退火温度对La4MgNi17. 5Co1. 5贮氢合金结构和性能的影响

蔡鑫; 魏范松; 胥小丽; 肖佳宁; 魏范娜

doi:10.13228/j.boyuan.issn 1005- 8192.2015037

金属功能材料 ›› 2015, Vol. 22 ›› Issue (4) : 16-20. DOI: 10.13228/j.boyuan.issn 1005- 8192.2015037

退火温度对La4MgNi17. 5Co1. 5贮氢合金结构和性能的影响

蔡鑫，魏范松，胥小丽，肖佳宁, 魏范娜

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Influences of different temperatures of annealing treatment on electrochemical properties of La4MgNi17. 5Co1. 5 hydrogen storage alloy

CAI Xin，WEI Fan- song，XU Xiao- li，XIAO Jia- ning， WEI Fan- na

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摘要

研究了不同退火温度对La4MgNi17. 5Co1. 5合金相结构及电化学性能的影响。XRD分析表明，合金主要由LaNi5相 (CaCu5结构)和La4MgNi19相(Ce5Co19+Pr5Co19)组成，且退火温度的增加，可使La4MgNi19的相丰度和晶胞体积增大。但退火温度提高到1 173 K时，La4MgNi19有所减少并出现富Ni相。电化学性能测试表明，随着退火温度提高到1 123 K，合金电极的最大放电容量(Cmax)明显增大，循环寿命(S100)和高倍率放电性能(HRD900)也得到了明显改善。但退火温度进一步提高到1 173 K时，上述电化学性能均有所下降。如：Cmax和S100分别从铸态时的369. 66 mA·h/g和59. 96%提高到1 123 K时的375. 33 mA·h/g和65. 52%，然后又下降到1 173 K时的312. 44 mA·h/g和62. 82%。研究认为退火温度的提高可以改善成分的均匀性，提高La4MgNi19相的含量。但温度进一步提高则可能增加Mg的挥发，导致La4MgNi19相发生分解。

Abstract

The influences of different temperatures of annealing treatment on the phase structure and electrochemical properties of La4MgNi17. 5Co1. 5 hydrogen storage alloy were investigated. The XRD analysis reveals that the alloys consist of LaNi5 phase and La4MgNi19 phase. With the increase of the temperature of annealing, the cell volume and the abundance of La4MgNi19 phase increases. While the temperature is up to 1 173 K, the abundance of La4MgNi19 phase decreases and the Ni- riched phase appears. The electrochemical measurement shows that the maximum discharge capacity increases obviously when the temperature is up to 1 123 K. The high- rate discharge ability(HRD) and cyclic stability(S100) are also improved. But when the temperature is up to 1 173 K, the electrochemical properties above are all decreased. For example, Cmax and S100 are increased from (369. 66 mA·h/g, 59. 96%)(as- cast) to (375. 33 mA·h/g, 65. 52%)(1 123 K) and then decreased to (312. 44 mA·h/g, 62. 82%)(1 173 K). It is found that the increase of the temperatures of annealing treatment can improve the uniformity of the phase structure. But when the temperature increases further, it will increase the volatilization of Mg and lead to the decomposing of La4MgNi19 phase.

关键词

关键词：贮氢合金 / A5B19型 / 退火 / 电化学性能

Key words

Key words: hydrogen storage alloys / A5B19 type / annealing / electrochemical property

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蔡鑫, 魏范松, 胥小丽, 等. 退火温度对La4MgNi17. 5Co1. 5贮氢合金结构和性能的影响[J]. 金属功能材料, 2015, 22(4): 16-20 https://doi.org/10.13228/j.boyuan.issn 1005- 8192.2015037

CAI Xin, WEI Fan-Song, XU Xiao-Li, et al. Influences of different temperatures of annealing treatment on electrochemical properties of La4MgNi17. 5Co1. 5 hydrogen storage alloy[J]. Metallic Functional Materials, 2015, 22(4): 16-20 https://doi.org/10.13228/j.boyuan.issn 1005- 8192.2015037

参考文献

[1] Yongquan Lei.New energy materials[M]. Tianjin: Tianjin University Press, 2000: 44-45
[2]Kohno T, Yoshida H, Kawashima F, etal.Hydrogen storage properties of new ternary system alloys: LaMg2Ni9,La5Mg2Ni23,La3MgNi14[J].Alloys Comp, 2000, 311(2):L5-L7
[3]刘永峰, 潘洪革, 高明霞, 等.稀土镁基贮氢电极合金的结构与电化学性能研究[J].金属学报, 2003, 39(6):666-672
[4]王大辉, 罗永春, 闫汝煦, 等.La0.67Mg033Ni2.5Co0.5贮氢合金的制备和MH电极性能的研究[J].稀有金属材料与工程, 2004, 33(12):1283-1286
[5]董小平, 杨丽颖, 陈荣, 等.复相--系贮氢合金制备技术新进展[J].稀有金属与硬质合金, 2010, 38(3):57-62
[6]韩树民, 李媛.稀土-镁-镍基贮氢合金的研究进展[J].燕山大学学报, 2010, 34(4):283-288
[7] Hayakawa H, Akiba E, Gotoh M, et al.Crystal Structures of La-Mg-Ni_x(x=3-4) System Hydrogen Storage Alloys.[J].Materials Transactions, 2005, 46(6):1393-1394
[8]Zhang Y H, Li B W, Ren H P, et al.Influence of Substituting Ni with Fe on Cycle Stabilities of As-cast and As-quenched La075Mg0.3Co0.45Ni2.55-xFex(x=0-0.4) Electrode Alloys[J].Rare Metal Materials and Engineering, 2009, 38(6):941-946
[9]Miao H, Gao M X, Li D F, et al.Effect of Boron Addition on Structure and Electrochemical Properties of La-Mg-Ni-Co System Hydrogen Storage Electrode Alloys[J].Rare Metal Materials and Engineering, 2009, 38(2):0193-0197
[10] Chai Y J, Sakaki K, Asano K, Enoki H, Akiba E, Kohno T.Crystal structure and hydrogen storage properties of La-Mg-Ni-Coalloy with superstructure[J].Scripta Materialia, 2007 , 57(6):545-548
[11]Pan C C, Cai W P, et al.Microstructure and Electrochemical Properties of Melt-spun Nd08 Mg0.2(Ni0.8Co0.2)3.8 Hydrogen Storage Alloy[J].Journal of Rare Earths, 2010, 28(1):100-103
[12]陈江平, 罗永春, 张法亮, 等.退火处理对..贮氢合金相结构和电化学性能的影响[J].稀有金属材料与工程, 2006, 35(10):1572-1576
[13]唐仁衡, 周顺, 肖方明, 等.热处理温度对.储氢合金结构与性能的影响[J].材料导报, 2015, 22(1):48-52
[14]邓安强, 罗永春, 樊静波.铸态及退火处理后...储氢合金相结构的研究[J].热加工工艺, 2015, 44(3):99-101
[15]李蒙, 朱磊, 尉海军, 简旭宇.La-Mg-Ni系A5B19相储氢合金热处理工艺研究[J].稀有金属, 2012, 36(2):236-241
[16]邓安强, 樊静波, 钱克农, 等.热处理对储氢电极合金结构和性能的影响[J].物理化学学报, 2011, 27(1):103-107
[17] Alzic G D, Johnson J R, Mukerjee S, McBreen J, Reilly J J.Function of cobalt in AB5Hx electrodes[J].Journal of Alloys and Compounds, 1997, 253-254(1-2):579-582
[18] Cocciantellik J M, Bernard P, Fenandez S, Atkin J.The influence of Co and various additives on the performance of MmNi4.3-xMn0.33A10.4Cox hydrogen storage alloys and Ni/MH prismatic sealed cells[J].Journal of Alloys and Compounds, 1997, 253-254(1-2):642-647
[19] Chartouni D, Meli F, ZUttel A, Gross K, Schlapbach L.The influence of cobalt on the electrochemical cycling stability of La-Ni5-based hydride forming alloys[J].Journal of Alloys and Compounds, 1996, 241(1-2):160-166
[20] Hayakawa H, Akiba E, Gotoh M, et al.Crystal structure of La-Mg-Nix(x=3~4) system hydrogen storage alloys[J].Matericals Transactions, 2005, 46(6):1393-1394
[21]董小平, 张羊换, 吕反修, 等.退火对..=, .合金结构与电化学性能影响[J].功能材料, 2008, 39(2):238-241
[22]Wei Fan-song, Lei Yong-quan, Chen Li-xin, Ying Tiao, Ge Hong-wei, Lü Guang-lie.Influence of material processing on crystallographic and electrochemical properties of cobalt-free LaNi495Sn0.3 hydrogen storage alloy[J].Transactions of Nonferrous Metals Society of China, 2006, 16(3):527-531