非晶纳米晶PrMg12 型合金微观结构及吸放氢热力学与动力学性能

doi:10.19799/j.cnki.2095-4239.2022.0247

摘要/Abstract

摘要：

采用机械球磨法制备了非晶纳米晶PrMg₁₂+x%Ni(x=0、10、20、30)合金，系统地研究了镍含量对该合金储氢热力学与动力学的影响。利用X射线衍射(XRD)、高分辨透射电子显微镜(HRTEM)两种方法分析了合金的相组成及微观组织结构。结果表明：PrMg₁₂+x%Ni(x=0、10、20、30)合金的微观结构主要为非晶纳米晶；加入镍前，吸氢前后的主相分别为PrMg₁₂相、MgH₂相以及PrH_2.92相；加入镍后，吸氢前后的主相分别为Ni相、PrMg₁₂相、MgH₂相以及Mg₂NiH₄相。采用Sieverts装置测定了合金的P-C-T曲线与吸放氢动力学曲线，并结合Van't Hoff方程、JMAK模型和Arrhenius法计算了热力学与动力学参数。结果表明：随着镍含量由0%增加至30%，合金氢化物的放氢焓值由89.881 kJ/mol降低至82.764 kJ/mol，放氢活化能由126 kJ/mol降低至90 kJ/mol，这进一步证明添加镍可以显著改善球磨PrMg₁₂型合金氢化物的释氢热力学和动力学。

关键词: PrMg₁₂合金, 机械球磨法, 热力学性能, 动力学性能, 活化能

Abstract:

Amorphous and nanocrystalline PrMg₁₂+x%Ni (x=0, 10, 20, or 30) alloys were prepared by mechanical milling, and the effects of the nickel content on the thermodynamics and kinetics of hydrogen storage in the alloys were studied systematically. The phase composition and microstructure of the alloy were analyzed by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The PrMg₁₂+x%Ni (x=0, 10, 20, or 30) alloy was mainly amorphous and nanocrystalline. Before adding nickel, the main phases before and after hydrogen absorption were the PrMg₁₂ phase, MgH₂ phase, and PrH_2.92 phase, respectively. After adding nickel, the main phases before and after hydrogen absorption were a Ni phase, PrMg₁₂ phase, MgH₂ phase, and Mg₂NiH₄ phase. The P-C-T curves and hydrogen absorption and desorption kinetic curves of the alloy were measured using a Sieverts apparatus, and the thermodynamic and kinetic parameters were calculated by combining the Van't Hoff equation, the JMAK model, and the Arrhenius method. The hydrogen desorption enthalpy of the alloy hydride decreased from 89.881 kJ/mol to 82.764 kJ/mol as the Ni content was increased from 0% to 30%, and the hydrogen desorption activation energy decreased from 126 kJ/mol to 90 kJ/mol. Hence, adding nickel can significantly improve the hydrogen release thermodynamics and kinetics of ball-milled PrMg₁₂-type alloy hydrides.

Key words: PrMg₁₂ alloy, mechanical ball milling, hydrogen storage thermodynamics, hydrogen storagedynamics, activation energy

中图分类号:

TG 139.7

段亚楠, 胡锋, 夏婷, 李永治, 赵鑫, 蔡颖. 非晶纳米晶PrMg₁₂ 型合金微观结构及吸放氢热力学与动力学性能[J]. 储能科学与技术, 2022, 11(10): 3151-3160.

Yanan DUAN, Feng HU, Ting XIA, Yongzhi LI, Xin ZHAO, Ying CAI. Microstructure and hydrogenation/dehydrogenation thermodynamic and kinetic properties of PrMg₁₂ type alloy with amorphous and nanocrystalline structure[J]. Energy Storage Science and Technology, 2022, 11(10): 3151-3160.

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物料	0%Ni	10%Ni	20%Ni	30%Ni
PrMg₁₂	10 g	9.0909 g	8.3333 g	7.6923 g
Ni	0 g	0.9091 g	1.6667 g	2.3077 g

PrMg₁₂+ x%Ni	吸氢		放氢
PrMg₁₂+ x%Ni	ΔH/(kJ/mol)	ΔS/(J/mol·K)	ΔH/(kJ/mol)	ΔS/(J/mol·K)
x=0	-85.999	-152.64	89.881	154.205
x=10	-84.949	-149.28	88.078	151.519
x=20	-82.482	-146.09	84.707	147.211
x=30	-80.880	-144.29	82.764	144.051

温度/K	0%Ni	10%Ni	20%Ni	30%Ni
553	4.319	5.348	5.744	6.721
573	4.489	5.273	5.780	6.734
593	4.578	5.344	5.804	6.757
623	5.032	5.385	5.885	6.772

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非晶纳米晶PrMg₁₂ 型合金微观结构及吸放氢热力学与动力学性能

Microstructure and hydrogenation/dehydrogenation thermodynamic and kinetic properties of PrMg₁₂ type alloy with amorphous and nanocrystalline structure

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