汽车电池负极用储氢合金的相结构与性能研究

doi:10.19964/j.issn.1006-4990.2024-0371

Abstract

Abstract:

In order to improve the electrochemical performance of RENi_3.2Mn_0.2Al_0.15 hydrogen storage alloy（RE is a composite rare earth Y_1-_x La _x ） for automotive battery anodes，RENi_3.2Mn_0.2Al_0.15 hydrogen storage alloy was prepared by vacuum arc melting method，the effects of rare earth Y_1-_x La _x composite addition and x value on the phase structure，morphology and electrochemical performance of the hydrogen storage alloy were investigated.The results indicated that when x=0 and 0.15，the hydrogen storage alloy was mainly composed of LaNi₅ and Ce₂Ni₇ phases.When x=0.25，0.33，and 0.50，the hydrogen storage alloy was mainly composed of Ce₅Co₁₉ type and Ce₂Ni₇ type phases.When x=0.75 and 1.00，hydrogen storage alloys were mainly composed of PuNi₃ type，LaNi₅ type，and Ce₂Ni₇ type phases.Different types of phases exhibited different diffraction contrast under scanning electron microscopy，and the microscopic morphology observed by scanning electron microscopy was consistent with the X-ray diffraction pattern test results.When x=0~1.00，the activation frequency of hydrogen storage alloys was ranged from 2 to 4 times.As x was increased from 0 to 1.00，the abundance of Ce₂Ni₇ phase，discharge capacity，and capacity retention rate at 100 cycles（S₁₀₀） in the hydrogen storage alloy showed trend of firstly increased and then decreased.At x=0.33，the maximum abundance of Ce₂Ni₇ phase（93.07%），maximum discharge capacity（372.6 mA·h/g），and maximum S₁₀₀ value（89.01%） were obtained.The trend of discharge capacity change in the hydrogen storage alloy was consistent with that of Ce₂Ni₇ phase abundance.The corrosion current density i of hydrogen storage alloy electrodes was negatively correlated with S₁₀₀，indicating that the corrosion resistance of hydrogen storage alloys was the main factor affecting cycling performance.The hydrogen diffusion coefficient D₀ of hydrogen storage alloys was positively correlated with HRD₉₀₀，indicating that the high rate discharge performance of hydrogen storage alloys was determined by the diffusion rate of hydrogen.

Key words: battery anode, RENi_3.2Mn_0.2Al_0.15, hydrogen storage alloy, phase structure, electrochemical performance

CLC Number:

TG139.7

CHEN Chengchun, LI Yunqin, ZHAO Meiqin. Study on phase structure and properties of hydrogen storage alloy for automotive battery anode[J]. Inorganic Chemicals Industry, 2025, 57(7): 73-79.

Figures/Tables 10

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Table 1

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Table 2

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References 21

[1]	臧金环，李春玲.《新能源汽车产业发展规划（2021—2035年）》调整解读［J］.汽车工艺师，2021（S1）：32-34.
	ZANG Jinhuan， LI Chunling.Interpretation of the adjustment of the development plan for the new energy vehicle industry（2021-2035）［J］.Auto Manufacturing Engineer，2021（S1）：32-34.
[2]	李瑾瑜.稀土储氢合金产业现状及发展趋势［J］.稀土信息，2023（6）：30-34.
	LI Jinyu.The current situation and development trend of rare earth hydrogen storage alloy industry［J］.Rare Earth Information，2023（6）：30-34.
[3]	LI Jinyu.Current situation and development trends of rare earth hydrogen storage alloy industry［J］.China Rare Earth Information，2023，29（2）：12-20.
[4]	熊玮，周淑娟，赵玉园，等.超晶格稀土储氢合金材料的研究进展［J］.稀土，2023，44（4）：40-57.
	XIONG Wei， ZHOU Shujuan， ZHAO Yuyuan，et al.Review of rare earth hydrogen storage alloy materials with superlattice structures［J］.Chinese Rare Earths，2023，44（4）：40-57.
[5]	李媛，张璐，韩树民.稀土-镁-镍系超晶格合金结构与储氢性能研究及进展［J］.燕山大学学报，2020，44（3）：323-330.
	LI Yuan， ZHANG Lu， HAN Shumin.Development in structure and hydrogen storage properties of rare earth-magnesium-nickel-based super-lattice alloys［J］.Journal of Yanshan University，2020，44（3）：323-330.
[6]	TANG Rui， LIU Liqin， LIU Yongning，et al.Study on the microstructure and the electrochemical properties of Ml_0.7Mg_0.2Ni_2.8Co_0.6 hydrogen storage alloy［J］.International Journal of Hydrogen Energy，2003，28（8）：815-819.
[7]	JIANG Zhaojun， WANG Jun， CAO Dongmei.Research progress of rare earth-based hydrogen storage alloys［J］.Key Engineering Materials，2020，861：354-362.
[8]	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.
[9]	LI Jiaxuan， HE Xiangyang， XIONG Wei，et al.Phase forming law and electrochemical properties of A₂B₇-type La-Y-Ni-based hydrogen storage alloys with different La/Y ratios［J］.Journal of Rare Earths，2023，41（2）：268-276.
[10]	鲁航，王文凤，陶旭杰，等.AB₄相对A₅B₁₉型稀土镁镍系合金储氢性能的影响研究［J］.稀土，2023，44（1）：157-164.
	LU Hang， WANG Wenfeng， TAO Xujie，et al.Effect of AB₄ phase on hydrogen storage properties of A₅B₁₉-type RE-Mg-Ni-based alloy［J］.Chinese Rare Earths，2023，44（1）：157-164.
[11]	熊玮，张旭，周淑娟，等.不同化学计量比La-Y-Ni系储氢合金的研究Ⅰ：表面状态与组织结构［J］.稀土，2020，41（6）：9-17.
	XIONG Wei， ZHANG Xu， ZHOU Shujuan，et al.Study on La-Y-Ni hydrogen storage alloys with different stoichiometric ratiosⅠ：Surface state and structure［J］.Chinese Rare Earths，2020， 41（6）：9-17.
[12]	同艳维，李娜丽，张雪峰.稀土Ce添加量对钒基储氢合金显微组织和电化学性能的影响［J］.稀有金属与硬质合金，2021，49（6）：42-46.
	TONG Yanwei， LI Nali， ZHANG Xuefeng.Effect of addition amount of rare earth Ce on microstructure and electrochemical properties of vanadium-based hydrogen storage alloys［J］.Rare Metals and Cemented Carbides，2021，49（6）：42-46.
[13]	WU Ran， YUAN Huiping， LIU Yuru，et al.Effect of carbon coating on electrochemical properties of AB_3.5-type La-Y-Ni-based hydrogen storage alloys［J］.Journal of Rare Earths，2022，40（8）：1264-1271.
[14]	范庆科，孟庆华.汽车用La_0.79Mg_0.21Ni_3.95储氢合金的制备与电化学性能研究［J］.无机盐工业，2022，54（3）：71-76.
	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.
[15]	ZHOU Na， DU Wenbo， ZHANG Peilong，et al.Microstructure and electrochemical properties of La_0.8– _x MM _x Mg_0.2Ni_3.1Co_0.3Al_0.1 （x=0，0.1，0.2，0.3） alloys［J］.Rare Metals，2017，36（8）：645- 650.
[16]	邵光俭，王克乐.成分对汽车用（La_0.7Mg_0.3）Ni_x合金储氢特性的影响［J］.无机盐工业，2021，53（9）：51-56.
	SHAO Guangjian， WANG Kele.Effect of composition on hydrogen storage characteristics of （La_0.7Mg_0.3）Ni _x alloy for vehicle［J］.Inorganic Chemicals Industry，2021，53（9）：51-56.
[17]	LIN Shuangping， NIE Zuoren， HUANG Hui，et al.Annealing behavior of a modified 5083 aluminum alloy［J］.Materials & Design，2010，31（3）：1607-1612.
[18]	徐津，李宝犬，王利，等.A₂B₇型La-Y-Ni与La-Mg-Ni储氢合金电化学性能研究［J］.有色金属工程，2020，10（12）：9-15， 37.
	XU Jin， LI Baoquan， WANG Li，et al.Study on the electrochemical properties of La-Y-Ni and La-Mg-Ni hydrogen storage alloys with A₂B₇ type［J］.Nonferrous Metals Engineering，2020，10（12）：9-15，37.
[19]	李英杰，姚继伟，雍辉，等.稀土掺杂对稀土-镁基合金储氢性能的影响［J］.材料导报，2022，36（20）：187-194.
	LI Yingjie， YAO Jiwei， YONG Hui，et al.Effect of rare earth doping on hydrogen storage properties of RE-Mg based hydrogen storage alloys［J］.Materials Reports，2022，36（20）：187-194.
[20]	李通，罗新宇，陈子然.退火温度对汽车镍氢电池用储氢合金电化学性能的影响［J］.稀土，2022，43（5）：93-101.
	LI Tong， LUO Xinyu， CHEN Ziran.Effect of annealing temperature on electrochemical properties of hydrogen storage alloys for Ni-MH battery［J］.Chinese Rare Earths，2022，43（5）：93- 101.
[21]	GUO Jin， LI Chonghe， LIU Honglin，et al.Effect of rare earth compositions on the hydrogen storage properties of AB₅-type alloys and pattern recognition analysis［J］.Journal of the Electrochemical Society，2019，144（7）：2276-2278.

x值	相结构	晶格常数			相丰度/ %
x值	相结构	a/nm	c/nm	V/nm³	相丰度/ %
0	LaNi₅	0.502 3	0.398 3	0.086 4	47.47
0	Ce₂Ni₇	0.499 3	2.441 6	0.524 7	52.53
0.15	LaNi₅	0.501 5	0.400 6	0.086 7	38.84
0.15	Ce₂Ni₇	0.500 3	2.432 5	0.524 9	61.16
0.25	Ce₅Co₁₉	0.494 5	4.878 5	1.029 4	21.20
0.25	Ce₂Ni₇	0.502 2	2.439 7	0.530 3	78.80
0.33	Ce₅Co₁₉	0.498 7	4.861 2	1.043 4	6.93
0.33	Ce₂Ni₇	0.502 6	2.435 8	0.533 4	93.07
0.50	Ce₅Co₁₉	0.491 4	4.868 0	1.025 3	37.98
0.50	Ce₂Ni₇	0.502 1	2.432 9	0.529 6	62.02
0.75	PuNi₃	0.502 7	2.432 1	0.530 7	28.09
	LaNi₅	0.502 7	0.406 5	0.089 4	11.60
	Ce₂Ni₇	0.499 2	2.458 0	0.528 9	60.31
1.00	PuNi₃	0.499 9	2.436 5	0.525 8	17.59
	LaNi₅	0.506 9	0.402 5	0.089 0	33.64
	Ce₂Ni₇	0.499 8	2.458 9	0.530 3	48.77

x值	循环100次时的容量保持率（S₁₀₀）/%	腐蚀电位（E）/V	腐蚀电流密度（i）/ （mA·cm^-2）	高倍率放电性能（HRD₉₀₀）/%	氢扩散系数（D₀）/ （10^-10cm²·s^-1）
0.00	14.34	-0.924	8.85	68.23	0.95
0.15	33.70	-0.916	8.84	75.11	1.82
0.25	74.02	-0.901	6.68	82.77	2.67
0.33	89.01	-0.900	5.92	83.53	2.80
0.50	77.98	-0.904	6.90	75.73	1.43
0.75	78.36	-0.908	6.80	74.55	1.12
1.00	79.06	-0.905	6.84	81.03	1.39

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Study on phase structure and properties of hydrogen storage alloy for automotive battery anode

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