水熱法合成及成長Hematite-還原至Magnetite的動力學探討及其鋰電池應用

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研究生：	呂潔峰 Lu, Jie Feng
論文名稱：	水熱法合成及成長Hematite-還原至Magnetite的動力學探討及其鋰電池應用 Hydrothermal Growth of Hematite Particles-Kinetic of Reduction to Magnetite and Its Application for Lithium Ion Battery
指導教授：	蔡哲正 Tsai, Cho Jen
口試委員:	廖建能鄭如忠顏光甫甘炯耀蔡哲正
學位類別：	博士 Doctor
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2016
畢業學年度：	104
語文別：	英文
論文頁數：	69
中文關鍵詞：	水熱法、相變化、鋰電池
外文關鍵詞：	hydrothermal, phase transformation, lithium ion battery
相關次數：	點閱：3 下載：0
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從三氧化二鐵相還原至四氧化三鐵相的相變化可經由水熱法製程在添加KOH及EDA的含鐵離子溶液中並加熱至180-220oC的條件下而產生。這個反應首先形成六角片狀的α-Fe2O3 粒子，隨著反應時間增加，六角片狀的α-Fe2O3 粒子開使溶解而釋放出Fe3+離子而Fe3+ 離子還原至Fe2+離子也同時進行著，然後Fe3O4多面體粒子開始成核成長。從三氧化二鐵相還原至四氧化三鐵相的相變化活化能為96.411, 113.15, and 118.311 kJ/mol ; 這是在水熱法製程下分別添加0.5、1 和 1.5 ml EDA的條件下獲得，而這樣的值與在氫氣氛圍條件下從三氧化二鐵相還原至四氧化三鐵相的相變化所得的值是相近的。
在水熱法製程裡於含鐵溶液中依照不同的水與EDA溶積比並加熱至180OC的條件下可生成不規則多面體、雙六角錐、拉長雙錐體、斜方六面體的α-Fe2O3 奈米粒子。以這些不同形狀當電極材料的鋰電池，經由電化學量測可知以雙六角錐α-Fe2O3 奈米粒子當電極的電池有最好的電容量以及變速率偱環壽命表現。此結果顯示除了粒子的尺寸以外，粒子的形狀並其上的面是另一個影响電池在電化學量測表現上的重要因素。

Phase transform of α-Fe2O3 to Fe3O4 were observed by hydrothermal treatment of ferric solution at 160-220 oC with the addition of both KOH and EDA into the reaction system. The reactions began with the formation of α-Fe2O3 hexagonal plates followed by the phase transformation involving dissolution of the α-Fe2O3 hexagonal platelets, the reduction of Fe3+ to Fe2+, and the nucleation and growth of new Fe3O4 polyhedral particles. The activation energies for the phase transformation of α-Fe2O3 to Fe3O4 in hydrothermal condition are estimated to be 96.411, 113.15, and 118.311 kJ/mol for the case of addition of 0.5, 1 and 1.5 ml of EDA, respectively, which are about the same for typical phase transformation of α-Fe2O3 to Fe3O4 in hydrogen ambient. Hematite (α-Fe2O3) nanoparticles with irregular polyhedron, hexagonal bipyramid, elongated bipyramid, and rhombohedron shapes were prepared by hydrothermal treatment of ferric solution at 180 oC with the addition of different amount of water to EDA ratio in the reaction systems. The electrochemical measurements of these different particle shapes as materials for lithium ion battery showed that the best performance both in specific capacity and rate capacity were observed to be the shape of hexagonal bipyramid. The results show that, beside the size of the particles, the shape of the particles which is confined with specific surfaces is another important factor that dictates the electrochemical performance of α-Fe2O3.

Abstract    I
Acknowledgement    III
Content    IV
Chapter 1 Introduction    1
1-1   The properties of iron oxides    1
1-1.1    Iron Oxides    1
1-1.2    α-Fe2O3    2
1-1.3   Fe3O4    3
1-2    Hydrothermal Methods for Growth of α-Fe2O3 and Fe3O4 Nanostructure    5
1-3    Phase transformation from α-Fe2O3 to Fe3O4    5
1-3.1   Non-redox transformations between magnetite and hematite    5
1-3.2    Phase transformation induced by thermal annealing under hydrogen ambient    6
1-3.3    Reducing agents induce phase transformation    7
1-3.4    Mechanochemical reaction induce phase transformation    7
1-4    Lithium ion battery    7
1-4.1     Background    7
1-4.2    Lithiation/delithiation mechanism    9
1-4.2.1   Intercalation    10
1-4.2.2   Alloying    10
1-4.2.3   Conversion    11
1-4.3    Fe2O3 as an anode electrode    11
1-5    Motivation    12
Chapter 2 Experimental Procedures    14
2-1    Hydrothermal Synthesis of Iron Oxides Micro/Nanoparticles    14
2-2    Preparation of α-Fe2O3 anode material electrode    18
2-3    Scanning Electron Microscope Observation (SEM)     20
2-4    X-ray Diffraction Analysis (XRD)     20
2-5    Transmission Electron Microscope Observation (TEM)    20
2-6    Vibrating sample magnetometer (VSM)    21
2-7    Electrochemical characterization    21
Chapter 3 Results and Discussion     22
3-1    Synthesize of Hematite and Magnetite     22
3-1.1    Phase transformation of iron oxides    24
3-1.2    The role of K+ ions and NO3- ions    30
3-1.3    The role of pH values    33
3-1.4   Reduction kinetics of Hematite to Magnetite    37
3-1.5     The magnetic properties of iron oxide particles    43
3-2    -Fe2O3 particles as anode materials for lithium ion battery    45
3-2.1    Synthesize of various shape of -Fe2O3 nanoparticles    45
3-2.2    Shapes Dependence of the Electrochemical Properties of α-Fe2O3 Particles as Anode Materials for Lithium Ion Battery    52
Chapter 4 Conclusions     62
References    64

                                

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