【摘要】：釩基固溶體型儲氫合金具有可逆儲氫量高、可在常溫常壓下吸放氫等優(yōu)點,但純金屬釩的成本高,采用釩鐵中間合金代替純釩能夠大幅降低合金成本。本課題以具有工業(yè)80VFe比例的二元V-Fe為基礎(chǔ)開展研究,采用XRD、SEM、DSC等材料分析方法以及吸放氫動力學(xué)、PCT曲線等儲氫性能測試手段,系統(tǒng)的研究了多元合金化對V-Fe系合金儲氫性能的影響規(guī)律,以期得到高容量低成本的釩基BCC固溶體型儲氫合金。本文首先設(shè)計了V/Fe與工業(yè)80VFe相近的二元V85Fe15合金,通過添加1 at.%Ce大幅改善了其活化及吸氫動力學(xué)性能。對比V85Fe15-1 at.%Ce及V-1 at.%Ce吸放氫性能發(fā)現(xiàn),合金V85Fe15-1 at.%Ce的儲氫量及吸放氫平臺壓大幅降低,氫化物分解焓(絕對值)變大,其最大吸氫量約1.8wt.%,放氫平臺壓約0.00961 MPa,氫化物分解焓約-45.01 kJ/mol。為了提高合金V85Fe15-1 at.%Ce的吸放氫平臺壓,本文研究了不同合金元素M(M=Cr, Mo,Al)及其含量(x=1,3,5)對V85Fe15-1 at.%Ce組織結(jié)構(gòu)及儲氫性能的影響。結(jié)果表明,各合金均呈BCC及Ce02兩相組成,由于元素替代量較小,合金B(yǎng)CC晶格常數(shù)隨M變化較小,因此各合金最大吸氫量與V85Fe15-1 at.%Ce基本接近。但由于BCC基體四面體間隙尺寸隨著M含量的增加逐漸減小,合金(V0.85Fe0.15)100-xMx-1 at.%Ce吸放氫平臺壓隨元素替代量的增加近似線性增大。本階段優(yōu)選出具備較高吸放氫平臺壓的5-1 at.%Ce合金,其在303 K下的放氫平臺壓約1.49 MPa。為了增大合金5-1 at.%Ce及V85Fe15-1 at.%Ce的儲氫量,本文進(jìn)一步研究了添加不等量元素Ti(0-30 at.%)對合金(V0.85Fe0.15)95Al5-1 at.%Ce及V85Fe15-1 at.%Ce組織結(jié)構(gòu)及儲氫性能的影響。Ti含量低于20 at.%的合金保持BCC及Ce02兩相組成,高于20 at.%Ti的合金基體中出現(xiàn)少量富鈦第三相,合金B(yǎng)CC基體晶格常數(shù)隨Ti含量的增加線性增大,因此在Ti含量低于20 at.%時合金最大吸氫量逐漸增大,在Ti含量為25 at.%時由于富鈦相的出現(xiàn)吸氫量有所降低。合金(V0.85Fe0.15)95-xAl5Tix-1 at.%Ce吸氫平臺及(V0.85Fe0.15)100-xTix-1 at.%Ce的吸放氫平臺壓隨著Ti含量的增加出現(xiàn)較大波動,并在x=20處達(dá)到最優(yōu)值。本階段優(yōu)選出了具備較優(yōu)儲氫性能的合金(V0.85Fe0.15)80Ti20-1 at.%Ce,其最大吸氫量約3.74、wt.%,303 K下的放氫平臺壓約0.06MPa。為了提高優(yōu)選合金(V0.85Fe0.15)80Ti20-1 at.%Ce的放氫平臺壓,本文通過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)的組織結(jié)構(gòu)及儲氫性能。與三元V-Fe-M合金相似,合金元素Mo、Cr的添加顯著提高了基體合金吸放氫平臺壓,但吸放氫量有所降低。在優(yōu)選合金(V0.85Fe0.15)80Ti20-1 at.%Ce成分附近,本文進(jìn)一步通過正交設(shè)計實驗研究了合金(V0.85Fe0.15)100-x-y-zTixMoyAlz-1 at.%Ce的組織結(jié)構(gòu)及儲氫性能。正交設(shè)計試驗直觀分析結(jié)果表明,各因素對合金儲氫性能影響的顯著性呈TiAlMo的趨勢,Al元素對提高合金平臺壓效果顯著,將Ti含量控制在20 at.%能夠獲得較良好的綜合儲氫性能。
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【學(xué)位授予單位】：北京有色金屬研究總院
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TG139.7

【參考文獻(xiàn)】

相關(guān)博士學(xué)位論文 前1條

1 嚴(yán)義剛;V-Ti-Cr-Fe貯氫合金的結(jié)構(gòu)與吸放氫行為研究[D];四川大學(xué);2007年

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