La-Mg-Ni系A5B19超晶格负极材料相结构及电化学性能

doi:10.11868/j.issn.1001-4381.2018.001448

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摘要

感应熔炼制备La_0.8-xCe_xMg_0.2Ni_3.8（x=0，0.1，0.3，0.5），研究Ce替代部分La对La₄MgNi₁₉超晶格负极材料相结构及电化学性能的影响。研究表明，La₄MgNi₁₉合金相由LaNi₅，（La，Mg）₂Ni₇，（La，Mg）₅Ni₁₉（3R-Ce₅Co₁₉）相组成。加入Ce后，（La，Mg）₂Ni₇相消失，出现2H-Pr₅Co₁₉结构的（La，Mg）₅Ni₁₉相，同时随着Ce替代量的增多，（La，Mg）₅Ni₁₉相含量增多，LaNi₅相随之减少，Ce加入有利于形成A₅B₁₉相，特别是形成2H-Pr₅Co₁₉结构。电化学放电容量随着x值的增加呈现先增后减趋势，x=0.1时样品的电化学放电容量380.36 mAh/g最佳。合金电极活化次数、容量保持率和倍率放电性能随着Ce含量增加而增大。H在合金中的扩散速率是影响其倍率放电性能主要因素。

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关键词 ： La-Mg-Ni系, A₅B₁₉超晶格负极材料, 稀土Ce替代, 电化学性能

Abstract：

The quaternary alloys La_0.8-xCe_xMg_0.2Ni_3.8 (x=0, 0.1, 0.3, 0.5) were prepared by induction melting, and the effects of partial substitution of Ce for La on the phase structure and electrochemical performances of super lattice La₄MgNi₁₉ negative materials were investigated. Results show that La₄MgNi₁₉ alloys contain LaNi₅ phase, (La, Mg)₂Ni₇(3R-Ce₂Ni₇ and 2H-Gd₂Co₇) phase, (La, Mg)₅Ni₁₉ (3R-Ce₅Co₁₉) phase. The 2H-Pr₅Co₁₉ type phase appears while (La, Mg)₂Ni₇ phase disappears, after partial substitution of Ce for La. The increase of Ce element substitution has led to an obvious increase of the abundance of A₅B₁₉ phase and decrease of AB₅ phase accordingly. Ce contributes to the formation of A₅B₁₉ phase, especially 2H-Pr₅Co₁₉ type phase. With the increase of Ce content from 0 to 0.5, the maximum discharge capacity of alloy electroded increases firstly and then decreased. The x=0.1 alloy exhibits a maximum discharge capacity of 380.36 mAh/g. It is also found that this substitution has caused a significant increase in the activation number, the cyclic stability, high-rate discharge ability. The well performance demonstrates that it is the hydrogen diffusion in the alloy that controls the high rate discharge.

Key words： La-Mg-Ni based super lattice A₅B₁₉ negative material rare earth Ce substitution electrochemical performance

收稿日期: 2018-12-13 出版日期: 2020-03-03

中图分类号:	TG139⁺.7
	TG146.4

基金资助:内蒙古自然科学基金项目(2017MS（LH）0519);内蒙古自然科学基金项目(2017MS（LH）0516);国家自然科学基金(51501095)

通讯作者: 许剑轶 E-mail: xujiany@yeah.net

作者简介: 许剑轶(1974—), 男, 副教授, 研究方向为功能材料, 联系地址:内蒙古包头市昆区阿尔丁大街7号内蒙古科技大学材料与冶金学院(014010), E-mail:xujiany@yeah.net

引用本文:

许剑轶, 张国芳, 胡峰, 王瑞芬, 寇勇, 张胤. La-Mg-Ni系A₅B₁₉超晶格负极材料相结构及电化学性能[J]. 材料工程, 2020, 48(2): 46-52.
Jian-yi XU, Guo-fang ZHANG, Feng HU, Rui-fen WANG, Yong KOU, Yin ZHANG. Phase structure and electrochemical performance for super lattice La-Mg-Ni based A₅B₁₉ type negative materials. Journal of Materials Engineering, 2020, 48(2): 46-52.

链接本文:

http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2018.001448 或 http://jme.biam.ac.cn/CN/Y2020/V48/I2/46

Table 1 退火合金成分ICP-AES分析

Fig.1 退火合金XRD(a)和x=0时退火合金XRD全谱拟合图谱(b)

Table 2 退火合金晶胞参数和相丰度

Fig.2 退火合金丰度(a)和合金各相的晶胞体积(b)与Ce含量关系曲线

Fig.3 x含量不同时退火合金的背散射电子图像
(a)x=0;(b)x=0.1;(c)x=0.3;(d)x=0.5

Fig.4 合金电极放电容量和循环次数关系曲线

Table 3 合金电极电化学性能参数

Fig.5 合金电极Tafel极化曲线

Fig.6 合金电极的高倍率放电性能曲线

Fig.7 合金电极的线性极化曲线

Fig.8 合金电极电化学阻抗图谱

Fig.9 合金电极阳极极化曲线

1	KADIR K , SAKAI T , UEHARA I . Synthesis and structure determination of a new series of hydrogen storage alloys; RMg₂Ni₉ (R=La, Ce, Pr, Nd, Sm and Gd) built from MgNi₂ Laves-type layers alternating with AB₅ layers[J]. J Alloy and Comp, 1997, 257, 115- 121. doi: 10.1016/S0925-8388(96)03132-5
2	MARTYNA D , MAREK N , MIECZYSLAW J , et al. Electrochemical characterization of nanocrystalline hydrogen storage La_1.5Mg_0.5Ni_6.5Co_0.5 alloy covered with amorphous nickel[J]. J Alloy and Comp, 2019, 780, 697- 704. doi: 10.1016/j.jallcom.2018.11.196
3	王瑞芬, 张胤, 许剑轶, 等. 化学镀铜对贮氢合金La_0.75Mg_0.25Ni_3.2Co_0.2Al_0.1电极性能的影响[J]. 材料工程, 2013, (5): 44- 49. doi: 10.3969/j.issn.1001-4381.2013.05.009
3	WANG R F , ZHANG Y , XU J Y , et al. Effects of Cu-P coatings on electrochemical properties of La_0.75Mg_0.25Ni_3.2Co_0.2Al_0.1 hydrogen storage alloy electrode[J]. Journal of Materials Engineering, 2013, (5): 44- 49. doi: 10.3969/j.issn.1001-4381.2013.05.009
4	魏范松, 胥小丽, 肖佳宁, 等. La₄MgNi_19-xCo_x(x=0~2)贮氢合金的相结构和电化学性能[J]. 中国有色金属学报, 2016, 26 (3): 586- 590.
4	WEI F S , XU X L , XIAO J N , et al. Phase structure and electrochemical properties of La₄MgNi_19-xCo_x (x=0-2) hydrogen storage alloys[J]. Transactions of Nonferrous Metals Society of China, 2016, 26 (3): 586- 590.
5	ZHAO Y M , ZHANG S , LIU X X , et al. Phase formation of Ce₅Co₁₉-type super-stacking structure and its effect on electrochemical and hydrogen storage properties of La_0.60M_0.20Mg_0.20Ni_3.80 (M=La, Pr, Nd, Gd) compounds[J]. International Journal of Hydrogen Energy, 2018, 43 (37): 17809- 17820. doi: 10.1016/j.ijhydene.2018.07.183
6	刘黎黎, 闫慧忠, 曹慧, 等. 热处理对A₂B₇型La_0.6Sm_0.15Nd_0.1Mg_0.15Ni_3.4Al_0.1贮氢合金微观结构和电化学性能的影响[J]. 稀土, 2016, 37 (2): 117- 121.
6	LIU L L , YAN H Z , CAO H , et al. Influence of heat treatment on microstructure and electrochemical properties of A₂B₇La_0.6Sm_0.15Nd_0.1Mg_0.15Ni_3.4Al_0.1hydrogen strange alloy[J]. Chinese Rare Earths, 2016, 37 (2): 117- 121.
7	李健靓, 王瑶, 张欣, 等. 稀土镁基贮氢合金的研究进展[J]. 金属功能材料, 2013, 20 (4): 49- 53.
7	LI J L , WANG Y , ZHANG X , et al. Research development of La-Mg-Ni system hydride storage alloys[J]. Metallic Functional Materials, 2013, 20 (4): 49- 53.
8	LIU J J , ZHU S , CHENG H H , et al. Enhanced cycling stability and high rate dischargeability of A₂B₇-type La-Mg-Ni-based alloys by in-situ formed (La, Mg)₅Ni₁₉ superlattice phase[J]. J Alloy and Comp, 2019, 777, 1087- 1097. doi: 10.1016/j.jallcom.2018.11.094
9	LIU J J , HAN S M , LI Y , et al. Phase structures and electrochemical properties of La-Mg-Ni-based hydrogen storage alloys with superlattice structure[J]. Int J of Hydrogen Energy, 2016, 41, 20261- 20275. doi: 10.1016/j.ijhydene.2016.08.149
10	WU C , YANG S , LI Y , et al. Microstructural evolution and electrochemical properties of the ultra-high pressure treated La_0.70Mg_0.30Ni_3.3 hydrogen storage alloy[J]. J Alloy and Comp, 2016, 665, 231- 239. doi: 10.1016/j.jallcom.2016.01.039
11	NOWAK M , BALCERZAK M , JURCZYK M . Hydrogen storage and electrochemical properties of mechanically alloyed La_1.5-xGd_xMg_0.5Ni₇ (0≤x≤1.5)[J]. Int J Hydrogen Energy, 2018, 43 (18): 8897- 8906. doi: 10.1016/j.ijhydene.2018.03.130
12	GAO Z J , ZHANG B , LUO Y C , et al. Correlation between phase structure and electrochemical properties of Ce₂Ni₇-type La-RE-Mg-Ni (RE=Nd, Sm, Y) alloys: a comparative study[J]. Journal of the Taiwan Institute of Chemical Engineers, 2018, 89, 183- 190. doi: 10.1016/j.jtice.2018.05.013
13	ZHANG Y H , LI Y Q , SHANG H W , et al. Electrochemical hydrogen storage performance of as-cast and as-spun RE-Mg-Ni-Co-Al-based alloys applied to Ni/MH battery[J]. Transactions of Nonferrous Metals Society of China, 2018, 28 (4): 711- 721. doi: 10.1016/S1003-6326(18)64703-X
14	ZHANG D , YAMAMOTO T , INUI H , et al. Characterization of stacking faults on basal planes in intermetallic compounds La₅Ni₁₉ and La₂Ni₇[J]. Intermetallics, 2000, 8 (4): 391- 397. doi: 10.1016/S0966-9795(99)00121-1
15	BUSCHOW K H J , VAN DER GOOT A S . The crystal structure of rare-earth nickel compounds of the type R₂Ni₇[J]. Journal of the Less Common Metals, 2000, 22, 419- 428.
16	LIU Y F , PAN H G , GAO M X , et al. XRD study on the electrochemical hydriding/dehydriding behavior of the La-Mg-Ni-Co-type hydrogen storage alloys[J]. J Alloy and Comp, 2018, 43 (24): 11079- 11084.
17	ZHANG Q, CHEN Z, LI Y, et al. Comparative investigations on hydrogen absorption-desorption properties of Sm-Mg-Ni compounds: the effect of [SmNi₅]/[SmMgNi₄] unit ratio[J]. Journal of Physical Chemistry C, 2018, 43(24): 11079-11084
18	LI F , YOUNG K , OUCHI T , et al. Annealing effects on structural and electrochemical properties of (LaPrNdZr)_0.83Mg_0.17(NiCoAlMn)_3.3 alloy[J]. J Alloys Comp, 2009, 471 (1/2): 371- 377.
19	PAN H G , MA J X , WANG C S , et al. Studies on the electrochemical properties of MlNi_4.3-xcoAl_0.7 hydride alloy electrodes[J]. J Alloys Comp, 1999, 293/295, 648- 652. doi: 10.1016/S0925-8388(99)00359-X

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