微量LaNi5合金與機械球磨對Mg3MnNi2合金電化學特性之影響

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郭峻誠(Chun-Cheng Kuo) 查詢紙本館藏

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能源工程研究所

論文名稱

微量LaNi5合金與機械球磨對Mg3MnNi2合金電化學特性之影響
(The study of ball-milling and LaNi5 alloy additive on the electrochemical performances of Mg3MnNi2 alloy)

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摘要(中)

利用恆溫揮發鑄造法（Isothermal Evaporation Casting Process，IECP）製備Mg3MnNi2合金，藉由機械球磨法與添加微量LaNi5合金，觀察各合金之結構變化與電化學特性之影響。
Mg3MnNi2合金經由機械球磨法減少顆粒及晶粒尺寸，導致比表面積的增加與吸放氫擴散路徑的縮小，進而改善Mg3MnNi2合金放電電容量，球磨30分鐘有最大放電電容量206 mAh/g較鑄態合金提升40 mAh/g，但經球磨過之合金其放電循環壽命則會大幅降低。
此外，將球磨30分鐘Mg3MnNi2合金添加 x wt.% LaNi5 (x=10,20及30)合金藉由球磨法形成複合材料，發現隨著LaNi5合金的含量增加，球磨30分鐘Mg3MnNi2合金放電循環壽命隨之提升，球磨30分鐘Mg3MnNi2-30 wt.% LaNi5合金擁有最佳放電電容量與放電循環壽命。

摘要(英)

Mg3MnNi2 alloy were prepared by IECP. The Mg3MnNi2 alloy were modified by mechanical ball-milling and LaNi5 alloy additive on the Mg3MnNi2 alloy. The phase structures and electrochemical properties of the ball-milled Mg3MnNi2 alloys and Mg3MnNi2-LaNi5 composites were studied.
The surface modification of the alloys by mechanical ball-milling led to improvement of the discharge capacity, due to increment surface area and decrement diffusion length for the desorption of absorbed hydrogen. The ball-milled 30 min of Mg3MnNi2 alloy had the largest discharge capacity 206 mAh/g that was higher than the as-cast Mg3MnNi2 alloy 40 mAh/g, but the ball-milled alloys cycle life decreased obviously.
The ball-milled 30 min Mg3MnNi2- x wt.% as-cast LaNi5 (x=10,20 and 30) composites were fabricated by mechanical ball-milling. It was found that the ball-milled 30 min 30 min Mg3MnNi2 alloy increased cycle life with increment the LaNi5 alloy content. And the ball-milled 30 min Mg3MnNi2-30 wt.% as-cast LaNi5 alloy was effectively maintained high discharge capacity and cycle life.

關鍵字(中)

★ 鎂基合金電極
★ 機械球磨法
★ 恆溫揮發鑄造法

關鍵字(英)

★ ball-milling
★ Mg-based alloy electrode
★ IECP method

論文目次

中文摘要.................................................i
英文摘要.................................................ii
謝誌.................................................iii
總目錄.................................................iv
圖目錄.................................................vi
表目錄................................................viii
一、前言 .................................................1
二、文獻回顧..............................................3
2-1 氫能源之開發...........................................3
2-2 氫能經濟系統...........................................3
2-3鎳氫電池簡介............................................5
2-3-1 電池之簡介...........................................5
2-3-2 鎳氫電池之構造.......................................7
2-3-3 鎳氫電池之運作原理...................................8
2-3-4 鎳氫電池之儲氫合金選用..............................10
2-4 儲氫合金簡介..........................................10
2-4-1儲氫合金種類介紹.....................................10
2-4-4 商業化儲氫合金......................................11
2-4-5 Mg2Ni與Mg-Ni儲氫合金性質介紹........................12
2-5 Mg-Ni合金製備方式.....................................14
2-5-1 恆溫揮發鑄造法 (IECP)...............................14
2-5-2 機械合金法..........................................16
三、研究目的與動機.......................................19
四、實驗步驟與方法.......................................20
4-1 合金製備..............................................20
4-1-1 恆溫揮發鑄造法(IECP)................................20
4-1-2 電弧熔煉法..........................................21
4-2 球磨法製備合金........................................21
4-3 X光繞射分析...........................................22
4-4 合金粉末粒徑分析......................................22
4-5 合金粉末表面型態分析..................................22
4-6 合金腐蝕性質分析......................................22
4-7 放電電容量與放電循環壽命測試..........................23
五、結果與討論...........................................24
5-1 球磨Mg3MnNi2合金之性質分析............................24
5-2 球磨30分鐘Mg3MnNi2合金添加鑄態LaNi5合金之性質分析.....31
5-3 鑄態與改質Mg3MnNi2合金之性質分析......................45
六、結論.................................................47
七、未來工作.............................................48
八、參考文獻.............................................49
圖目錄
圖2.1 氫能經濟示意圖.......................................3
圖2.2 圓柱型、鈕扣型及長方體型鎳氫電池內部構造.............8
圖2.3 鎳氫電池充放電反應之模型圖...........................9
圖2.4 Mg2Ni-x Mg3MnNi2系統合金放電電容曲線(a) x=0 (b) x=15 (c) x=30 (d) x=60 (e)x=100................................13
圖2.5 Mg-Ni 二元相圖......................................15
圖2.6 恆溫鑄造揮發法圖示 (a) 升溫曲線 (b) 熔煉流程........16
圖2.7 機械合金法 : A為冷焊、B為脆裂.......................17
圖2.8 粉末粒徑與球磨時間之關係曲線圖......................17
圖2.9 鑄態與球磨Mg2Ni合金之放電電容量.....................18
圖2.10 不同球磨間對Mg2Ni合金之放電電容量..................18
圖4.1 實驗流程圖..........................................20
圖4.2 Mg3MnNi2合金熔煉流程圖..............................21
圖5.1 Mg3MnNi2合金X光繞射分析 (a) 鑄態 (b) 球磨15分鐘 (c) 球磨30分鐘 (d) 球磨60分鐘 (e) 球磨90分鐘....................24
圖5.2 Mg3MnNi2合金粉體表面型態 (a) 鑄態 (b) 球磨15分鐘 (c) 球磨30分鐘 (d) 球磨60分鐘 (e) 球磨90分鐘..................26
圖5.3 Mg3MnNi2合金粒徑分析 (a) 鑄態 (b) 球磨15分鐘 (c) 球磨30分鐘 (d) 球磨60分鐘 (e) 球磨90分鐘......................27
圖5.4 Mg3MnNi2合金放電電容量曲線 (a) 鑄態 (b) 球磨15分鐘 (c) 球磨30分鐘 (d) 球磨60分鐘 (e) 球磨90分鐘..............28
圖5.5 Mg3MnNi2合金放電循環壽命測試曲線 (a) 鑄態 (b) 球磨15分鐘 (c) 球磨30分鐘 (d) 球磨60分鐘 (e) 球磨90分鐘...........29
圖5.6 Mg3MnNi2合金腐蝕電流曲線 (a) 鑄態 (b) 球磨15分鐘 (c) 球磨30分鐘 (d) 球磨60分鐘 (e) 球磨90分鐘..................30
圖5.7 球磨30分鐘Mg3MnNi2合金添加x wt.% 鑄態LaNi5合金X光繞射分析 (a) 鑄態LaNi5 (b) x=0 (c) x=10 (d) x=20 (e) x=30.....32
圖5.8合金放電循環壽命測試曲線 (a) 鑄態LaNi5合金 (b) 球磨30分鐘Mg3MnNi2合金............................................33
圖5.9 鑄態LaNi5合金經過不同次數充放電循環測試後之粉體表面型態 (a) 第0次 (b) 第3次 (c) 第6次 (d) 第9次................34
圖5.10 球磨30分鐘Mg3MnNi2合金添加x wt.% 鑄態LaNi5合金放電循環壽命測試曲線之理論值與實驗值 (a) x=10 (b) x=20 (c) x=30.36
圖5.11 球磨30分鐘Mg3MnNi2合金添加x wt.% 鑄態LaNi5合金放電循環壽命測試曲線 (a) x=10 (b) x=20 (c) x=30.................38
圖5.12 合金電極經8次充放電循環測試後腐蝕電流曲線 (a) 球磨30分鐘Mg3MnNi2合金 (b) 球磨30分鐘Mg3MnNi2-30 wt.% LaNi5複合材料........................................................40
圖5.13 球磨30分鐘Mg3MnNi2-30 wt.% LaNi5合金球磨後之X光繞射分析 (a) 球磨0秒 (b) 球磨30秒 (c) 球磨60秒..................41
圖5.14 球磨30分鐘Mg3MnNi2-30 wt.% LaNi5合金球磨後之粉末表面型態 (a) 球磨0秒 (b) 球磨30秒 (c) 球磨60秒................42
圖5.15 球磨冷焊效應示意圖.................................42
圖5.16 球磨30分鐘Mg3MnNi2-30 wt.% LaNi5合金球磨後之粒徑分析 (a) 球磨 0 秒 (b) 球磨30秒 (c) 球磨60秒...................43
圖5.17 球磨30分鐘Mg3MnNi2-30 wt.% LaNi5合金球磨後之放電循環壽命測試 (a) 球磨0秒 (b) 球磨30秒 (c) 球磨60秒............44
圖5.18 Mg3MnNi2合金放電循環壽命測試曲線 (a) 鑄態 (b) 改質型........................................................46
表目錄
表2-1 各種儲存氫氣方式中體積密度的比較.....................4
表2-2電池種類表............................................6
表2-3 二次電池比較表.......................................7
表2-4 儲氫合金特性........................................11
表2-5 AB2與AB5型儲氫合金之特性比較........................12
表2-6 添加元素對Mg2Ni儲氫合金電化學影響...................14
表5-1 Mg3MnNi2合金之晶粒尺寸..............................25
表5-2 Mg3MnNi2合金之粉末顆粒尺寸與比表面積................27
表5-3 Mg3MnNi2合金放電電容量與放電循環壽命衰退比率........29
表5-4 Mg3MnNi2合金之腐蝕電位與腐蝕電流....................31
表5-5球磨30分鐘Mg3MnNi2合金添加x wt.% 鑄態LaNi5合金放電循環壽命衰退比率之理論值與實驗值..............................37
表5-6 球磨30分鐘Mg3MnNi2合金添加x wt.% 鑄態LaNi5合金放電電容量與放電循環壽命衰退比率..................................38
表5-7合金電極經8次充放電循環測試後之腐蝕電位與腐蝕電流....40
表5-8 球磨30分鐘Mg3MnNi2-30 wt.% LaNi5合金之粉末顆粒尺寸..43
表5-9 球磨30分鐘Mg3MnNi2- 30 wt.% LaNi5合金球磨後之放電電容量與放電循環壽命衰退比率..................................45
表5-10 鑄態與改質Mg3MnNi2合金放電電容量與放電循環壽命衰退比率........................................................46

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指導教授

李勝隆(Sheng-Long Lee)

審核日期

2011-8-13

推文