球磨CeMg12+100wt%Ni+Ywt%TiF3(Y=0、3、5)合金微观结构及电化学储氢性能

doi:10.3724/SP.J.1077.2013.12180

摘要/Abstract

摘要：

用球磨法制备具有非晶纳米晶结构的CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0、3、5)电极合金, 研究在球磨过程中加入不同含量的TiF₃对合金的微观结构及电化学性能影响。主要从电化学放电容量、循环稳定性以及电化学动力学方面对制备的合金电化学性能进行探讨, 并运用电化学PCT(压力-组成-温度)法从热力学角度进一步研究制备合金电化学性能变化的内在原因。结果表明: TiF₃有助于增强球磨CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0、3、5)储氢合金玻璃化形成能力, 改善合金的电化学与动力学性能。另外, 球磨过程中加入TiF₃可以在一定程度上降低合金氢化物的热稳定性, 有利于电化学释氢反应的进行。

关键词: 储氢合金, 热力学性能, 非晶纳米晶, 电化学PCT

Abstract:

The nanocrystalline and amorphous CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0, 3, 5) alloy samples were synthesized by ball milling technology. The infulence of TiF₃ on microstructure and electrochemical properties of milling alloys were investigated. The electrochemical performance of prepared alloy samples was studied through discharge capacity, cycle stability and electrochemical kinetic, meantime. By using electrochemical PCT (pressure-concentration- isotherm) curves the change law of electrochemical performance of ball-milled alloys was further explained from the view of thermodynamics. The result showed that TiF₃ was helpful for enhancing the nanocrytstalline and glass forming ability of milled CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0, 3, 5) hydrogen storage alloys, improving the electrochemical and kinetic properties. On the other hand, in milling process, addition of TiF₃ reduced the hot stability of alloy hydride to some degree, accelerating the electrochemical dehydriding reaction.

Key words: hydrogen alloy, thermodynamic property, nanocrystalline and amorphous, electrochemical PCT

中图分类号:

TG139

胡锋, 张羊换, 张胤, 侯忠辉1, 董忠平, 邓磊波. 球磨CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0、3、5)合金微观结构及电化学储氢性能[J]. 无机材料学报, 2013, 28(2): 217-223.

HU Feng, ZHANG Yang-Huan, ZHANG Yin, HOU Zhong-Hui, DONG Zhong-Ping, DENG Lei-Bo. Microstructure and Electrochemical Hydrogen Storage Characteristics of CeMg₁₂+100wt%Ni +Ywt%TiF₃ (Y=0, 3, 5) Alloys Prepared by Ball Milling[J]. Journal of Inorganic Materials, 2013, 28(2): 217-223.

图/表 9

图1 经过60 h球磨F0、F3、F5合金的XRD图谱

Fig. 1 XRD patterns of the F0, F3, F5 alloys milled for 60 h

图2 球磨F0(a)、F3(b)合金SEM照片与相应EDS图谱

Fig. 2 SEM images of ball-milled F0, F3 alloys together with typical EDS patterns (a) F0 alloy milled for 60 h; (b) F3 alloy milled for 60 h

图3 球磨F0, F3合金颗粒粒径分布

Fig. 3 Size distribution of ball milling F0, F3 alloys

图4 球磨态合金高分辨率透射电镜(HRTEM)照片

Fig. 4 HRTEM micrographs of ball milling alloy

图5 经过60 h 球磨制备的F0、F3、F5合金放电容量与循环次数的关系图谱

Fig. 5 Discharge capacity dependence of cycle number of the F0, F3 and F5 alloys milled for 60 h

图6 球磨F0、F3、F5合金高倍率放电能力(HRD)与TiF3百分含量的关系

Fig. 6 Evolution of the high rate discharge ability (HRD) of milled F0, F3 and F5 alloys of milled F0, F3, F5 alloys with the change of TiF3 content

图7 球磨F0、F3、F5合金在50%放电深度下的线性极化曲线

Fig. 7 Linear polarization curves of ball-milled F0, F3 and F5 alloys at 50% depth of discharge

图8 球磨F0、F3、F5合金在50%放电深度下的阳极电流对响应时间的半对数曲线

Fig. 8 Semilogarithmic curves of anodic current vs time responses of ball-milled F0, F3 and F5 alloys at 50% depth of discharge

图9 球磨F0、F3和F5合金样品电化学PCT曲线

Fig. 9 Electrochemical PCT curves of the ball-milled F0 , F3 and F5 alloy samples

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球磨CeMg₁₂+100wt%Ni+Ywt%TiF₃(Y=0、3、5)合金微观结构及电化学储氢性能

Microstructure and Electrochemical Hydrogen Storage Characteristics of CeMg₁₂+100wt%Ni +Ywt%TiF₃ (Y=0, 3, 5) Alloys Prepared by Ball Milling

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