臺灣博碩士論文加值系統

本研究使用氫化鎂與鋁氫化鋰做為研究的混合金屬氫化物材料，然而先前實驗室研究成果中利用臨場同步X光繞射已經了解混合粉體放氫的機制，其中氫化鎂為可逆性材料，因此本研究著重在複合金屬氫化物的吸氫行為。實驗以機械球磨法均勻混合MgH2與LiAlH4，利用高壓熱重分析儀(HPTGA)測定混合粉體吸氫性質，並藉由臨場同步X光繞射技術(In-situ synchrotron XRD)探討混合粉體在吸氫過程中反應現象。
使用臨場同步X光繞射分析的結果可知，MgH2與LiAlH4混合粉體確實有可逆吸氫的行為發生，且吸氫的條件與環境溫度有關，當溫度上升到400 oC才有反應反生，因此以此溫度作為充氫時的環境溫度。結果顯示，溫度維持在400 oC下持續升壓，使壓力到達3.1MPa可使4MgH2-1LiAlH4有3 wt%的吸氫量，且在0.17 MPa ~1.38 MPa的壓力區間有較快的吸氫速率為0.065 wt%/min，之後則以0.0072 wt%/min進行吸氫。為了了解不同莫耳比的混合粉體在吸氫過程中的反應機構，將壓力升至0.7、1.4、2.4 MPa之X光繞射分析圖可得知，在MgH2-1LiAlH4 莫耳比(1：1) 的吸氫行為發生在0.7 MPa ~ 1.4 MPa之間，由Mg17Al12與Mg2Al3進行吸氫反應；莫耳比(2：1) 吸氫行為發生在0.7 MPa之前，由Mg、Li0.92Mg4.08、Mg17Al12先行吸氫生成MgH2，以及部份的Mg17Al12吸氫生成Mg2Al3，當壓力持續上升到1.4 MPa則由Mg2Al3進行吸氫反應；莫耳比(4：1) 同樣在0.7 MPa之前即有產物Mg、Li0.92Mg4.08進行吸氫產生氫化鎂，但其產生MgH2量較少，而在繼續升壓的過程中則由Mg17Al12進行吸氫反應，且從圖上可知，主要吸氫生成MgH2的化合物為Mg17Al12。
在吸氫速率較快的壓力區間取1.03 MPa作為恆壓壓力並恆壓一小時及兩小時，結果顯示4MgH2-1LiAlH4混合粉體未能到達實驗所測得的最大吸氫量3 wt%，且與4MgH2-1LiAlH4混合粉體直接升壓至3.1 MPa的曲線比較下，相同吸氫量所要花費的時間也較長，進一步取1.72 MPa恆壓一小時，有較快吸氫速率區間出現，可到達2.9 wt%的吸氫量，因此可再將低恆壓壓力，取臨界壓力1.38 MPa恆壓一小時，可達到3 wt%吸氫量。結果顯示選擇臨界壓力1.38 MPa並恆壓一小時可以有較好的吸氫效率。
進一步做4MgH2-1LiAlH4三次循環放氫/吸氫的測試。在第一次循環放氫/吸氫中，LiAlH4的起始放氫溫度為175 oC而MgH2的起放氫溫度為310 oC，吸氫量可到達3 wt%。第二次循環放氫/吸氫的結果顯示，MgH2的起始放氫溫度相較於第一次循環放氫時的MgH2的起始放氫溫度高，在385 oC開始釋氫，顯示LiAlH4有催化MgH2的效果使之起始放氫溫度提前，然而第二次循環放氫/吸氫的總吸氫量降低，然而卻有100 %的吸氫程度，顯示可逆效果佳，而第三次循環測試總吸量再度降低，吸氫程度也下降10 %，但仍然有不錯的可逆反應發生。

Rehydrogenation behavior of the discharged MgH2-LiAlH4 composites was investigated by using thermal gravimetric analysis (TGA) and in situ synchrotron X-ray diffraction (XRD) technique. For 4MgH2-LiAlH4 composite, the experimental results showed that at least 3 wt% of hydrogen could be recharged during rising pressure to 3.1MPa/H2 at 400 °C to form MgH2 after its first dehydrogenation reaction. The faster hydrogen absorption rate 0.065 wt%/min happened between 0.17 MPa ~ 1.38 MPa. The XRD results indicated that it would have different absorption reaction in the various pressure interval by using various MgH2-LiAlH4 composite. (Table 1) Not only Mg but also Mg17Al12 and Mg2Al3 could be rehydrogenated in the hydrogen atmosphere investigated although LiAlH4 was found irreversible. In the experiment of isobaric, we know that it must be more than 1.38 MPa would have a better amount of hydrogen absorption and reaction time. In the cyclic test, the second test had the extent of hydrogen absorption 100 %, and the third one had 90%. Both of them were good. The In-situ synchrotron XRD results indicated that the reversibility of the MgH2-LiAlH4 composite which was temperature-dependent.

摘要 I
EXTENDED ABSTRACT III
誌謝 XIII
總目錄 XV
圖目錄 XVII
表目錄 XX
一、前言 1
二、研究背景及文獻回顧 9
2-1固態金屬氫化物儲氫系統 9
2-1鋁氫化鋰之基本性質 11
2-2氫化鎂之基本性質 13
2-3氫化物複合系統開發 14
三、研究方法與實驗步驟 26
3-1氫化鎂-鋁氫化鋰混合粉體之製備 26
3-2材料基本特性分析 27
3-2-1微觀結構分析 27
3-2-2微晶結構分析 27
3-3臨場同步X光繞射分析 27
3-4熱重分析 28
四、結果與討論 36
4-1 MgH2-LiAlH4混合粉體之基本性質分析 36
4-1-1混合粉體的形貌觀察 36
4-1-2混合粉體的結晶結構 36
4-2 MgH2-LiAlH4混合粉體釋氫行為比較 37
4-3 MgH2-LiAlH4混合粉體吸氫行為比較 40
4-3-1臨場同步輻射X光繞射分析 (in-situ XRD) 41
4-3-2吸氫溫度、吸氫量、吸氫壓力 41
4-3-3吸氫反應機構 42
4-3-4恆壓對混合粉體吸氫行為之影響 44
4-4粉體放氫/吸氫循環特性 45
4-4-1 4MgH2-LiAlH4混合粉體 45
4-4-2 球磨0.5小時之氫化鎂 46
五、結論 73
六、參考文獻 76

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