臺灣博碩士論文加值系統

近年來，由於電動車市場的崛起，鋰電池的需求已由原先高能量密度轉變為高功率密度和長循環壽命。因此，本研究擬定針對高功率密度與長循環壽命之LiNi0.5Mn1.5O4正極材料及Li4Ti5O12負極材料進行研究。
藉由改良式固態法可有效合成多孔性無雜相之LiNi0.5Mn1.5O4正極材料。隨著多孔性結構形成，電容量由原先的105增加至120 mA/g而且循環壽命也從65 % (充放電500圈)提昇至80 % (充放電1000圈)。
調整煆燒溫度(700～800 0C)製備出LiNi0.5Mn1.5O4擁有Fd3m與(Fd3m+P4332)混合之space group。在55 0C，Fd3m與混合相(Fd3m+P4332)結構之LiNi0.5Mn1.5O4在150圈充放電後，電容量仍有77 與83 %。擁有Fd3m 結構 之LiNi0.5Mn1.5O4電容量衰退可歸咎於Mn3+的分解((Mn3+→Mn2+ + Mn4+)。
經由混合LiCl、TiCl4與草酸經過兩階段燒結過程製備出多孔性負極材料Li4Ti5O12。此多孔性Li4Ti5O12負極材料在0.5、1、5、10 C的充放電速率下，分別出現167、133、100、70 mAh/g且在充放電200圈後，電容量仍然維持超過98 %。
經由調整第一階段燒結溫度的調整能有效使Li2TiO3產生，此化合物能進一步與rutile TiO2反應成純相Li4Ti5O12。純相Li4Ti5O12在0.5與1 C的充放電速率下，能呈現出169與150 mAh/g的電容量且在150圈充放電後，電容量仍然維持超過98 %，然而，有TiO2雜相出現時，在相同的充放電速率下，只有148與125 mAh/g。
為了全面性改善Li4Ti5O12導電性差之缺點，結合Ru doping 與carbon coating的技術來改善Li4Ti5O12粉體內部導電度和降低外部Li4Ti5O12粉體間的傳輸阻抗。在5與10 C的充放電速率且充放電100圈後， Li4Ru0.01Ti4.99O12/C 仍出現120與110 mAh/g。由改質結果可知，Li4Ru0.01Ti4.99O12/C擁有最好的充放電能力與最佳的電容量。

List of Tables III
Figure Captions IV
Abstract X
Chapter 1 Introduction 1
1.1 Lithium ion battery 1
1.2 Motivations 2
1.2.1 Cathode material LiNi0.5Mn1.5O4 2
1.2.2 Anode material Li4Ti5O12 4
Chapter 2 Literature Review 6
2.1 History of Lithium Ion Battery 6
2.2 Cathode material in lithium ion battery 9
2.2.1 The requirement of cathode materials 9
2.2.2 Layer-Structured LiCoO2 and LiNiO2 10
2.2.3 Olivine LiFePO4 14
2.2.4 Spinel LiMn2O4 16
2.2.5 Evolution of 5V cathode materials LiNi0.5Mn1.5O4 19
2.2.6 The electrochemical performance of spinel LiNi0.5Mn1.5O4 with different space group (Fd3m and P4332) 28
2.3 Anode material in lithium ion battery 32
2.3.1 Carbon 32
2.3.2 Stannum (Sn) 35
2.3.3 Lithium titanate (Li4Ti5O12) 37
Chapter 3 Experimental Procedure 53
3.1 A modified solid state method 53
3.1.1 Cathode material LiNi0.5Mn1.5O4 53
3.1.2 Anode material Li4Ti5O12 53
3.2 Characterization and analysis 54
3.2.1 Composition evaluation 54
3.2.2 TGA analysis 54
3.2.3 Phase identification 55
3.2.4 Morphological observation and specific surface area 55
3.2.5 Electrochemical impedance spectroscopy (EIS) 56
3.2.6 Fourier transform infrared spectrophotometer (FTIR) 56
3.2.7 Electrochemical measurement 56
Chapter 4 Results and Discussion 61
4.1 Synthesis of porous and impurity-free LiNi0.5Mn1.5O4 cathode material to improve extended cycling life and rate capability 61
4.1.1 A modified solid state method 61
4.1.2. Compositional Evaluation 65
4.1.3. Phase identification and morphology observation 67
4.1.4. Electrochemical performance 75
4.2. Comparison of electrochemical properties of LiNi0.5Mn1.5O4 with Fd3m space group and with mixed Fd3m and P4332 space groups 82
4.2.1 FTIR analysis for LiNi0.5Mn1.5O4 with different space group 82
4.2.2 Electrochemical performance and ICP analysis 85
4.3 Porous Li4Ti5O12 anode material synthesized by a modified solid state method for electrochemical properties enhancement 91
4.3.1 Phase identification and morphology observation for porous Li4Ti5O12 91
4.3.2 Electrochemical performance and impedance measurement 94
4.4 Fabrication of pure and highly crystalline spinel Li4Ti5O12 anode material by two-step heat treatment method 104
4.4.1 XRD analysis of different preheating temperature 104
4.4.2 Morphology of Li4Ti5O12 fabricated by two-step heat treatment 110
4.4.3. Electrochemical performance of Li4Ti5O12 with and without impurity TiO2 112
4.5 Improved capacity and rate capability of Ru-doped and carbon-coated Li4Ti5O12 anode material 119
4.5.1 The reason for choosing the Ru element 120
4.5.2 The XRD and morphology of Li4Ti5O12, Li4Ti5O12/C, Li4Ru0.01Ti4.99O12 and Li4Ru0.01Ti4.99O12/C 121
4.5.3 Electrochemical performance and impedance analysis results of Li4Ti5O12, Li4Ti5O12/C, Li4Ru0.01Ti4.99O12 and Li4Ru0.01Ti4.99O12/C 126
Chapter 5 Conclusions 134
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