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

doi:10.19964/j.issn.1006-4990.2024-0003

Abstract

Abstract:

In order to improve the electrochemical performance of hydrogen storage alloys for automotive battery cathodes，as-cast Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloys were annealed at 850~1 050 ℃ holding for 4 h，the phase composition，microstructure and electrochemical properties（charge discharge curve，pressure composition temperature curve，cycle curve，polarization curve，and rate discharge curve） of as-cast and annealed hydrogen storage alloys at different temperatures were compared and analyzed.The results showed that the as-cast and low-temperature（850，900 ℃） annealed Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloys were mainly composed of CaCu₅ type phase，Ce₂Ni₇/Gd₂Co₇ type phase，and Ce₅Co₁₉ type phase，the hydrogen storage alloys annealed at 950 ℃ and above were mainly composed of Ce₂Ni₇ type phase and Ce₅Co₁₉ type phase.The maximum abundance of Ce₂Ni₇ type phase was obtained at 950 ℃.C_max of annealed hydrogen storage alloys was higher than that of cast hydrogen storage alloys，and with the increase of annealing temperature，the maximum discharge capacity of annealed Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloy was firstly increased and then decreased，the C_max was achieved（372.6 mA·h/g） at 950 ℃.With the increase of annealing temperature，the high rate discharge performance of Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloy was firstly increased and then decreased.At the same discharge current density，the high rate discharge performance of Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloy annealed at 950 ℃ was the highest.The high rate discharge performance of Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloy was mainly controlled by the hydrogen diffusion coefficient D₀，Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloy with good electrochemical performance could be obtained by adjusting the annealing temperature，and the suitable annealing temperature was 950 ℃.

Key words: Y_0.2La_0.8Ni_3.2Al_0.2Mn_0.2 hydrogen storage alloy, annealing temperature, phase structure, microscopic morphology, electrochemical performance

CLC Number:

TM911

HU Wenjuan, SHEN Xiaozhong, WANG Rujia, LU Lu, ZOU Lianli. 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.

Figures/Tables 10

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References 25

1	LI Ruyue， LU Hang， PAN Xiangyu，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.
2	陶炳全，张华，杨星焕，等.汽车氢镍电池负极材料的热处理与性能研究［J］.电源技术，2020，44（11）：1642-1646.
	TAO Bingquan， ZHANG Hua， YANG Xinghuan，et al.Study on heat treatment and performance of negative electrode material for vehicle NiMH battery［J］.Chinese Journal of Power Sources，2020，44（11）：1642-1646.
3	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.
4	李媛，陈康莉，王文凤，等.La-Mg-Ni系A₂B₇型合金相结构与储氢性能研究进展［J］.中国材料进展，2023，42（1）：30-38，46.
	LI Yuan， CHEN Kangli， WANG Wenfeng，et al.Investigation on phase structure and hydrogen storage properties of La-Mg-Ni-based A₂B₇-type alloys［J］.Materials China，2023，42（1）：30-38，46.
5	李亚琴，尚宏伟，查文珂，等.La-Mg-Ni系A₂B₇型电极材料的研究进展［J］.电池，2022，52（6）：698-702.
	LI Yaqin， SHANG Hongwei， ZHA Wenke，et al.Research progress in La-Mg-Ni system A₂B₇-type electrode materials［J］.Battery Bimonthly，2022，52（6）：698-702.
6	JIANG Weiqing， CHEN Yujie， HU Mengru，et al.Rare earth-Mg-Ni-based alloys with superlattice structure for electrochemical hydrogen storage［J］.Journal of Alloys and Compounds，2021，887：161381.
7	伏康康，赵鑫，可丹丹，等.Ce替代La对合金LaNi_4.5Al_0.5储氢性能及热力学的影响［J］.稀土，2023，44（2）：86-92.
	FU Kangkang， ZHAO Xin， KE Dandan，et al.Effect of Ce substitution for La on the hydrogen storage properties and thermodynamics of alloy LaNi_4.5Al_0.5 ［J］.Chinese Rare Earths，2023，44（2）：86-92.
8	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.
9	熊玮，周淑娟，赵玉园，等.不同化学计量比La-Y-Ni系储氢合金的研究Ⅱ：氢化反应与电极反应特性［J］.稀土，2022，43（4）：29-36.
	XIONG Wei， ZHOU Shujuan， ZHAO Yuyuan，et al.Study on La-Y-Ni hydrogen storage alloys with different stoichiometric ratios Ⅱ：Hydrogenation and electrode reaction characteristics［J］.Chinese Rare Earths，2022，43（4）：29-36.
10	邓剑锋，孔凡校，朱立宗，等.添加剂REMg₂Ni对Mg₂Ni储氢材料性能的影响研究［J］.电源技术，2022，46（11）：1261-1264.
	DENG Jianfeng， KONG Fanxiao， ZHU Lizong，et al.Effect of additive REMg₂Ni on properties of Mg₂Ni hydrogen storage materi-al［J］.Chinese Journal of Power Sources，2022，46（11）：1261-1264.
11	DENG Anqiang， LUO Yongchun， ZHOU Jianfei，et al.Effect of Mn element on the structures and properties of A₂B₇-type La-Y-Ni-based hydrogen storage alloys［J］.Metals，2022，12（7）：1122.
12	纪铭悦，田晓，刘昕瑀，等.铸态和快淬态La-Mg-Ni储氢合金的电化学性能及其对BH₄ ^-的催化氧化性能［J］.金属功能材料，2022，29（4）：56-63.
	JI Mingyue， TIAN Xiao， LIU Xinyu，et al.Electrochemical properties and catalytic oxidation properties for BH₄ ^- of the as-cast and rapid quenched La-Mg-Ni hydrogen storage alloys［J］.Metallic Functional Materials，2022，29（4）：56-63.
13	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 al-loy［J］.Chinese Rare Earths，2023，44（5）：117-126.
14	郑波，刘雯雯，任权兵，等.不同Mn含量对A₂B₇型La-Y-Ni储氢合金性能的影响［J］.有色金属（冶炼部分），2023（8）：82-88.
	ZHENG Bo， LIU Wenwen， REN Quanbing，et al.Effect of different Mn contents on properties of A₂B₇-type La-Y-Ni hydrogen storage alloy［J］.Nonferrous Metals（Extractive Metallurgy）， 2023（8）：82-88.
15	WANG Wenfeng， LIU Xiaoxue， ZHANG Lu，et al.The electrochemical characteristics of AB₄-type rare earth-Mg-Ni-based superlattice structure hydrogen storage alloys for nickel metal hydride battery［J］.Journal of Magnesium and Alloys，2021，9（6）：2039-2048.
16	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.
17	张旭，王利，李宝犬，等.Cu对La-Y-Ni系A₂B₇型储氢合金微观结构及电化学性能的影响［J］.稀有金属，2021，45（12）：1438-1447.
	ZHANG Xu， WANG Li， LI Baoquan，et al.Effects of substituting Ni with Cu on microstructure and electrochemical performance of A₂B₇-type La-Y-Ni-based hydrogen storage alloy［J］.Chinese Journal of Rare Metals，2021，45（12）：1438-1447.
18	王姗姗，裴婷，张新庄，等.La_0.7Mg_0.3Ni_2.5- _x Co_0.6Mn_0.4Cu _x_（ _x_=0～0.20）储氢合金的制备及电化学性能研究［J］.石油化工应用，2023，42（9）：96-98，102.
	WANG Shanshan， PEI Ting， ZHANG Xinzhuang，et al.Preparation and electrochemical properties of La_0.7Mg_0.3Ni_2.5- _x Co_0.6Mn_0.4Cu _x_（ _x_=0~0.20）hydrogen storage alloy［J］.Petrochemical Industry Application，2023，42（9）：96-98， 102.
19	DING Xin， CHEN Ruirun， ZHANG Jiaxin，et al.Achieving superior hydrogen storage properties via in situ formed nanostructures：A high-capacity Mg-Ni alloy with La microalloying［J］.International Journal of Hydrogen Energy，2022，47（10）：6755-6766.
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	朱晓梅，罗统钊，蒋志军，等.镁基储氢合金La0._47- _x Sm_0.53Mg _x Ni_3.35Al_0.15的制备和退火工艺研究［J］.稀土，2022，43（4）：121-128.
	ZHU Xiaomei， LUO Tongzhao， JIANG Zhijun，et al.Preparation and annealing technology of magnesium-based hydrogen storage alloy La_0.47- _x Sm_0.53Mg _x Ni_3.35Al_0.15 ［J］.Chinese Rare Earths，2022，43（4）：121-128.
22	LIN Shuangping， NIE Zuoren， HUANG Hui，et al.Annealing behavior of a modified 5083 aluminum alloy［J］.Materials & Design，2010，31（3）：1607-1612.
23	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.
24	刘雯雯，赖华生，王玉香，等.La/Y比对A₂B₇型La-Y-Ni储氢合金性能的影响［J］.矿冶工程，2023，43（2）：149-153.
	LIU Wenwen， LAI Huasheng， WANG Yuxiang，et al.Effect of La/Y ratio on properties of A₂B₇-type La-Y-Ni hydrogen storage alloy［J］.Mining and Metallurgical Engineering，2023，43（2）：149-153.
25	WAN Changpeng， ZHAO Shiqian， WANG Hui.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.

试样	相结构	晶格常数			相丰度/%
试样	相结构	a/Å	c/Å	V/Å³	相丰度/%
铸态	CaCu₅	5.020	3.986	86.5	22.25
	Ce₂Ni₇	5.001	24.467	527.6	41.61
	Gd₂Co₇	5.048	36.339	799.2	20.22
	Ce₅Co₁₉	4.936	48.831	1 025.6	15.92
850 ℃退火态	CaCu₅	5.032	4.002	87.3	11.69
	Ce₂Ni₇	5.021	24.364	529.4	58.57
	Gd₂Co₇	5.026	36.588	794.7	18.65
	Ce₅Co₁₉	4.999	47.691	1 027.6	11.08
900 ℃退火态	CaCu₅	5.180	3.981	86.7	9.67
	Ce₂Ni₇	5.029	24.334	530.6	72.97
	Gd₂Co₇	5.025	36.228	788.8	9.02
	Ce₅Co₁₉	4.957	48.864	1 035.4	8.35
950 ℃退火态	Ce₂Ni₇	5.026	24.358	532.5	93.29
950 ℃退火态	Ce₅Co₁₉	4.987	48.612	1 042.5	6.71
1 000 ℃退火态	Ce₂Ni₇	5.025	24.420	530.7	86.96
1 000 ℃退火态	Ce₅Co₁₉	4.944	48.880	1 030.2	13.04
1 050 ℃退火态	Ce₂Ni₇	4.993	24.303	522.4	77.97
1 050 ℃退火态	Ce₅Co₁₉	4.943	48.743	1 026.7	22.03

试样	活化次数Na	最大放电容量C_max/ （mA·h·g^-1）	循环稳定性 S₁₀₀/%	高倍率放电性能HRD₉₀₀/%	氢扩散系数D₀ /（10^-10 cm²·s^-1）	交换电流密度I₀/（mA·g^-1）
铸态	3	299.3	78.8	79.9	1.29	332.0
850 ℃ 退火态	3	348.3	79.3	81.4	1.68	279.7
900 ℃ 退火态	3	354.4	79.4	83.4	1.93	231.0
950 ℃ 退火态	3	372.6	90.0	84.5	2.79	244.6
1 000 ℃ 退火态	5	371.5	87.6	81.7	2.67	270.2
1 050 ℃ 退火态	6	366.3	82.6	77.5	2.43	322.6

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Effect of annealing temperature on phase structure and electrochemical performance of hydrogen storage alloys for automotive batteries

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