Structural and Electrochemical Properties of A2B7-type La1-xScxNi2.6Co0.3Mn0.5Al0.1 (x = 0~0.5) Hydrogen Storage Alloys

doi:10.15541/jim20150125

Abstract

Abstract:

A₂B₇-type La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0-0.5) hydrogen storage alloys were prepared by vacuum arc melting method and annealed at 1173 K. XRD and SEM-EDS results showed that the annealed alloys mainly consisted of La₂Ni₇, LaNi₅, LaNi, and ScNi₂phases. The enthalpy of formation calculation analyses showed that the enthalpy of formation of binary alloy of Sc-Ni was more negative than that of La-Ni and Mg-Ni. This was one of the main reasons that the phase rule of Sc-contained alloy was different from Mg-contained alloy, which facilitated forming ScNi₂phase. The electrochemical measurement results showed that the discharge capacity and the cycle stability of the alloys were all firstly increased and then decreased with the x value increasing. The discharge capacity and cyclic stability (S₁₀₀) of alloy electrodes reached the maximum of 261.1 mAh/g and 80.47%, respectively, when x value was equal to 0.2. The appropriate amount of Sc in alloy could obviously inhibit the hydrogen-induced amorphous, meanwhile the alloy with Sc content also tends to form the non-hydrogen absorbing ScNi₂ phase, which is the main reason that the discharge capacity of alloy electrode is not significantly improved.

Key words: Re-Ni based A2B7-type hydrogen storage alloys, Sc element substitution, microstructure, electrochemical properties

CLC Number:

TG146

MEI Xing-Zhi, LUO Yong-Chun, ZHANG Guo-Qing, KANG Long. Structural and Electrochemical Properties of A₂B₇-type La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5) Hydrogen Storage Alloys[J]. Journal of Inorganic Materials, 2015, 30(10): 1049-1055.

Figures/Tables 11

Fig. 1 XRD patterns of the annealed alloys La1-xScxNi2.6Co0.3Mn0.5Al0.1 (a) and the alloys after hydrogenation (b)

Fig. 2 Phases abundance in the annealed alloys versus Sc content (x)

Fig. 3 Unit cell volume of the annealed alloys versus Sc content (x)

Fig. 4 SEM back scattered electron images of the annealed alloys. (a) x = 0; (b) x = 0.2; (c) x = 0.5 (α: LaNi5 phase, β: La2Ni7 phase, γ: LaNi phase, δ: ScNi2 phase)

Table 1 EDS analysis results of the phase areas of the annealed alloys

Sample	Phase area	Phase composition / at%						Stoichiometric B/A
Sample	Phase area	La	Sc	Ni	Co	Mn	Al	Stoichiometric B/A
x = 0	α area /LaNi₅ type	16.7	0	60.1	6.8	12.5	3.9	4.99
	β area /La₂Ni₇ type	22.1	0	60.9	5.6	9.6	1.8	3.52
	γ area /LaNi type	48.7	0	50.5	0.6	0.1	0.1	1.05
x = 0.2	α area /LaNi₅ type	16.3	0.2	60.2	6.6	12.9	3.6	5.06
	β area /La₂Ni₇ type	20.3	2.0	58.7	5.4	9.9	1.7	3.48
	γ area /LaNi type	49.0	0.2	49.9	0.6	0.1	0.2	1.03
	δ area /ScNi₂ type	0.9	31.9	47.0	10.3	8.7	1.2	2.05
x = 0.5	α area /LaNi₅ type	16.6	0.3	61.2	5.9	11.9	4.1	5.02
	β area /La₂Ni₇ type	20.0	2.2	62.4	4.5	8.1	2.8	3.50
	γ area /LaNi type	48.5	0.4	50.1	0.5	0.2	0.3	1.04
	δ area /ScNi₂ type	0.8	32.2	46.4	9.5	9.7	1.4	2.03

Fig. 5 Curves of the enthalpy formation for binary alloy Mg-Ni, La-Ni and Sc-Ni

Fig. 6 Curves of the enthalpy formation for ternary alloy La1-x(Mg, Sc)xNi3.5

Fig. 7 Activation curves of the alloy electrodes

Fig. 8 Discharge curves of the alloy electrodes after activation

Fig. 9 Cycle stability curves of alloy electrodes

Fig. 10 Discharge capacity and cycle life of the alloy electrodes as a function of Sc content(x)

References 25

[1]	FENG F, GENG M, NORTHWOOD D O.Electrochemical behavior of intermetallic-based metal hydrides used in Ni/metal hydride (MH) batteries: a review.International Journal of Hydrogen Energy, 2001, 26(7): 725-734.
[2]	AKIBA E, HAYAKAWA H, KOHNO T. Crystal structures of novel La-Mg-Ni hydrogen absorbing alloys. Journal of Alloys and Compounds, 2006, 408-412: 280-283.
[3]	LIU Y F, CAO Y H, HUANG L, et al.Rare earth-Mg-Ni-based hydrogen storage alloys as negative electrode materials for Ni/MH batteries.Journal of Alloys and Compounds, 2011, 509(3): 675-686.
[4]	DENYS R V, RIABOV A B, YARTYS V A, et al.Mg substitution effect on the hydrogenation behavior, thermodynamic and structural properties of the La2Ni7-H(D)2 system.Journal of Solid State Chemistry, 2008, 181(4): 812-821.
[5]	DENYS R V, RIABOV B, YARTYS V A, et al. Hydrogen storage properties and structure of La1-xMgx(Ni1-yMny)3 intermetallic and their hydrides. Journal of Alloys and Compounds, 2007, 446-447: 166-172.
[6]	NWAKWUO C C, HOLM T, DENYS R V, et al.Effect of magnesium content and quenching rate on the phase structure and composition of rapidly solidified La2MgNi9 metal hydride battery electrode alloy.Journal of Alloys and Compounds, 2013, 555: 201-208.
[7]	DONG X P, LU F X, ZHANG Y H, et al.Effect of La/Mg on the structure and electrochemical performance of La-Mg-Ni system hydrogen storage electrode alloy.Materials Chemistry and Physics, 2008, 108(2): 251-256.
[8]	ZHANG F L, LUO Y C, CHEN J P, et al.La-Mg-Ni ternary hydrogen storage alloys with Ce2Ni7-type and Gd2Co7-type structure as negative electrodes for Ni/MH batteries.Journal of Alloys and Compounds, 2007, 430(1): 302-307.
[9]	ANTONOV V E, BASHKIN I O, FEDOTOV V K, et al.Crystal structure and lattice dynamics of high-pressure scandium trihydride.Physical Review B, 2006, 73(5): 054107.
[10]	YOSHIDA M, ISHIBASHI H, SUSA K, et al. Crystal structure, hydrogen absorbing properties and electrode performances of Sc-based Laves phase alloys. Journal of Alloys and Ccompounds, 1995, 226(1): 161-165.
[11]	YOSHIDA M, AKIBA E.Hydrogen absorbing properties of ScM2 Laves phase alloys (M=Fe, Co and Ni).Journal of Alloys and Compounds, 1995, 226(1): 75-80.
[12]	LI W H, TIAN B H, MA P, et al.Hydrogen storage properties of ScMn2 alloy.Acta Metallurgica Sinica, 2012, 48(7): 822-829.
[13]	UNDERWOOD E E.Microstructural Analysis: Quantitative Stereology for Microstructural Analysis. New York, Plenum Press, 1973: 35-66.
[14]	MIEDEMA A R, BOOM R, DE BOER F R. On the heat of formation of solid alloys.Journal of the Less Common Metals, 1975, 41(2): 283-298.
[15]	BOOM R, DE BOER F R, MIEDEMA A R. On the heat of mixing of liquid alloys-II.Journal of the Less Common Metals, 1976, 46(2): 271-284.
[16]	MIEDEMA A R, DE BOER F R, BOOM R. Model predictions for the enthalpy of formation of transition metal alloys.Calphad, 1977, 1(4): 341-359.
[17]	YAN X H, TANG W H, QIAO Z Y, et al.A method of calculating the ternary alloy generating heat.Journal of the Chinese Rare Earth Society, 1991, 12(3): 218-221.
[18]	高志杰. 稀土-镁-镍系A2B7型储氢合金结构和电化学性能研究. 兰州: 兰州理工大学博士学位论文, 2013.
[19]	CAHN R W.Phase Diagrams for Binary Alloys: A Desk Handbook. H Okamoto; ASM International, Materials Park , 2001.
[20]	LUO Y C, KANG L, ZHANG C Q, et al.Calculation of formation enthalpies for rare earth-based ternary hydrogen storage alloys.The Chinese Journal of Nonferrous Metals, 2000, 10(4): 480-483.
[21]	CHEN J, TAKESHITA H T, TANAKA H, et al.Hydriding properties of LaNi3 and CaNi3 and their substitutes with PuNi3 -type structure.Journal of Alloys and Compounds, 2000, 302(1): 304-313.
[22]	王稳. 轻质及含镁高熵合金的设计、微观组织及储氢性能研究. 兰州: 兰州理工大学硕士学位论文, 2014.
[23]	AOKI K, LI X G, MASUMOTO T.Factors controlling hydrogen-induced amorphization of C15 Laves compounds.Acta Metallurgica et Materialia, 1992, 40(7): 1717-1726.
[24]	ZHANG J, ZHOU G Y, CHEN G R, et al.Relevance of hydrogen storage properties of ANi3 intermetallic (A = La, Ce, Y) to the ANi2 subunits crystal structures.Acta Materialia, 2008, 56(19): 5388-5394.
[25]	SZAJEK A, JURCZYK M, RAJEWSHI W.The electronic and electrochemical properties of the LaNi5, LaNi4Al and LaNi3AlCo systems.Journal of Alloys and Compounds, 2000, 307(1): 290-296.

Structural and Electrochemical Properties of A₂B₇-type La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5) Hydrogen Storage Alloys

RichHTML

PDF (PC)

Knowledge

Cited

Abstract

Cite this article

share this article

Figures/Tables 11

References 25

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	FAN Wugang, CAO Xiong, ZHOU Xiang, LI Ling, ZHAO Guannan, ZHANG Zhaoquan. Anticorrosion Performance of 8YSZ Ceramics in Simulated Aqueous Environment of Pressurized Water Reactor [J]. Journal of Inorganic Materials, 2024, 39(7): 803-809.
[2]	CHEN Qian, SU Haijun, JIANG Hao, SHEN Zhonglin, YU Minghui, ZHANG Zhuo. Progress of Ultra-high Temperature Oxide Ceramics: Laser Additive Manufacturing and Microstructure Evolution [J]. Journal of Inorganic Materials, 2024, 39(7): 741-753.
[3]	JIANG Lingyi, PANG Shengyang, YANG Chao, ZHANG Yue, HU Chenglong, TANG Sufang. Preparation and Oxidation Behaviors of C/SiC-BN Composites [J]. Journal of Inorganic Materials, 2024, 39(7): 779-786.
[4]	ZHENG Yawen, ZHANG Cuiping, ZHANG Ruijie, XIA Qian, RU Hongqiang. Fabrication of Boron Carbide Ceramic Composites by Boronic Acid Carbothermal Reduction and Silicon Infiltration Reaction Sintering [J]. Journal of Inorganic Materials, 2024, 39(6): 707-714.
[5]	XUE Yifan, LI Weijie, ZHANG Zhongwei, PANG Xu, LIU Yu. Process Control of PyC Interphases Microstructure and Uniformity in Carbon Fiber Cloth [J]. Journal of Inorganic Materials, 2024, 39(4): 399-408.
[6]	SUN Chuan, HE Pengfei, HU Zhenfeng, WANG Rong, XING Yue, ZHANG Zhibin, LI Jinglong, WAN Chunlei, LIANG Xiubing. SiC-based Ceramic Materials Incorporating GNPs Array: Preparation and Mechanical Characterization [J]. Journal of Inorganic Materials, 2024, 39(3): 267-273.
[7]	ZHENG Jiaqian, LU Xiao, LU Yajie, WANG Yingjun, WANG Zhen, LU Jianxi. Functional Bioadaptability in Medical Bioceramics: Biological Mechanism and Application [J]. Journal of Inorganic Materials, 2024, 39(1): 1-16.
[8]	HE Danqi, WEI Mingxu, LIU Ruizhi, TANG Zhixin, ZHAI Pengcheng, ZHAO Wenyu. Heavy-Fermion YbAl₃ Materials: One-step Synthesis and Enhanced Thermoelectric Performance [J]. Journal of Inorganic Materials, 2023, 38(5): 577-582.
[9]	WU Shuang, GOU Yanzi, WANG Yongshou, SONG Quzhi, ZHANG Qingyu, WANG Yingde. Effect of Heat Treatment on Composition, Microstructure and Mechanical Property of Domestic KD-SA SiC Fibers [J]. Journal of Inorganic Materials, 2023, 38(5): 569-576.
[10]	XIE Jiaye, LI Liwen, ZHU Qiang. Contrastive Study on in Vitro Antibacterial Property and Biocompatibility of Three Clinical Pulp Capping Agents [J]. Journal of Inorganic Materials, 2023, 38(12): 1449-1456.
[11]	LI Jianbo, TIAN Zhen, JIANG Quanwei, YU Lifeng, KANG Huijun, CAO Zhiqiang, WANG Tongmin. Effects of Different Element Doping on Microstructure and Thermoelectric Properties of CaTiO₃ [J]. Journal of Inorganic Materials, 2023, 38(12): 1396-1404.
[12]	WU Dongjiang, ZHAO Ziyuan, YU Xuexin, MA Guangyi, YOU Zhulin, REN Guanhui, NIU Fangyong. Direct Additive Manufacturing of Al₂O₃-TiC_p Composite Ceramics by Laser Directed Energy Deposition [J]. Journal of Inorganic Materials, 2023, 38(10): 1183-1192.
[13]	ZHANG Ye, ZENG Yuping. Progress of Porous Silicon Nitride Ceramics Prepared via Self-propagating High Temperature Synthesis [J]. Journal of Inorganic Materials, 2022, 37(8): 853-864.
[14]	XIA Qian, SUN Shihao, ZHAO Yiliang, ZHANG Cuiping, RU Hongqiang, WANG Wei, YUE Xinyan. Effect of Boron Carbide Particle Size Distribution on the Microstructure and Properties of Reaction Bonded Boron Carbide Ceramic Composites by Silicon Infiltration [J]. Journal of Inorganic Materials, 2022, 37(6): 636-642.
[15]	HONG Du, NIU Yaran, LI Hong, ZHONG Xin, ZHENG Xuebin. Tribological Properties of Plasma Sprayed TiC-Graphite Composite Coatings [J]. Journal of Inorganic Materials, 2022, 37(6): 643-650.