Ce替代Y对Y_(1-x)Ce_xFe_2(x=0,0.15,0.25和0.50)合金吸氢性能的影响
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摘要
利用磁悬浮感应熔炼法制备了Y_(1-x)Ce_xFe_2(x=0,0.15,0.25,和0.50)合金,通过X射线衍射分析(XRD)、扫描电镜(SEM)、电子探针(EPMA)和定容法等测试方法,研究了Ce替代Y对Y_(1-x)Ce_xFe_2合金吸氢性能的影响。研究表明,Y_(1-x)Ce_xFe_2合金为多相结构,主相为MgCu_2型结构的YFe_2相,同时还含有Pu Ni3型结构的YFe_3第二相,且Ce元素有效替代了合金中的Y元素;当x≦0.25时,随着Ce替代量的增加,合金中YFe_3相增多,且合金的吸氢动力学性能和吸放氢循环稳定性得以改善,初始吸氢平衡时间t0.9由48 s降低至12 s,经7次吸放氢循环后,稳定吸氢容量由0.409%升高至0.598%(质量分数),吸氢容量衰减率由79%降低至55%,但合金初始吸氢容量有所下降;这主要归因于YFe_3相较之于YFe_2相结构更加稳定,但其吸氢容量更低;当x=0.50时,合金的吸氢容量及吸放氢循环稳定性均同步下降,此时合金中的YFe2相增多,合金吸氢后歧化反应加剧。因此,在Y_(1-x)Ce_xFe_2中,Ce对Y的替代量以小于0.50为宜。
The Y_(1-x)Ce_xFe_2 alloys were prepared by induction levitation melting method. The effect of Ce substitution for Y on hydrogen absorption properties of the alloys was investigated by X-ray diffraction( XRD),scanning electron microscope( SEM),electron probe microanalysis( EPMA) and Sievert's method. The results revealed that Y_(1-x)Ce_xFe_2 alloys had a multi-phase structure. The major phase was YFe_2 and second phase was YFe_3. In addition,Y element was substituted by Ce element efficiently in the alloys. When x ≦ 0. 25,the content of YFe_3 phase increased with the increase of Ce substitution for Y. The hydrogen absorption kinetics and cycle stability of the alloys were improved with the increase of Ce content due to more stable structure of YFe_3 than that of YFe_2. The initial hydrogen absorption equilibrium time t0. 9 decreased from 48 to 12 s. After 7 absorption and desorption cycles,the stable hydrogen absorption capacity increased from 0. 409% to 0. 598%( mass fraction),and the hydrogen absorption capacity decay rate decreased from79% to 55%. However,the hydrogen absorption capacity of the alloys decreased owing to much lower hydrogen storage capacity of YFe_3. When x = 0. 50,both the hydrogen absorption capacity and the cycle stability declined. Meantime,the content of YFe_2 phase increased significantly which intensified disproportionation after hydrogenation. Hence,the substitution of Ce for Y should be less than0. 50.
The Y_(1-x)Ce_xFe_2 alloys were prepared by induction levitation melting method. The effect of Ce substitution for Y on hydrogen absorption properties of the alloys was investigated by X-ray diffraction( XRD),scanning electron microscope( SEM),electron probe microanalysis( EPMA) and Sievert's method. The results revealed that Y_(1-x)Ce_xFe_2 alloys had a multi-phase structure. The major phase was YFe_2 and second phase was YFe_3. In addition,Y element was substituted by Ce element efficiently in the alloys. When x ≦ 0. 25,the content of YFe_3 phase increased with the increase of Ce substitution for Y. The hydrogen absorption kinetics and cycle stability of the alloys were improved with the increase of Ce content due to more stable structure of YFe_3 than that of YFe_2. The initial hydrogen absorption equilibrium time t0. 9 decreased from 48 to 12 s. After 7 absorption and desorption cycles,the stable hydrogen absorption capacity increased from 0. 409% to 0. 598%( mass fraction),and the hydrogen absorption capacity decay rate decreased from79% to 55%. However,the hydrogen absorption capacity of the alloys decreased owing to much lower hydrogen storage capacity of YFe_3. When x = 0. 50,both the hydrogen absorption capacity and the cycle stability declined. Meantime,the content of YFe_2 phase increased significantly which intensified disproportionation after hydrogenation. Hence,the substitution of Ce for Y should be less than0. 50.
引文
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[2]Niaz S,Manzoor T,Pandith A H.Hydrogen storage:materials,methods and perspectives[J].Renewable and Sustainable Energy Reviews,2015,50:457.
[3]Broom D P.Hydrogen storage materials:the characterisation of their storage properties[J].International Journal of Hydrogen Energy,2012,37(9):7950.
[4]Zhang B W,Liu G,Han K.The Fe-Y(iron-yttrium)system[J].Journal of Phase Equilibria,1992,13(3):304.
[5]Kardellass S,Servant C,Selhaoui N,Iddaoudi A,Amar M A,Bouirden L.A thermodynamic assessment of theiron-yttrium system[J].Journal of Alloys and Compounds,2014,583(1):598.
[6]Essen R H V,Buschow K H J.Hydrogen sorption characteristics of Ce-3d and Y-3d intermetallic compounds[J].Journal of the Less Common Metals,1980,70(2):189.
[7]Mal H H V,Buschow K H J,Miedema A R.Hydrogen absorption of rare-earth(3d)transition intermetallic compounds[J].Journal of the Less Common Metals,1976,49(1):473.
[8]Aoki K,Li H W,Dilixiati M.Formation of crystalline and amorphous hydrides by hydrogenation of C15 Laves phase YFe2[J].Materials Science and Engineering A,2007,449(12):2.
[9]Dilixiati M,Kanda K,Ishikawa K,Aoki K.Thermal analysis of hydrogen-induced amorphization in C15 Laves RFe2compounds[J].Journal of Alloys and Compounds,2002,330(1):743.
[10]Dilixiati M,Kanda K,Ishikawa K,Aoki K.Hydrogen induced amorphization in C15 Laves phases RFe2[J].Journal of Alloys and Compounds,2002,337(1):128.
[11]Aoki K.Amorphous phase formation by hydrogen absorption[J].Materials Science and Engineering:A,2001,304(1):45.
[12]Wang B P,Zhao L M,Wang X W,Hou C P.Structure and electrochemical properties of R-Mg-Ni-Based alloys with Sn substitution for Ni[J].Chinese Journal of Rare Metals,2015,39(6):487.(王北平,赵丽敏,王兴蔚,侯春平.Sn替代Ni对R-Mg-Ni基合金结构和电化学性能的影响[J].稀有金属,2015,39(6):487.)
[13]Wang W,Luo Y C,Qiu J P,Kang L.Microstructure and hydrogen storage properties of Sc-based laves phase alloys Sc0.8Zr0.1Y0.1Mn2-xNix(x=0~2.0)[J].Chinese Journal of Rare Metals,2015,39(8):696.(王稳,罗永春,邱建平,康龙.钪基Laves相合金Sc0.8Zr0.1Y0.1Mn2-xNix(x=0~2.0)的微观结构和储氢性能[J].稀有金属,2015,39(8):696.)
[14]Khatamian D,Manchester F D.The H-Y(HydrogenYttrium)system[J].Bulletin of Alloy Phase Diagrams,1988,9(3):252.
[15]Yannopoulos L N,Edwards R K,Wahlbeck P G.The thermodynamics of the tttrium-hydrogen system[J].The Journal of Physical Chemistry,1965,69(8):2510.
[16]Hirano K,Kadono J,Yamamoto S,Tanabe T,Miyake H.Hydrogen-absorbing characteristics of 15 rare earth elements[J].Journal of Alloys and Compounds,2006,37(16):351.