Mg2Ni1-xCox合金相的固溶烧结法制备及结构和储氢性能

doi:10.7503/cjcu20160284

摘要/Abstract

摘要：

采用固溶烧结法制备了Mg₂Ni_1-_xCo_x (x=0.10, 0.15, 0.20)合金, 利用X射线衍射仪和压力-组成-温度测试仪等研究了Co含量对合金相结构和储氢性能的影响. 结果表明, 合金由Mg₂Ni型Mg₂(Ni, Co)主相及少量Mg和MgNi₃Co新相组成. Mg₂(Ni, Co)具有良好的可逆储氢性能, 吸氢形成Mg₂Ni_0.9Co_0.1H₄型四元氢化物, 其具有与父系氢化物HT-Mg₂NiH₄相近的放氢焓变(ΔH_d=63.9 kJ/mol H₂). Mg₂Ni_1-_xCo_x (x=0.10, 0.15, 0.20)合金具有良好的放氢动力学性能, 二维相界面迁移为放氢过程的控制步骤. 随着Co含量的增加, 合金的放氢活化能(E_a)降低, 其中, Mg₂Ni_0.8Co_0.2的E_a降低到54.0 kJ/mol.

关键词: Mg2Ni型合金, Co合金化, 固溶烧结, Mg2Ni0.9Co0.1H4, 储氢性能

Abstract:

Mg₂Ni_1-_xCo_x (x=0.10, 0.15, 0.20) alloys were prepared by a novel method combining solid solution with sintering process. The effect of Co content on the phase structures and hydrogen storage properties were investigated by XRD and pressure-composition-temperature analyser. It was found that the alloys consisted of a Mg₂Ni-type major phase Mg₂(Ni, Co), minor Mg and a new phase MgNi₃Co. The Mg₂(Ni, Co) compounds displayed a reversible hydrogen storage process. After hydrogenation, the quaternary Mg₂Ni_0.9Co_0.1H₄-type hydride was formed with an enthalpy change of the hydrogen desorption(ΔH_d=63.9 kJ/mol H₂) approximate to the parent hydride HT-Mg₂NiH₄. The Mg₂Ni_1-_xCo_x(x=0.10, 0.15, 0.20) alloys showed a superior desorption kinetics and the desorption process was mainly controlled by two-dimensional phase-boundary migration. For the Mg₂Ni_1-_xCo_x (x=0.10, 0.15, 0.20) alloys, the activation energy of hydrogen desorption (E_a) decreased with the increase of Co content. As a result, the E_a value of the Mg₂Ni_0.8Co_0.2 alloy was significantly lowered to 54.0 kJ/mol.

Key words: Mg2Ni-type alloy, Co-alloying, Solid solution sintering, Mg2Ni0.9Co0.1H4, Hydrogen storage property

中图分类号:

O614

TrendMD:

马勇, 李祥志, 李永涛, 柳东明, 张庆安, 斯庭智. Mg₂Ni_1-_xCo_x合金相的固溶烧结法制备及结构和储氢性能. 高等学校化学学报, 2016, 37(10): 1776.

MA Yong, LI Xiangzhi, LI Yongtao, LIU Dongming, ZHANG Qing’an, SI Tingzhi. Phase Structures and Hydrogen Storage Properties of Mg₂Ni_1-_xCo_x Alloys Prepared by Solid Solution Sintering^†. Chem. J. Chinese Universities, 2016, 37(10): 1776.

图/表 11

Fig.1 XRD patterns of Ni1-xCox (x=0.10, 0.15, 0.20) solid solutions(a—c) and Ni0.9Co0.1 mixture without milling(d)a.x =0.10; b. x =0.15; c. x =0.20.

Fig.2 XRD patterns of the sintered Mg2Ni1-xCox alloysa. x=0.10; b. x =0.15; c. x =0.20.

Table 1 Atomic coordinates, occupation factors(g) and isotropic thermal parameters(B) of MgNi3Co refined from X-ray powder diffraction data

Atom	Site	g	Coordinate			B/nm²
Atom	Site	g	x		y	z
Mg	1a	1	0	0	0	0.026(1)
Ni	3c	1	0	1/2	1/2	0.016(8)
Co	1b	1	1/2	1/2	1/2	0.022(3)

Fig.3 Rietveld refinement of the observed XRD pattern for the sintered Mg2Ni0.85Co0.15 alloyThe calculated(line) and observed(+) X-ray diffraction patterns for sintered Mg2Ni0.85Co0.15 alloy are displayed above the vertical bars, below which shows the difference between the observed and calculated patters.

Table 2 Structural parameters and phase abundance of the sintered Mg2Ni1-xCox (x=0.10, 0.15, 0.20) alloys

Sample	Phase	Space group	R_I(%)	Lattice parameter/nm		Abundance(%)
Sample	Phase	Space group	R_I(%)	a		c
Mg₂Ni_0.9Co_0.1	Mg₂(Ni, Co)	P6₂22	3.43	0.5216(1)	1.3283(2)	91
R_wp=6.58%	Mg	P6₃/mmc	3.99	0.3207(2)	0.5208(2)	4
S=1.8	MgNi₃Co	Pm $3 ˉ$ m	2.80	0.3810(1)		5
Mg₂Ni_0.85Co_0.15	Mg₂(Ni, Co)	P6₂22	4.84	0.5218(1)	1.3284(2)	90
R_wp=7.00%	Mg	P6₃/mmc	4.29	0.3208(2)	0.5209(2)	4
S=1.9	MgNi₃Co	Pm $3 ˉ$ m	7.63	0.3813(1)		6
Mg₂Ni_0.8C $o 0 . 2$	Mg₂(Ni, Co)	P6₂22	4.68	0.5218(1)	1.3291(1)	89
R_wp=6.54%	Mg	P6₃/mmc	4.83	0.3207(1)	0.5207(2)	5
S=1.4	MgNi₃Co	Pm $3 ˉ$ m	5.59	0.3811(1)		6

Table 2 Structural parameters and phase abundance of the sintered Mg2Ni1-xCox (x=0.10, 0.15, 0.20) alloys

Sample	Phase	Space group	R_I(%)	Lattice parameter/nm		Abundance(%)
Sample	Phase	Space group	R_I(%)	a		c
Mg₂Ni_0.9Co_0.1	Mg₂(Ni, Co)	P6₂22	3.43	0.5216(1)	1.3283(2)	91
R_wp=6.58%	Mg	P6₃/mmc	3.99	0.3207(2)	0.5208(2)	4
S=1.8	MgNi₃Co	Pm $3 ˉ$ m	2.80	0.3810(1)		5
Mg₂Ni_0.85Co_0.15	Mg₂(Ni, Co)	P6₂22	4.84	0.5218(1)	1.3284(2)	90
R_wp=7.00%	Mg	P6₃/mmc	4.29	0.3208(2)	0.5209(2)	4
S=1.9	MgNi₃Co	Pm $3 ˉ$ m	7.63	0.3813(1)		6
Mg₂Ni_0.8C $o 0 . 2$	Mg₂(Ni, Co)	P6₂22	4.68	0.5218(1)	1.3291(1)	89
R_wp=6.54%	Mg	P6₃/mmc	4.83	0.3207(1)	0.5207(2)	5
S=1.4	MgNi₃Co	Pm $3 ˉ$ m	5.59	0.3811(1)		6

Table 3 Occupation factor(g) of Co atoms in Ni(3d) sites of the Mg2(Ni, Co) phases

Sample	Mg₂Ni_0.9Co_0.1	Mg₂Ni_0.85Co_0.15	Mg₂Ni_0.8Co_0.2
g(Ni/Co)	0.84/0.16(2)	0.72/0.28(5)	0.64/0.36(3)

Fig.4 XRD patterns of the hydrogenated(A) and dehydrogenated(B) Mg2Ni1-xCox(x =0.10, 0.15, 0.20) alloys a. x=0.10; b. x =0.15; c. x =0.20.

Fig.5 P-C isotherms of hydrogen absorption/desorption for the Mg2Ni1-xCox (x =0.10, 0.15, 0.20) alloys(A)—(C) and van’t Hoff plots in dehydriding process(D)(A) x =0.10; (B) x =0.15; (C) x =0.20. a. Mg2Ni0.9Co0.1-H2; b. Mg2Ni0.85Co0.15-H2; c. Mg2Ni0.8Co0.2-H2.

Fig.6 Isothermal hydrogen desorption curves of the Mg2Ni1-xCox (x =0.10, 0.15, 0.20) alloys(A) x=0.10; (B) x=0.15; (C) x=0.20.

Fig.7 Plots of 1-(1-α)1/2 vs. t for the Mg2Ni1-xCox (x =0.10, 0.15, 0.20)-H2 systems at various temperatures(A) x=0.10; (B) x=0.15; (C) x=0.20.

Fig.8 Arrhenius plots for hydrogen desorption of the Mg2Ni1-xCox (x =0.10, 0.15, 0.20) alloysa. x=0.10; b. x =0.15; c. x =0.20.

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Mg₂Ni_1-_xCo_x合金相的固溶烧结法制备及结构和储氢性能

Phase Structures and Hydrogen Storage Properties of Mg₂Ni_1-_xCo_x Alloys Prepared by Solid Solution Sintering^†

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