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title page
Contents
(Abstract) 9
I. Literature survey 10
1. Batteries 10
A. Components of cells and batteries 10
B. Theoretical cell voltage, capacity and energy 11
2. Lithium ion secondary batteries 18
3. Cathode materials for lithium ion secondary batteries 23
4. Spinel type cathode materials 27
A. The Li-Mn-O phase diagram 27
B. The structure of LiMn₂O₄ 30
II. Introduction 34
III. Experimental 35
1. Powder preparation 35
2. Powder characteristics 35
3. Electrochemical characteristics 36
IV. Results and discussions 39
1. Powder characteristics 39
A. X-ray diffraction 39
B. Scanning electron microscopy 44
C. X- ray photo-electron spectroscopy 46
2. Electrochemical characteristics 52
V. Conclusions 58
References 59
(국문초록) 63
Table. 1.1. Characteristics of electrode materials 15
Table. 1.2. Voltage, capacity and specific energy of major battery systems -Theoretical and practical values 16
Table. 1.3. Performances, properties, and applications of secondary batteries 21
Table. 1.4. Comparisons of cathode materials 26
Table. 4.1. Lattice parameters of the samples which were synthesised by solid state reaction 41
Table. 4.2. Lattice parameters and average manganese valences of various manganese based spinel oxide made at 800℃ 43
Table. 4.3. XPS survey scan data sheet for LiNi0.5Mn1.5O4 spinel 48
Fig. 1.1. Schematic representation of (a) the sony rocking-chair cell and (b) a rechargeable lithium cell with a lithium metal negative electrode. The maximum lithium content in ordered graphite is LiC6.(이미지참조) 22
Fig. 1.2. The Li-Mn-O phase diagram. 29
Fig. 1.3. An expanded section of the phase diagram showing the compositions of spine & defect spine1 and rock salt structures. 29
Fig. 1.4. Schematic drawing of the LiMn₂O₄spinel structure. 31
Fig. 1.5. Schematic drawing of lattice surroundings and nearest neighbors for (a) the tetrahedral A-site (8a), (b) the octahedral B-site (16d), and the tetrahedral anion O-site (32e). 32
Fig. 1.6. The three-dimensional interstitial pathways for lithium-ion diffusion. 33
Fig. 3.1. Experimental steps for the preparation of LiM0.5 Mn1.5 O₄(M=Co, Ni, Cr, Al) powder.(이미지참조) 38
Fig. 4.1. X-ray diffraction patterns of samples which synthesised by solid state reaction. 40
Fig. 4.2. X-ray powder diffraction patterns of LiMn₂-y-zMy LizO₄synthesized by solid-state reaction at 800℃.(이미지참조) 42
Fig. 4.3. Scanning electron microscope images of representative smaples. 45
Fig. 4.4. XPS survry scan spectra of LiNi0.5Mn1.5O₄ spinel type cathode material.(이미지참조) 47
Fig. 4.5. XPS narrow scan spectra of Mn 2p3 and Ni 2p3 peak in LiNi0.5Mn1.5O₄ and LiA10.1Ni0.4Mn1.5O₄.(이미지참조) 49
Fig. 4.6. XPS narrow scan spectra of Mn 2p3 and Co 2P3 peak in LiCo0.5Mn1.5O₄ and LiAl0.1Co0.4Mn1.5O₄.(이미지참조) 50
Fig. 4.7. XPS narrow scan spectra of Mn 2p3 and Cr 2p3 peak in LiCr0.5Mn1.5O₄ and LiAl0.1Cr0.4Mn1.50 O₄.(이미지참조) 51
Fig. 4.8. Discharge capacities of LiMxMn2-xO₄ in the voltage range of 3.5~5.2 V at a current density of 0.65 mA/㎠ LiNi0.5Mn1.5O₄ and LiAl0.1Ni0.4Mn1.5O₄.(이미지참조) 53
Fig. 4.9. Discharge capacities of LiMxMn2-xO₄ in the voltage range of 3.5~5.2 V at a current density of 0.65 mA/㎠ LiCo0.5Mn1.5O₄ and LiAl0.1Co0.4Mn1.5O₄.(이미지참조) 54
Fig. 4.10. Discharge capacities of LiMxMn₂-xO₄ in the voltage range of 3.5~5.2 V at a current density of 0.65 mA/㎠ LiCr0.5Mn1.5O₄ and LiAl0.1Cr0.4Mn1.5O₄.(이미지참조) 55
Fig. 4.11. Differential vs. capacity diagram of LiCo0.5Mn1.5O₄ and LiAl0.1Co0.4Mn1.5O₄.(이미지참조) 56
Fig. 4.12. Differential vs. capacity diagram of LiCr0.5Mn1.5O₄ and LiAl0.1Cr0.4Mn1.5O₄.(이미지참조) 57
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