Effect of Annealing Treatment on the Phase Structure and ElectrochemicalPropertiesof La0.63(Pr0.1Nd0.1Y0.6Sm0.1Gd0.1)0.2Mg0.17Ni3.1Co0.3Al0.1 A2B7-type Hydrogen Storage Alloys
DENG Anqiang1,2, LUO Yongchun1,2, WANG Hao1, ZHAO Lei1, LUO Yuankui1
1 School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050; 2 State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals,Lanzhou University of Technology, Lanzhou 730050
Abstract: La0.63(Pr0.1Nd0.1Y0.6Sm0.1Gd0.1)0.2Mg0.17Ni3.1Co0.3Al0.1 hydrogen storage alloys were prepared by high frequency induction melting, and the as-cast alloy was annealed at 900 ℃ for 24 h. A structural analysis of the alloys showed that the as-cast alloy was composed of CaCu5-type, Ce5Co19-type and Ce2Ni7-type phases, while the annealed alloy was a single phase Ce2Ni7-type structure. Both the as-cast and annealed alloy electrodes had good activation properties. Discharge curve platform became flatter and wider after annealing treatment. The corrosion potential of the two alloy electrode was basically the same, but the as-cast alloy electrode bear higher corrosion current. The cycle stability of the annealed alloy electrode (S100=83.5%) was obviously better than that of the as-cast alloy electrode (S100=69%). In 100 electrochemical charge/discharge cycles, when the charge capacity was low, the capacity of the alloy electrodes did not degraded. 90% Cmax was the charging capacity critical point of alloy electrode capacity attenuation. The kinetic properties of both the as-cast and annealed alloy electrodes were almost the same. High rate dischargeability characteristics of as-cast alloy electrode was controlled by the hydrogen diffusion rate in alloy bulk, while the annealed alloy electrode was controlled by the charge transfer on alloys surface.
邓安强, 罗永春, 王浩, 赵磊, 罗元魁. 退火处理对A2B7型La0.63(Pr0.1Nd0.1Y0.6Sm0.1Gd0.1)0.2Mg0.17Ni3.1Co0.3Al0.1[J]. 材料导报, 2018, 32(15): 2565-2570.
DENG Anqiang, LUO Yongchun, WANG Hao, ZHAO Lei, LUO Yuankui. Effect of Annealing Treatment on the Phase Structure and ElectrochemicalPropertiesof La0.63(Pr0.1Nd0.1Y0.6Sm0.1Gd0.1)0.2Mg0.17Ni3.1Co0.3Al0.1 A2B7-type Hydrogen Storage Alloys. Materials Reports, 2018, 32(15): 2565-2570.
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].Journal of Alloys and Compounds,1997,257:115. 2 Kohno T, Yoshida H, Kawashima F, et al. Hydrogen storage pro-perties of new ternary system alloys: La2MgNi9, La5Mg2Ni23, La3MgNi14[J].Journal of Alloys and Compounds,2000,311:L5. 3 Verbovyts’kyi Y V, Zavalii I Y. New metal-hydride electrode materials based on R1-xMgxNi3-4 alloys for chemical current sources[J].Materials Science,2016,51:443. 4 Deng A Q,Fan J B,Qian K N,et al. Effect of heat treatment on the structure and properties of La4MgNi19 hydrogen storage electrode alloys[J].Acta Physico-Chimica Sinica,2011,27(1):103(in Chinese). 邓安强,樊静波,钱克农,等.热处理对La4MgNi19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. 5 Aoki K, Masumoto T. Hydrogen-induced amorphization of intermetallics[J].Journal of Alloys and Compounds,1995,231:20. 6 Chung U I, Lee J Y. A study on hydrogen-induced amorphization in the La-Ni system[J].Journal of Non-Crystalline Solids,1989,110:203. 7 Gal L, Charbonnier V, Zhang J X, et al. Optimization of the La substitution by Mg in the La2Ni7 hydride-forming system for use as negative electrode in Ni-MH battery[J].International Journal of Hydrogen Energy,2015,40:17017. 8 Denys R V, Riabov A B, Yartys V A, et al. Mg substitution effect on the hydrogenation behaviour, thermodynamic and structural properties of the La2Ni7-H(D)2 system[J].Journal of Solid State Chemistry,2008,181:812. 9 Zhang Y H, Yang T, Zhai T T, et al. Effects of stoichiometric ratio La/Mg on structures and electrochemical performances of as-cast and annealed La-Mg-Ni-based A2B7-type electrode alloys[J].Transactions of Nonferrous Metals Society of China,2015,25:1968. 10 Iwase K, Terashita N, Mori K, et al. Structural parameters of Pr3MgNi14 during hydrogen absorption-desorption process[J].Inorganic Chemistry,2012,51:11805. 11 Ma S, Gao M X, Li R, et al. A study on the structural and electrochemical properties of La0.7-xNdxMg0.3Ni2.45Co0.75Mn0.1Al0.2 (x=0.0-3.0) hydrogen storage alloys[J].Journal of Alloys and Compounds,2008,457:457. 12 Zhang Q A, Chen Z L, Li Y T, et al. Comparative investigations on hydrogen absorption-desorption properties of Sm-Mg-Ni compounds: The effect of [SmNi5]/[SmMgNi4] unit ratio[J].The Journal of Physical Chemistry C,2015,119:4719. 13 Charbonnier V, Monnier J, Zhang J X, et al. Relationship between H2 sorption properties and aqueous corrosion mechanisms in A2Ni7 hydride forming alloys ( A=Y, Gd or Sm)[J].Journal of Power Sources,2016,326:146. 14 Li Y, Han D, Han S M, et al. Effect of rare earth elements on electrochemical properties of La-Mg-Ni-based hydrogen storage alloys[J].International Journal of Hydrogen Energy,2009,34:1399. 15 Puga B, Joiret S, Vivier V, et al. Electrochemical properties and dissolution mechanism of A2Ni7 hydrides (A=Y, Gd, La-Sm)[J].ChemElectroChem,2015,2:1321. 16 Gao Z J, Kang L, Luo Y C. Microstructure and electrochemical hydrogen storage properties of La-R-Mg-Ni-based alloy electrodes[J].New Journal of Chemistry,2013,37:1105. 17 Roisnel T, Rodríquez-Carvajal J. WinPLOTR: A windows tool for powder diffraction pattern analysis[J].Materials Science Forum,2001,378-381:118. 18 Georg. Powder diffraction: The rietveld method and the two-stage method to determine and refine crystal structures from powder diffraction data[M].Heidelberg:Springer Press,2006:1 19 Okamoto H. La-Ni (lanthanum-nickel)[J].Journal of Phase Equilibria,2002,23(3):287. 20 Virkar A V, Raman A. Crystal structures of AB3 and A2B7 rare earth-nickel phases[J].Journal of the Less Common Metals,1969,18:59. 21 Iwase K, Sakaki K, Nakamura Y, et al. In situ XRD study of La2Ni7Hx during hydrogen absorption-desorption[J].Inorganic Chemistry,2013,52:10105. 22 潘金生.材料科学基础[M].北京:清华大学出版社,2011:127. 23 Charbonnier V, Zhang J X, Monnier J, et al. Structural and hydrogen storage properties of Y2Ni7 deuterides studied by neutron powder diffraction[J].The Journal of Physical Chemistry C,2015,119:12218. 24 Li F, Young K, Ouchi T, et al. Annealing effects on structural and electrochemical properties of (LaPrNdZr)0.83Mg0.17(NiCoAlMn)3.3 alloy[J].Journal of Alloys and Compounds,2009,471:371. 25 Notten P H L. Double-phase hydride forming compounds: A new class of highly electrocatalytic materials[J].Journal of the Electrochemical Society,1991,138:1877. 26 Zheng G. Electrochemical determination of the diffusion coefficient of hydrogen through an LaNi4.25Al0.75 electrode in alkaline aqueous solution[J].Journal of the Electrochemical Society,1995,142:2695.
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2018, Vol. 32 
