热处理对A_2B_7型RE-Mg-Ni合金相结构及性能的影响
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摘要
采用磁悬浮感应熔炼法制备了La0.35Gd0.2Sm0.2Y0.1Mg0.15Ni3.35Al0.15合金。通过XRD,SEM,PCT及电化学性能测试等方法,研究了热处理对于该合金相结构及性能的影响。结果表明:该合金主要由PuNi3型、CaCu5型、Ce2Ni7型和Ce5Co19型相组成,随着热处理温度的提高,合金中CaCu5型相减少,Ce2Ni7型相和Ce5Co19型相增加,热处理温度高于1223 K后,合金主相由PuNi3型相转为Ce2Ni7型相,合金的储氢量增加,吸放氢平台压及平台斜率降低,电化学循环稳定增强。
The as-cast La0. 35Gd0. 2Sm0. 2Y0. 1Mg0. 15Ni3. 35Al0. 15 alloy was prepared by vacuum induction levitation melting method. The influence of annealing treatment on the phase structure and properties of the as-cast alloy was investigated by X-ray diffraction( XRD),scanning electron microscopy( SEM),pressure composition temperature( PCT) and electrochemical test. The results showed that La0. 35Gd0. 2Sm0. 2Y0. 1Mg0. 15Ni3. 35Al0. 15 alloy was composed of PuNi3-type,CaCu5-type,Ce2Ni7-type and Ce5Co19-type phases. With increasing heat treatment temperature,the abundance of CaCu5-type phase decreased,and the abundance of Ce2Ni7-type and Ce5Co19-type phase increased.The structure of main phase of alloys was transformed from PuNi3-type into Ce2Ni7-type when the temperature of heat treatment was higher than 1223 K. These led a higher hydrogen storage capacity,a lower hydrogen storage plateau pressure,a smaller plateau slope and a better electrochemical cycling stability.
The as-cast La0. 35Gd0. 2Sm0. 2Y0. 1Mg0. 15Ni3. 35Al0. 15 alloy was prepared by vacuum induction levitation melting method. The influence of annealing treatment on the phase structure and properties of the as-cast alloy was investigated by X-ray diffraction( XRD),scanning electron microscopy( SEM),pressure composition temperature( PCT) and electrochemical test. The results showed that La0. 35Gd0. 2Sm0. 2Y0. 1Mg0. 15Ni3. 35Al0. 15 alloy was composed of PuNi3-type,CaCu5-type,Ce2Ni7-type and Ce5Co19-type phases. With increasing heat treatment temperature,the abundance of CaCu5-type phase decreased,and the abundance of Ce2Ni7-type and Ce5Co19-type phase increased.The structure of main phase of alloys was transformed from PuNi3-type into Ce2Ni7-type when the temperature of heat treatment was higher than 1223 K. These led a higher hydrogen storage capacity,a lower hydrogen storage plateau pressure,a smaller plateau slope and a better electrochemical cycling stability.
引文
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[2]周顺,孙泰,唐仁衡,肖方明.无镨钕AB5型Mm(Ni,Co,Mn,Al)5合金储氢及电化学性能研究[J].中国稀土学报,2013,31(1):60.Zhou S,Sun T,Tang R H,Xiao F M.Properties andelectrochemical performance of Pr/Nd-Free Mm(Ni,Co,Mn,Al)5hydrogen storage alloy[J].Journal of the Chinese Society of Rare Earths,2013,31(1):60.
[3]Liu Y F,Cao Y H,Huang L,Gao M X,Pan H G.Rare earth-Mg-Ni-based hydrogen storage alloys as negative electrode materials for Ni/MH batteries[J].J.Alloys Compd.,2011,509(3):675.
[4]Zhang F L,Luo Y C,Chen J P,Yan R X,Chen J H.La-Mg-Ni ternary hydrogen storage alloys with Ce2Ni7-type and Gd2Co7-type structure as negative electrodes for Ni/MH batteries[J].J.Alloys Compd.,2007,430(1-2):302.
[5]Wang B P,Chen Y Z,Wang L,Liu Y N.Effect o annealing time on the structure and electrochemica properties of La0.72Nd0.08Mg0.2Ni3.4Al0.1hydrogen storage alloys[J].J.Alloys Compd.,2012,541(15):305.
[6]Guo P P,Lin Y F,Zhao H H,Guo S H,Zhao D L.Structure and high-temperature electrochemical properties of La0.60Nd0.15Mg0.25Ni3.3Si0.10hydrogen storage alloys[J].J.Rare Earths,2011,29(6):574.
[7]Gao J,Yan X L,Zhao Z Y,Zhao Z Y,Chai Y J,Hou D L.Effect of annealed treatment on microstructure and cyclic stability for La-Mg-Ni hydrogen storage alloys[J].J.Power Sources,2012,209(1):257.
[8]Li Y,Han D,Han S M,Zhu X L,H L,Zhang L.Effect of rare earth elements on electrochemical properties of La-Mg-Ni-based hydrogen storage alloys[J].Int.J.Hydrogen Energy,2009,34(3):1399.
[9]Young K,Ouchi T,Huang B.Effects of annealing and stoichiometry to(Nd,Mg)(Ni,Al)3.5metal hydride alloys[J].J.Power Sources,2012,215(1):152.
[10]林振,罗永春,高志杰,康龙.钆对La-Mg-N系A2B7型储氢合金微观结构和电化学性能的影响[J].中国稀土学报,2011,29(3):345.Lin Z,Luo Y C,Gao Z J,Kang L.Effects of Gadolinium on microstructure and electrochemical properties o La-Mg-Ni based A2B7-Type hydrogen storage alloys[J].Journal of the Chinese Society of Rare Earths,2011,29(3):345.
[11]Zhang Y H,Hou Z H.Li B W,Ren H P,Zhang G F,Zhao D L.An investigation on electrochemical hydro-gen storage performances of the as-cast and annealed La0.8-xSmxMg0.2Ni3.35Al0.1Si0.05(x=0~0.4)alloy[J].J.Alloys Compd.,2012,537:175.
[12]Tang R,Wei X D,Liu Y N,Zhu C C,Zhu J W,Yu G.Effect of the Sm content on the structure and electrochemical properties of La1.3-xSmxCaMg0.7Ni9(x=0~0.3)hydrogen storage alloys[J].J.Power Sources,2006,155:456.
[13]邹欣伟,张敏刚,孙钢.稀土对La0.6R0.2Mg0.2(NiCOAlMn)3.3储氢合金相结构和电化学性能的影响[J].特种铸造及有色冶金,2011,31(3):255.Zou X W,Zhang M G,Sun G.Effect of Substition rare earth on the on the structure and electochemical properties of La0.6R0.2Mg0.2(NiCOAlMn)3.3hydrogen storage alloy[J].Journal of Special Casting and Nonferrous Metallurgy,2011,31(3):255.
[14]黄勇平,杨琨,谢亚林.钇替代镧对La-Mg-Ni系储氢合金晶体结构及其电化学性能的影响[J].中国稀土学报,2011,29(4):484.Huang Y P,Yang K,Xie Y L.Effect of substition Y for La on the structure and electochemical properties of La-Mg-Ni hydrogen storage alloy[J].Journal of the Chinese Society of Rare Earths,2011,29(4):484.
[15]Jian L,Jiang L J,Yuan H P.Effects of annealing treament and partial Sm and Y on the phase composition and hydrogen storage properties of A2B7-type La-Mg-Ni hydrogen storage electrode alloys[A].Proceedings of abstracts(S309),5th World Hydrogen Technologies Convention[C].Shanghai,China,2013.
[16]Akiba E,Hayakawa H,Kohno T.Crystal structures of novel La-Mg-Ni hydrogen absorbing alloys[J].J.Alloys Compd.,2006,408-412:280.
[17]Hayakawa H,Akiba E,Gotoh M,Kohno T.Crystal Structure of La-Mg-Nix(x=3~4)system hydrogen storage alloys[J].Mater.Trans.,2005,6(46):1393.
[18]Chai Y J,Sakaki K,Enoki H,Akiba E,Kohno T.Crystal structure and hydrogen storage properties of LaMg-Ni-Co alloy with superstructure[J].Scr.Mater.,2007,57(6):545.
[19]Liu Y F,Pan H G,Yue Y J,Wu X F,Chen N,Lei Y Q.Cycling durability and degradation behavior of La-Mg-Ni-Co-type metal hydride electrodes[J].J.Alloys Compd.,2005,395(1):291.
[20]Li F,Young K,Ouchi T,Fetcenko M A.Annealingeffects on structural and electrochemical properties of(LaPrNdZr)0.83Mg0.17(NiCoAlMn)3.3alloy[J].J.Alloys Compd.,2009,471(1-2):371.