汽车电池用LaNdMgNiAl储氢合金的相结构与电化学性能

doi:10.13251/j.issn.0254-6051.2025.11.017

摘要/Abstract

摘要： 为提升汽车镍氢电池用La_0.62Nd_0.15Mg_0.2Ni_3.48Al_0.12储氢合金的电化学性能,对储氢合金进行了880~1010 ℃的退火处理,对比分析了Pr₅Co₁₉单相和AB₄单相结构储氢合金的相结构和电化学性能。结果表明,1000 ℃以下退火态La_0.62Nd_0.15Mg_0.2Ni_3.48Al_0.12储氢合金由多相组成,当退火温度从1000 ℃升高至1010 ℃,储氢合金的物相由2H型Pr₅Co₁₉单相转变为3R型AB₄单相结构。随着放电电流密度增加,Pr₅Co₁₉单相结构储氢合金和AB₄单相结构储氢合金的放电容量都逐渐减小,AB₄单相结构储氢合金相较Pr₅Co₁₉单相结构储氢合金具有更好的循环稳定性、低温放电性能和高倍率放电性能。AB₄单相结构储氢合金的电荷转移速率和氢扩散速率高于Pr₅Co₁₉单相结构储氢合金,两种单相储氢合金的高倍率放电性能都由电荷转移速率和氢扩散速率共同决定。

关键词: 汽车电池, LaNdMgNiAl储氢合金, AB₄单相, Pr₅Co₁₉单相, 相结构, 电化学性能

Abstract: In order to improve the electrochemical properties of La_0.62Nd_0.15Mg_0.2Ni_3.48Al_0.12 hydrogen storage alloy for automotive batteries, the hydrogen storage alloy was annealed at 880-1010 ℃, and the phase structure and electrochemical properties of Pr₅Co₁₉ single-phase and AB₄ single-phase hydrogen storage alloys were compared and analyzed. The results show that the La_0.62Nd_0.15Mg_0.2Ni_3.48Al_0.12 hydrogen storage alloy annealed below 1000 ℃ is composed of multiple phases. When the annealing temperature increases from 1000 ℃ to 1010 ℃, the phase of the hydrogen storage alloy changes from 2H type Pr₅Co₁₉ single-phase to 3R type AB₄ single-phase structure. As the discharge current density increases, the discharge capacity of Pr₅Co₁₉ single-phase structure hydrogen storage alloy and AB₄ single-phase structure hydrogen storage alloy gradually decreases. AB₄ single-phase structure hydrogen storage alloy has better cycle stability, low-temperature discharge performance, and high rate discharge performance compared to Pr₅Co₁₉ single-phase structure hydrogen storage alloy. The charge transfer rate and hydrogen diffusion rate of AB₄ single-phase structure hydrogen storage alloy are higher than those of Pr₅Co₁₉ single-phase structure hydrogen storage alloy. The high rate discharge performance of both single-phase hydrogen storage alloys is determined by both the charge transfer rate and hydrogen diffusion rate.

Key words: automotive batteries, LaNdMgNiAl hydrogen storage alloy, AB₄ single-phase, Pr₅Co₁₉ single-phase, phase structure, electrochemical properties

中图分类号:

TG139.7

李婧芳, 王超, 赵学方, 刘宇辰. 汽车电池用LaNdMgNiAl储氢合金的相结构与电化学性能[J]. 金属热处理, 2025, 50(11): 118-125.

Li Jingfang, Wang Chao, Zhao Xuefang, Liu Yuchen. Phase structure and electrochemical properties of LaNdMgNiAl hydrogen storage alloy for automotive batteries[J]. Heat Treatment of Metals, 2025, 50(11): 118-125.

参考文献

[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): 23080129.
Zhang Fengxia, Tan Cheng. Research progress of advanced cathode electrode materials for nickel-metal hybrid battery[J]. Materials Reports, 2023, 37(S2): 23080129.
[2] 郭团生, 李媛, 韩树民. 城轨车辆镍氢电池负极材料的研究[J]. 燕山大学学报, 2024, 48(5): 463-470.
Guo Tuansheng, Li Yuan, Han Shumin. Study on hydrogen storage alloy materials for Ni/MH batteries used in rail transit[J]. Journal of Yanshan University, 2024, 48(5): 463-470.
[3] 王晨, 和豪涛, 张昊. 汽车电池用RE-Mg-Ni储氢合金的制备工艺与电化学性能[J]. 稀土, 2025, 46(1): 47-56.
Wang Chen, He Haotao, Zhang Hao. Preparation process and electrochemical properties of RE-Mg-Ni hydrogen storage alloy for automotive battery[J]. Chinese Rare Earths, 2025, 46(1): 47-56.
[4] 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.
[5] Li R Y, Lu H, Pan X Y, et al. Improvement on cyclic stability of AB₄-type La-Mg-Ni-based hydrogen storage alloys via merging Y element for nickel-metal hydride batteries[J]. International Journal of Hydrogen Energy, 2023, 48(84): 32849-32859.
[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 Metallurgy Engineering, 2024, 44(4): 90-94.
[7] 梁丽萍, 曾志伟. 电动汽车电池用储氢合金的制备与性能[J]. 电池, 2021, 51(3): 233-237.
Liang Liping, Zeng Zhiwei. Preparation and performance of hydrogen storage alloys of battery for electric vehicle[J]. Battery Bimonthly, 2021, 51(3): 233-237.
[8] 程丽群, 左付山. 新能源汽车电池用无镁储氢合金的制备与性能研究[J]. 无机盐工业, 2021, 53(11): 71-76.
Cheng Liqun, Zuo Fushan. Study on preparation and properties of magnesium free hydrogen storage alloys for new energy vehicle batteries[J]. Inorganic Chemicals Industry, 2021, 53(11): 71-76.
[9] Chen Y J, Mo X H , Huang Y, et al. The role of magnesium on properties of La_3-xMg_xNi₉ (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.
[10] 苏张磊, 李玮, 罗志敏. 汽车电池负极材料的制备与电化学性能研究[J]. 现代化工, 2022, 42(7): 141-146.
Su Zhanglei, Li Wei, Luo Zhimin. Preparation of anode materials for automotive batteries and research on their electrochemical properties[J]. Modern Chemical Industry, 2022, 42(7): 141-146.
[11] Wang Y J, Li H, Zhang J S, et al. Effect of Y content on the microstructure and hydrogen storage properties of annealed La_1-xY_xMgNi_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: 175868-175872.
[12] Liu J J, Li Y, Han D, et al. Electrochemical performance and capacity degradation mechanism of single-phase La-Mg-Ni-based hydrogen storage alloys[J]. Journal of Power Sources, 2015, 300: 77-86.
[13] 彭卫锋, 施卫. Co替代Ni对汽车电池用La_0.8Mg_0.2Ni_3.8-xCo_x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-xCo_x hydrogen storage alloy for automotive batteries[J]. Inorganic Chemicals Industry, 2024, 56(11): 65-71.
[14] 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.
[15] 曹生亮, 郑标帝, 周曦, 等. Nd替代Y对汽车电池负极用储氢合金电化学性能的影响[J]. 无机盐工业, 2025, 57(4): 45-51.
Cao Shengliang, Zheng Biaodi, Zhou Xi, et al. Effect of Nd replacing Y on electrochemical performance of hydrogen storage alloys for automotive battery anodes[J]. Inorganic Chemicals Industry, 2025, 57(4): 45-51.
[16] 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.
[17] Jin S, Ren K L, Liang J, et al. A novel sheet perovskite type oxides LaFeO₃ anode for nickel-metal hydride batteries[J]. Journal of Materials Science & Technology, 2024, 195: 218-226.
[18] Guo Y N,Wang W F, Su H H, 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.
[19] 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.
[20] 朱家麒, 胡锋, 李永治, 等. 元素替代对La-Y-Ni系储氢合金微观组织、储氢性能及循环性能的影响[J]. 中国稀土学报, 2025, 43(1): 111-128.
Zhu Jiaqi, Hu Feng, Li Yongzhi, et al. Effect of element substitution on microstructure, hydrogen storage properties and cycling properties of La-Y-Ni hydrogen storage alloys[J]. Journal of the Chinese Society of Rare Earths, 2025, 43(1): 111-128.
[21] 刘冬梅, 肖润谋, 佘翔. 新能源汽车用储氢合金的制备与电化学性能研究[J]. 化工新型材料, 2021, 49(6): 131-136.
Liu Dongmei, Xiao Runmou, She Xiang. Preparation and electrochemical properties of hydrogen storage alloys for new energy vehicle[J]. New Chemical Materials, 2021, 49(6): 131-136.
[22] Yin W X, Tang A C, Wan C B, et al. Understanding lanthanum effects on the structure and properties of La_xY_1-xMgNi₄ hydrogen storage alloys[J]. International Journal of Hydrogen Energy, 2024, 50: 444-454.
[23] Wan C P, Zhao S Q, Wang H. Tuning phase structure and electrochemical hydrogen storage properties of A₅B₁₉-type La-Y-Ni-Mn-based superlattice alloys by partial Al substitution[J]. International Journal of Hydrogen Energy, 2024, 49: 51-58.
[24] Zhang A, Li R, Lu H, et al. Effects of Mn and Fe elements on the electrochemical hydrogen storage properties of the A₅B₁₉-type La-Y-Mg-Ni-Al alloy for nickel metal hydride battery[J]. Journal of Alloys and Compounds, 2024, 992: 174229-174233.