合金化对V-Fe系合金储氢性能的影响
发布时间：2018-10-08 16:34
【摘要】：钒基固溶体型储氢合金具有可逆储氢量高、可在常温常压下吸放氢等优点,但纯金属钒的成本高,采用钒铁中间合金代替纯钒能够大幅降低合金成本。本课题以具有工业80VFe比例的二元V-Fe为基础开展研究,采用XRD、SEM、DSC等材料分析方法以及吸放氢动力学、PCT曲线等储氢性能测试手段,系统的研究了多元合金化对V-Fe系合金储氢性能的影响规律,以期得到高容量低成本的钒基BCC固溶体型储氢合金。本文首先设计了V/Fe与工业80VFe相近的二元V85Fe15合金,通过添加1 at.%Ce大幅改善了其活化及吸氢动力学性能。对比V85Fe15-1 at.%Ce及V-1 at.%Ce吸放氢性能发现,合金V85Fe15-1 at.%Ce的储氢量及吸放氢平台压大幅降低,氢化物分解焓(绝对值)变大,其最大吸氢量约1.8wt.%,放氢平台压约0.00961 MPa,氢化物分解焓约-45.01 kJ/mol。为了提高合金V85Fe15-1 at.%Ce的吸放氢平台压,本文研究了不同合金元素M(M=Cr, Mo,Al)及其含量(x=1,3,5)对V85Fe15-1 at.%Ce组织结构及储氢性能的影响。结果表明,各合金均呈BCC及Ce02两相组成,由于元素替代量较小,合金BCC晶格常数随M变化较小,因此各合金最大吸氢量与V85Fe15-1 at.%Ce基本接近。但由于BCC基体四面体间隙尺寸随着M含量的增加逐渐减小,合金(V0.85Fe0.15)100-xMx-1 at.%Ce吸放氢平台压随元素替代量的增加近似线性增大。本阶段优选出具备较高吸放氢平台压的5-1 at.%Ce合金,其在303 K下的放氢平台压约1.49 MPa。为了增大合金5-1 at.%Ce及V85Fe15-1 at.%Ce的储氢量,本文进一步研究了添加不等量元素Ti(0-30 at.%)对合金(V0.85Fe0.15)95Al5-1 at.%Ce及V85Fe15-1 at.%Ce组织结构及储氢性能的影响。Ti含量低于20 at.%的合金保持BCC及Ce02两相组成,高于20 at.%Ti的合金基体中出现少量富钛第三相,合金BCC基体晶格常数随Ti含量的增加线性增大,因此在Ti含量低于20 at.%时合金最大吸氢量逐渐增大,在Ti含量为25 at.%时由于富钛相的出现吸氢量有所降低。合金(V0.85Fe0.15)95-xAl5Tix-1 at.%Ce吸氢平台及(V0.85Fe0.15)100-xTix-1 at.%Ce的吸放氢平台压随着Ti含量的增加出现较大波动,并在x=20处达到最优值。本阶段优选出了具备较优储氢性能的合金(V0.85Fe0.15)80Ti20-1 at.%Ce,其最大吸氢量约3.74、wt.%,303 K下的放氢平台压约0.06MPa。为了提高优选合金(V0.85Fe0.15)80Ti20-1 at.%Ce的放氢平台压,本文通过Mo、Cr的添加研究了合金[(V0.85Fe0.15)80Ti20]100-xMx-1 at.%Ce(M=Cr, Mo; x=0,1,3,5)的组织结构及储氢性能。与三元V-Fe-M合金相似,合金元素Mo、Cr的添加显著提高了基体合金吸放氢平台压,但吸放氢量有所降低。在优选合金(V0.85Fe0.15)80Ti20-1 at.%Ce成分附近,本文进一步通过正交设计实验研究了合金(V0.85Fe0.15)100-x-y-zTixMoyAlz-1 at.%Ce的组织结构及储氢性能。正交设计试验直观分析结果表明,各因素对合金储氢性能影响的显著性呈TiAlMo的趋势,Al元素对提高合金平台压效果显著,将Ti含量控制在20 at.%能够获得较良好的综合储氢性能。
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【学位授予单位】：北京有色金属研究总院
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TG139.7
本文编号：2257478
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【学位授予单位】：北京有色金属研究总院
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TG139.7
【参考文献】
相关博士学位论文 前1条
1 严义刚;V-Ti-Cr-Fe贮氢合金的结构与吸放氢行为研究[D];四川大学;2007年
，本文编号：2257478
本文链接：https://www.wllwen.com/kejilunwen/jinshugongy/2257478.html
教材专著
