare earth element substitution on phase structure and electrochemical properties of hydrogen storage alloys for automotive battery cathodes

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