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

摘要/Abstract

摘要：

为了提升汽车电池负极用RENi_3.2Mn_0.2Al_0.15储氢合金（RE为复合稀土Y_1-_x La _x ）的电化学性能，采用真空电弧熔炼法制备RENi_3.2Mn_0.2Al_0.15储氢合金，考察了稀土Y_1-_x La _x 复合添加及x值对储氢合金相结构、显微形貌和电化学性能的影响。结果表明，RENi_3.2Mn_0.2Al_0.15储氢合金在x=0、0.15时由LaNi₅+Ce₂Ni₇型相组成，在x=0.25、0.33和0.50时由Ce₅Co₁₉+Ce₂Ni₇型相组成，在x=0.75和1.00时由PuNi₃+LaNi₅+Ce₂Ni₇型相组成。不同类型的物相在扫描电镜下呈现不同的衍射衬度，扫描电镜显微形貌观察结果与X射线衍射谱图测试结果保持一致。x=0~1.00时储氢合金的活化次数介于2~4次；随着x从0增加至1.00，储氢合金中Ce₂Ni₇型相丰度、放电容量和循环100次时的容量保持率（S₁₀₀）先增大后减小，在x=0.33时取得Ce₂Ni₇型相丰度最大值（93.07%）、放电容量最大值（372.6 mA·h/g）和S₁₀₀最大值（89.01%），储氢合金的放电容量变化趋势与Ce₂Ni₇型相丰度变化趋势相同。储氢合金电极的腐蚀电流密度（i）与S₁₀₀负相关，表明储氢合金的耐腐蚀性能是影响循环性能的主要因素；储氢合金的氢扩散系数（D₀）与高倍率放电性能（HRD₉₀₀）正相关，表明储氢合金的高倍率放电性能由氢的扩散速率决定。

关键词: 电池负极, RENi_3.2Mn_0.2Al_0.15, 储氢合金, 相结构, 电化学性能

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

中图分类号:

TG139.7

陈成春, 李云琴, 赵美琴. 汽车电池负极用储氢合金的相结构与性能研究[J]. 无机盐工业, 2025, 57(7): 73-79.

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.

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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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