Sm对La0.5Nd0.35-xSmxMg0.15Ni3.5合金晶体结构和储氢性能的影响

doi:10.19799/j.cnki.2095-4239.2020.0068

摘要/Abstract

摘要：

金属Sm替代La_0.5Nd_0.35Mg_0.15Ni_3.5合金中的Nd用以提高合金性价比。通过多种研究手段分析了La_0.5Nd_0.35-_xSm_xMg_0.15Ni_3.5合金的相结构、合金形貌以及电化学储氢性能。所制备合金为A₂B₇、A₅B₁₉主相和AB₅残余相组成的多相结构。随着Sm替代量增加（x值由0增加至0.3），相丰度的变化规律为主相A₂B₇和A₅B₁₉先升高后降低，而AB₅残余相相丰度呈相反的变化趋势。合金最大放电容量由334.6 mA·h/g(x=0)升高至346.5 mA·h/g(x=0.20)，当x=0.30时，最大放电容量为331.1 mA·h/g。高倍率放电性能（HRD₂₀₀₀）由41.4%(x=0)升高至63.8%(x=0.20)，当x=0.30时，HRD₂₀₀₀为52.1%。100周期容量循环保持率呈单调上升趋势，由65.6%(x=0)升高至69.2%(x=0.30)。

关键词: La-Mg-Ni储氢合金, 电化学性能, 电化学动力学性能, 超晶格结构

Abstract:

The Nd in the La_0.5Nd_0.35Mg_0.15Ni_3.5 alloy has been substituted with Sm to improve the performance to price ratio. Herein, the phase structures, morphologies, and hydrogen storage properties of the La_0.5Nd_0.35-_xSm_xMg_0.15Ni_3.5 alloys are studied using different methods. The Rietveld analysis pattern showed that the phase composition of the alloys containing multiphase structures, including the major phases (i.e., A₂B₇ and A₅B₁₉) and the residual phase (i.e., AB₅), remained unchanged after the partial substitution of Sm instead of Nd. Increasing the content of the substituted Sm (x=0-0.30) changes the phase abundance, causing the A₂B₇ and A₅B₁₉ phases to increase before decreasing, whereas the AB₅phase showed the reverse trend. The a-axis parameter, c-axis, and unit cell volume of the major phases and the residual phase gradually decreased with the increasing Sm content. Further, the electrochemical properties of the alloy electrodes were improved by substituting Nd with Sm. The maximum discharge capacity of the alloy electrodes initially increased from 334.6 mA·h/g(x=0)to 346.5 mA·h/g (x=0.20). Then, it decreased to 331.1 mA·h/g(x=0.30). The high-rate dischargeability at a discharge current density of 2000 mA/g(HRD2000)initially increased from 41.4%(x=0) to 63.8% (x=0.20). Subsequently, it decreased to 52.1% (x = 0.30). The cycling capacity retention rate at the 100th cycle monotonically increased from 65.6% (x = 0) to 69.2% (x = 0.30), which should be attributed to the improvement in corrosion resistance of the alloy electrodes during the charge-discharge cycle.

Key words: La-Mg-Ni-based alloy, electrochemical characteristics, electrochemical kinetic property, superlattice structure

中图分类号:

TG 139.7

赵鑫, 可丹丹, 吉力强, 胡锋, 蔡颖. Sm对La_0.5Nd_0.35-_xSm_xMg_0.15Ni_3.5合金晶体结构和储氢性能的影响[J]. 储能科学与技术, 2020, 9(4): 1066-1073.

ZHAO Xin, KE Dandan, JI Liqiang, HU Feng, CAI Ying. Crystallographic and electrochemical hydrogen storage properties of Sm substitute Nd for La_0.5Nd_0.35_-_xSm_xMg_0.15Ni_3.5 alloys[J]. Energy Storage Science and Technology, 2020, 9(4): 1066-1073.

图/表 10

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参考文献 24

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alloys		Str. type	a/?	c/?	V/?³	abundance /%
x = 0	R_p=2.94 R_wp=3.94	Ce₂Ni₇	5.0226	24.356	532.10	29.11
		Gd₂Co₇	5.0239	36.421	796.10	45.77
		Pr₅Co₁₉	5.0348	32.355	710.30	7.58
		Ce₅Co₁₉	5.0275	48.368	1058.8	13.76
		CaCu₅	5.0055	3.982	86.411	3.77
x = 0.1
	R_p=2.82 R_wp=3.76	Ce₂Ni₇	5.0233	24.390	532.99	32.95
		Gd₂Co₇	5.0262	36.431	797.02	45.48
		Pr₅Co₁₉	5.0277	32.561	712.79	6.16
		Ce₅Co₁₉	5.0200	48.532	1059.2	13.95
		CaCu₅	4.9986	3.9829	86.183	1.46
x = 0.2
	R_p=2.76 R_wp=3.64	Ce₂Ni₇	5.0160	24.356	532.70	31.16
		Gd₂Co₇	5.0190	36.358	793.39	51.35
		Pr₅Co₁₉	5.0191	32.550	710.12	5.71
		Ce₅Co₁₉	5.0197	48.991	1069.0	11.25
		CaCu₅	4.9976	3.9584	85.837	0.52
x = 0.3
	R_p=2.64 R_wp=3.56	Ce₂Ni₇	5.0161	24.272	528.89	26.40
		Gd₂Co₇	5.0157	36.335	791.62	37.41
		Pr₅Co₁₉	5.0207	32.497	709.44	9.81
		Ce₅Co₁₉	5.0114	48.335	1051.2	22.60
		CaCu₅	4.9880	3.9776	85.706	3.78

x	R_p/mΩ·g	I₀/mA·g^-1	D (× 10¹¹)/cm²·s^-1
0	219.3	117.1	2.72
0.10	172.3	149.0	5.74
0.20	128.8	199.4	8.39
0.30	148.7	172.7	7.29

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