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姓名 江承恩(Cheng-en Jiang) 查詢紙本館藏 畢業系所 材料科學與工程研究所 論文名稱 Mg2(Cu1-xNix)儲氫合金結構與吸放氫特性之研究
(Structural and hydrogen storage characteristics ofMg2(Cu1-xNix) alloys)相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 本實驗利用自行開發之恆溫揮發熔煉鑄造製程(Isothermal Evaporation Casting Process，IECP)製備高純度Mg2Cu儲氫合金，並於熔配過程中添加不同比例之Ni元素取代Cu元素進行合金改質，配製Mg2(Cu1-xNix)(X=0.2、0.4、0.6、0.8、1.0)儲氫合金，驗證IECP法於熔配過程添加第三元素之穩定度，並觀察不同Ni、Cu含量對於Mg-Cu-Ni三元儲氫合金系統之結構變化與吸放氫特性之影響。
IECP法可成功製備高純度且均質之Mg2(Cu1-xNix)合金，且由X光繞射分析得知Mg2Cu合金為Face-Centered-Cubic結構，而Ni含量的添加(X為0.2以上)，均轉變為與Mg2Ni相同之Hexagonal結構；同時合金之吸氫速率及飽和吸氫量亦隨著Ni添加量的增加而提升。Mg2(Cu1-xNix)(X=0.6、0.8)合金不同於其餘成分合金，其PCI曲線有雙平台區，且第一平台為Mg2Ni + 2H2 --> Mg2NiH4 之氫化反應，而第二平台則為2Mg2Cu + 3H2 --> 3MgH2 + MgCu2之氫化反應，然而受到固溶體晶格擴張侷限(Lattice Expansion Limitation of Additives effect)之影響使第一平台壓由300oC Mg2NiH4 之8 atm提升至15 atm以上，而第二平台壓亦由300oC MgH2 + MgCu2 之17 atm提升至25 atm，且由吸放氫前後之晶體結構變化，觀察於Mg基地之Cu元素與Ni元素其催化性質，發現Cu本身不參與氫化反應形成含Cu之氫化物，而且Cu本身會犧牲部分吸氫量。DSC曲線觀察到Mg2Cu合金之放氫溫度比純Mg放氫溫度約低20℃，表示Cu的添加能加速MgH2之放氫反應，而氫化後之Mg2(Cu1-xNix)(X=0.2、0.4、0.6、0.8)合金於放氫過程均有鑄態結構生成回復整理之吸熱反應。摘要(英) This research purpose lies in preparing high-purity Mg2Cu alloy
by useful method Isothermal Evaporation Casting Process(IECP) and
fabricating Mg2(Cu1-xNix)(X=0.2、0.4、0.6、0.8、1.0) hydrogen storage
alloys by different ratio of nickel substituting for copper in Mg2Cu
alloy. It is verify that controlling addition of the third element
in melting process by IECP and the effect of nickel and copper content
on the structure and hydrogen storage properties for the ternary
Mg2(Cu1-xNix) alloys are investigated.
It is successful to fabricate high-purity and homogeneous
Mg2(Cu1-xNix) alloys .Mg2Cu alloy is face-centered orthorhombic
structure and Mg2(Cu1-xNix) alloys in the composition range of
1.0≧X≧0.2 are hexagonal structure. The absorption rate and
capacity of the alloys increase with nickel content increasing. The
PCI curves show two plateaus for the Mg2(Cu1-xNix)(X=0.6,0.8) alloys.It
is found that the hydriding mechanism of the first plateau is Mg2Ni
+ 2H2 Mg2NiH4 and second plateau is 2Mg2Cu + 3H2 3MgH2 + MgCu2.
However, lattice expansion limitation of additives effect makes that
the first and second plateau pressure are raise to 15 atm from 4 atm and 25 atm from 17 atm, respectively. X-ray analysis indicate that
the crystal structure are changed in hydriding process, and the
catalytic character of nickel and copper element in the magnesium
matrix are observed. We find out that copper isn’t concerned in
hydriding reaction. Nevertheless, addition of copper makes hydrogen
storage capacity reducing. From DSC curves, the dehydriding
tempreature of Mg2Cu alloy is lower than pure magnesium about 20
℃ and it announces that addition of copper can accelerate the
dehydriding reaction of magnesium. Besides, the endothermic reaction
that as-cast structure are formed for the hydriding
Mg2(Cu1-xNix)(X=0.2,0.4,0.6,0.8) alloys in dehydriding process are
observed.關鍵字(中) ★ XRD
★ 固溶體晶格擴張侷限
★ DSC
★ 儲氫合金
★ Mg2(Cu1-xNix)合金關鍵字(英) ★ hydrogen storage alloys
★ Mg2(Cu1-xNix) alloys
★ XRD
★ lattice論文目次 總目錄
中文摘要....................................................i
英文摘要..................................................iii
謝 誌....................................................v
總 目 錄...................................................vi
圖 目 錄.................................................viii
表 目 錄....................................................x
一、前言與文獻回顧..........................................1
1.1 儲氫合金簡介..........................................1
1.2 儲氫合金吸放氫原理介紹 ...............................2
1.2.1 動力學性質........................................2
1.2.2 熱力學性質........................................4
1.3 儲氫合金種類介紹......................................8
1.4 Mg-Cu-Ni儲氫合金介紹..................................9
1.5 研究背景與目的.......................................11
二、實驗步驟與方法.........................................13
2.1 IECP法製備Mg2(Cu1-x Nix)合金流程 .......................14
2.2 感應耦合電漿質譜儀(Inductively coupled plasma-mass
spectrometry)成分分析.................................14
2.3 X光繞射分析(X-ray diffraction methods，XRD) ...........15
2.3.1 X光粉末繞射分析（X-Ray Powder Diffraction，XRPD） .15
2.3.2 X光單晶繞射分析（Single-Crystal Diffractometer，
X-RAY/CCD) .......................................15
2.4 合金儲放氫特性 ......................................16
2.4.1 吸氫速率(Rate of absorption)測試.................16
2.4.2 PCI曲線(Pressure-composition-isothermal curves，
PCI)測試.........................................17
2.5 微差掃描熱分析(Differential scanning calorimetry，DSC ).17
三、結果與討論.............................................18
3.1 IECP 法製備Mg2(Cu1-x Nix)合金...........................18
3.1.1 Mg2(Cu1-x Nix)合金成分分析..........................18
3.1.2 Mg2(Cu1-x Nix)合金XRD分析 .........................19
3.2 儲放氫特性分析.......................................21
3.2.1 合金吸氫速率測試.................................21
3.2.2 合金PCI曲線量測..................................23
3.3合金吸氫過程之結構分析 ...............................26
3.4 固溶體氫化擴張侷限(Lattice expansion limitation
affected by additives)...............................31
3.4.1 Mg2Cu固溶體氫化擴張侷限..........................32
3.4.2 Mg2(Cu0.4Ni0.6)與Mg2(Cu0.2Ni0.8)固溶體氫化擴張侷限 .....33
3.5 合金放氫熱行為.......................................36
3.5.1 低溫區(200℃~320℃)合金放氫熱行為................36
3.5.2 高溫區(320℃~460℃)合金放氫熱行為................37
四、結論...................................................42
五、未來研究方向...........................................44
六、參考文獻...............................................45參考文獻 [1]T. Graham, “On the Relation of Hydrogen to Palladium”, J. Franklin Inst., Vol.87, 1869, pp.256-266.
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