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研究生： 丁淑菱
Damayanti, Mia Kristina
論文名稱： 合成路徑對鎳錳層狀氧化物正極材料LiNi0.5Mn0.5O2 之結構與電化學行為之影響
Effect of Processing Routes on Electrochemical/Structural Behaviour of Co-free Layered LiNi0.5Mn0.5O2 Cathode for Li-ion Battery Application
指導教授： 方冠榮
Fung, Kuan-Zong
學位類別： 碩士
Master
系所名稱： 工學院 - 尖端材料國際碩士學位學程
International Curriculum for Advanced Materials Program
論文出版年： 2019
畢業學年度： 107
語文別： 英文
論文頁數： 86
外文關鍵詞： Co-Free, Layered LiNi0.5Mn0.5O2, Sol-gel, Solid-state
相關次數： 點閱：61  下載：0 
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    • High-capacity cathode materials typically contain a certain amount of Cobalt for stabilization and promoting their electrochemical properties. However, Co price has gone up significantly so high that Co-free cathode materials have been proposed and investigated recently. Co-free layered LiNi0.5Mn0.5O2 has received considerable attention due to high theoretical capacity (280 mAh g-1) and low cost comparable than LiCoO2. The ability of nickel to be oxidized (Ni2+/Ni3+/Ni4+) acts as electrochemical active and has a low activation energy barrier, while the stability of Mn4+ provides a stable host structure.
    However, selection of appropriate preparation method and condition are critical to providing an ideal layered structure of LiNi0.5Mn0.5O2 with good electrochemical performance. Layered LiNi0.5Mn0.5O2 has been synthesized using sol-gel and solid-state routes. FT-IR and X-Ray diffraction investigated thermal decomposition and phase formation growth, respectively. Scanning Electron Microscopy examined particle size and morphology. X-ray photoelectron spectroscopy and Four Point Probe were used to confirm the valence state of Ni2+/Mn4+ and electronic conductivity, respectively. Relative pure phase can be obtained by the sol-gel method at low temperature, due to the short distance among lithium and transition metal formed in the precursor. Conversely, incompletely three-phase transformation occurs on the solid-state method at the same temperature, indicate the deficient of energy. Materials prepared by sol-gel show better electrochemical performance instead of solid-state, correspond to the discharge capacity and cycle life performance.

    Abstract ii Acknowledgements iii Contents iv List of Tables vii List of Figures viii Chapter 1 Introduction 1 1.1 General Background 1 1.2 Motivation 7 1.3 Research Objective 8 Chapter 2 Theoretical Background 9 2.1 Lithium-Ion Battery 9 2.1.1 Working Principle 9 2.1.2 Galvanostatic cell cycling 10 2.1.3 Electrolyte and Binders 12 2.2 Layered Structure Metal Oxide 12 2.2.1 Lithium Cobalt Oxide (LiCoO2) 13 2.2.2 Lithium Nickel Oxide (LiNiO2) 14 2.2.3 Lithium Nickel Manganese Oxide (LiNi0.5Mn0.5O2) 14 2.3 Overview whole Characteristic of LiNi0.5Mn0.5O2 15 2.3.1 State of the art 15 2.3.2 The binary stoichiometric of LiNi0.5Mn0.5O2 16 2.3.3 Ordering Paradigm 17 2.3.4 Electronic Structure 18 2.3.5 Electrochemical Principle 19 2.3.6 Cathode Degradation 21 2.4 Synthesis Routes for Layered LiNi0.5Mn0.5O2 21 2.4.1 Solid-state reaction by high energy ball-milling 22 2.4.2 Co-precipitation 22 2.4.3 Hydrothermal 23 2.4.4 Spray Pyrolysis 23 2.4.5 Sol-gel 23 2.5 Structural and Phase Transformation LiNi0.5Mn0.5O2 26 2.5.1 The Li-Mn-Ni Oxide Pseudo-Ternary System 26 2.5.2 Phase Tranformation 27 Chapter 3 Experimental 32 3.1 Materials Synthesis 32 3.2 Sample Preparation 33 3.2.1 Sol-gel synthesis 33 3.2.2 Solid State 34 3.2.3 Preparation of Electrodes 36 3.3 Materials Characterization and Measurement 37 3.3.1 Weight Loss Measurement 37 3.3.2 X-Ray Diffraction (XRD) 37 3.3.3 Scanning Electron Microscopy (SEM) 38 3.3.4 Electronic Conductivity 38 3.3.5 Fourier Transform Infrared Spectroscopy (FTIR) 39 3.3.6 X-ray Photoelectron spectroscopy (XPS) 39 3.4 Electrochemical Testing 40 3.4.1 Coin Test Cell Assembly 40 3.4.2 Galvanostatic Measurement 42 Chapter 4 Result and Discussion 43 4.1 Thermal Decomposition and Reaction precursor 43 4.1.1 Weight loss analysis 43 4.1.2 FT-IR Confirmation 45 4.2 Purpose Mechanism of Gel Formation and Reaction Equation 46 4.2.1 Possible Equation Reaction and Weight Lost Estimation 49 4.3 Crystal Structure Analysis 50 4.3.1 Phase Transition 50 4.3.2 Lattice Constant 58 4.4 Effect of Temperature 59 4.4.1 Crystallite size and morphology 59 4.4.2 Electrochemical Performance 61 4.5 Effect of Synthesis Routes 64 4.5.1 Particle size and Morphology 64 4.5.2 Electronic Conductivity 66 4.5.3 Oxidation State of Transition Metals 66 4.5.4 Electrochemical Performance 72 Chapter 5 Conclusion 76 References 77

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