Annealing Temperature on Structural and Electrochemical Property of Mg-free La-Y-Ni Based A2B7-type Hydrogen Storage Alloys

doi:10.15541/jim20170222

Abstract

Abstract:

Effects of annealing temperature on the microstructure and electrochemical properties of A₂B₇-type La_0.33Y_0.67Ni_3.25Mn_0.15Al_0.1 hydrogen storage alloys were systematically investigated by XRD, SEM, EDS, and electrochemical measurements. Results showed that the alloy was composed of CaCu₅-type, 2H-Ce₂Ni₇-type, 3R-Gd₂Co₇-type and 3R-Ce₅Cu₁₉-type phases. Both abundance and unit cell volume of Ce₂Ni₇-type phase increased gradually with the anneale temperature increase when the annealing temperature was lower than 950℃. CaCu₅-type and Gd₂Co₇-type phases disappeared at 950℃, but both abundance and unit cell volume of the Ce₂Ni₇-type phase maximized. When annealing temperature was higher than 950℃, Ce₂Ni₇-type phase decreased while Ce₅Co₁₉type phase increased. The alloy, annealed at 950℃, had the lowest hydrogen desorption platform pressure (0.0192~0.087 atm), maximum hydrogen storage capacity (1.35wt%) and high electrochemical discharge capacity (371 mAh/g) with the maximum capacity retention S₁₀₀ at 89% after 100 cycle. The high rate discharge ability (HRD) of the annealed alloys were significantly improved, the alloy annealed at 950℃ had the best performance and HRD₉₀₀ was up to 83.4%. These well performances demonstrated that it is the hydrogen diffusion in the alloys that controls the high rate discharge.

Key words: hydrogen storage materials, La-Y-Ni-based electrode material, heat treatment, microstructure, electrochemical properties

CLC Number:

TG146
TG139

WANG Hao, LUO Yong-Chun, DENG An-Qiang, ZHAO Lei, JIANG Wan-Ting. Annealing Temperature on Structural and Electrochemical Property of Mg-free La-Y-Ni Based A₂B₇-type Hydrogen Storage Alloys[J]. Journal of Inorganic Materials, 2018, 33(4): 434-440.

Figures/Tables 12

Fig. 1 Backscattered SEM images of the La0.33Y0.67Ni3.25Mn0.15Al0.1 alloys annealed at different temperatures (a) As cast; (b) 850℃; (c) 900℃; (d) 950℃; (e) 1000℃; (f) 1050℃

Table 1 Element compositions by ICP for the as-cast alloy and EDS results of the annealed alloys in phase regions

Alloy	Phase area	Atomic ratios of different elements/at%					Stoichiometric B/A
Alloy	Phase area	La	Y	Ni	Mn	Al	Stoichiometric B/A
As-cast (ICP) As-cast	CaCu₅-type	5.3	16.7	69.9	4.4	3.7	3.54
	CaCu₅-type	3.4	14.1	76.0	4.2	2.3	4.71
	Ce₂Ni₇(Gd₂Co₇)-type	4.6	15.0	74.4	3.8	2.2	3.42
	Ce₅Ni₁₉-type	3.8	15.4	74.5	3.7	3.0	4.08
850℃	CaCu₅-type	3.1	13.7	76.3	3.2	3.8	4.95
	Ce₂Ni₇(Gd₂Co₇)-type	5.0	15.5	73.8	3.4	3.3	3.41
	Ce₅Ni₁₉-type	4.0	15.7	73.6	3.7	3.0	4.08
900℃	CaCu₅-type	3.1	13.8	75.0	3.8	3.6	5.06
	Ce₂Ni₇(Gd₂Co₇)-type	5.5	16.2	71.4	3.7	2.5	3.58
	Ce₅Ni₁₉-type	4.3	16.1	72.1	3.5	3.4	3.76
950℃	Ce₂Ni₇-type	6.2	16.0	71.4	3.3	3.1	3.41
950℃	Ce₅Co₁₉-type	5.1	15.8	72.1	4.0	3.0	3.85
1000℃	Ce₂Ni₇-type	5.8	16.4	70.6	4.7	2.5	3.47
1000℃	Ce₅Co₁₉-type	4.8	15.9	71.4	4.9	3.3	3.90
1050℃	Ce₂Ni₇-type	5.2	16.5	72.0	4.5	2.6	3.51
1050℃	Ce₅Co₁₉-type	4.6	16.2	72.1	4.6	2.5	3.81

Fig. 2 XRD patterns of La0.33Y0.67Ni3.25Mn0.15Al0.1 alloys annealed at different temperatures (a), (b) and Rietveld reﬁnement pattern of the alloy annealed at 950℃ (c)

Fig. 3 Dependence of the phases abundance on annealing temperature

Fig. 4 Correlation of cell volume of the phases with annealing temperature

Fig. 5 Activation curves of the alloy electrodes annealed at different temperatures

Fig. 6 Electrochemical P-C desorption isotherms at 298 K of the alloy electrodes annealed at different temperatures

Fig. 7 Discharge capacity versus the number of cycles for the alloy electrodes annealed at different temperatures

Table 2 Hydrogen storage and electrochemical properties of La0.33Y0.67Ni3.25Mn0.15Al0.1 alloy electrodes annealed at different temperatures

Alloy	N_a	C_max/(mAh•g^-1)		(H/M)/wt%	S₁₀₀/%	HRD₉₀₀/%	I₀/(mA•g^-1)	D₀/ (×10^-10, cm²•s^-1)	I_corr/(mA•g^-1)
Alloy	N_a	60/(mA•g^-1)	100/(mA•g^-1)	(H/M)/wt%	S₁₀₀/%	HRD₉₀₀/%	I₀/(mA•g^-1)	D₀/ (×10^-10, cm²•s^-1)	I_corr/(mA•g^-1)
As-cast	3	299.2	252.4	1.07	77.7	78.8	330.9	1.18	6.82
850℃	3	347.2	303.5	1.10	78.2	80.3	278.6	1.57	6.19
900℃	3	353.3	318.5	1.21	78.3	82.3	229.9	1.82	6.14
950℃	3	371.5	365.2	1.35	88.9	83.4	243.5	2.68	5.01
1000℃	5	370.4	358.6	1.34	86.5	80.6	269.1	2.56	5.12
1050℃	6	365.2	356.7	1.28	81.5	76.4	321.5	2.32	5.23

Fig. 8 Tafel polarization curves of the alloy electrodes annealed at different temperatures

Fig. 9 High-rate discharge ability (HRD) at 298 K of the alloy electrodes at different annealing temperatures

Fig. 10 Effect of annealing temperature on I0 and D0 for the alloy electrodes

References 22

[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. Alloys Compd., 1997. 257(1/2): 115-121.
[2]	KOHNO T, YOSHIDA H, KAWASHIMA F,et al. Hydrogen storage properties of new ternary system alloys: La2MgNi9, La5Mg2Ni23, La3MgNi14. J. Alloys Compd., 2000, 311(2): L5-L7.
[3]	LIU Y F, PAN H G, GAO M,et al. Advanced hydrogen storage alloys for Ni/MH rechargeable batteries. J. Mater. Chem., 2011, 21(13): 4743-4755.
[4]	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. Int. J. Hydrogen Energy, 2016, 41(44): 20261-20275.
[5]	YASUOKA S, MAGARI Y, MURATA T,et al. Development of high-capacity nickel-metal hydride batteries using superlattice hydrogen-absorbing alloys. J. Power Sources, 2006, 156(2): 662-666.
[6]	DENYS V R., 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. Solid State Chem., 2008, 181(4): 812-821.
[7]	GAL L, CHARBONNIER V, ZHANG J, et al. Optimization of the La substitution by Mg in the La2Ni7 hydride-forming system for use as negative electrode in Ni-MH battery. Int. J. Hydrogen Energy, 2015, 40(47): 17017-17020.
[8]	MONNIER J, CHEN H, JOIRET S, et al. Identiﬁcation of a new pseudo-binary hydroxide during calendar corrosion of (La, Mg)2Ni7-type hydrogen storage alloys for nickel-metal hydride batteries. J. Power Sources, 2014, 266: 162-169.
[9]	BADDOUR R H, MEYER L, PEREIRA RAMOS J P,et al. An electrochemical study of new La1-xCexY2Ni9(0≤x≤1) hydrogen storage alloys. Electrochim. Acta, 2001, 46(15): 2385-2393.
[10]	BEREZOVETS V V, DENYS R V, RYABOV O B,et al. Hydrides of substituted derivatives based on the YNi3 compound. Mater. Sci., 2007, 43(4): 499-507.
[11]	CHARBONNIER V, MONNIER J, ZHANG J,et al. Relationship between H2 sorption properties and aqueous corrosion mechanisms in A2Ni7 hydride forming alloys (A = Y, Gd or Sm). J. Power Sources, 2016, 326: 146-155.
[12]	YAN H Z, XIONG W, WANG L,et al. Investigations on AB3-, A2B7- and A5B19-type La-Y-Ni system hydrogen storage alloys. Int. J. Hydrogen Energy, 2017, 42(4): 2257-2264.
[13]	长崎诚三, 平林真. 二元合金状态相图集. 北京: 冶金工业出版社, 2004: 197.
[14]	SUBRAMANIAN P R, SMITH J F.Thermodynamics of formation of Y-Ni alloys.Metallurgical Transactions B, 1985, 16B: 577-584.
[15]	YOUNG R A. The Rietvld Method.London: Oxford University Press, 1995.
[16]	YAMAMOTO T, INUI H, YAMAGUCHI M,et al. Microstructures and hydrogen absorption/desorption properties of La-Ni alloys in the composition range of La-(77.8-83.2)at%Ni. Acta Materialia, 1997, 45(12): 5213-5218.
[17]	XIONG W, YAN H Z, WANG L,et al. Effects of annealing temperature on the structure and properties of the LaY2Ni10Mn0.5 hydrogen storage alloy. Int. J. Hydrogen Energy, 2017, 42(22): 15319-15327.
[18]	LUO G, HU X C, LI S L,et al. Hydrogen storage properties of La1-xYxNi5-yAly Alloys. Rare Metal Materials and Engineering, 2012, 41(10): 1693-1699.
[19]	LIU J J, LI Y, HAN D,et al. Electrochemical performance and capacity degradation mechanism of single-phase La-Mg-Ni-based hydrogen storage alloys. J. Power Sources, 2015, 300: 77-86.
[20]	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. Phys. Chem. C, 2015, 119(9): 4719-4727.
[21]	NOTTEN P H L, HOKKELING P. Double phase hydride forming compounds: a new class of highly electrocatalytic materials.J. Electrochem. Soc., 1991, 138(7): 1877-1885.
[22]	ZHENG G, POPOV B N, WHITE R E.Electrochemical determination of the diffusion coefficient of hydrogen through an LaNi4.25Al0.75 electrode in alkaline aqueous solution. J. Electrochem. Soc., 1995, 142(8): 2695-2698.

Annealing Temperature on Structural and Electrochemical Property of Mg-free La-Y-Ni Based A₂B₇-type Hydrogen Storage Alloys

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