臺灣博碩士論文加值系統

利用共沉法並進行800到1000oC的熱處理合成出層狀的Li(Ni1/3Co1/3Mn1/3)O2正極材料，並藉由XRD、SEM及循環充放電分析結果對合成粉末之特性及電化學性質進行研究。為了改善Li(Ni1/3Co1/3Mn1/3)O2正極粉末之循環充放電性，分別在共沉法合成過程中，在前驅物中添加乙炔碳黑，在過渡金屬離子溶液中添加PEG或蔗糖等改良製程進行合成Li(Ni1/3Co1/3Mn1/3)O2。以在過渡金屬離子溶液中添加1 wt%蔗糖是最為有效的改善方法。雖然在前驅物中添加乙炔碳黑能也可使晶粒細化，略為改善其循環充放電特性，但合成粉末中卻會生成CoCx雜相。而在過渡金屬離子溶液中添加PEG對Li(Ni1/3Co1/3Mn1/3)O2正極材料特性反而有負面的影響。

Layered Li(Ni1/3Co1/3Mn1/3)O2 cathode materials were prepared with co-precipitation method followed by heat-treatment at temperatures between 800 and 1000oC. The characterization and electrochemical properties of the prepared powders were studied with XRD, SEM, and capacity retention study. In order to improve the cycleability and rate capability of Li(Ni1/3Co1/3Mn1/3)O2 cathode material, amended co-precipitation methods with addition of acetylene black in precursor for heat-treatment and addition of PEG or sucrose into transition metal ion solution before co-precipitation were used to prepared Li(Ni1/3Co1/3Mn1/3)O2 powders. Among them, the co-precipitation with method sucrose added into transition metal ion solution before co-precipitation is the most effective one. Though the average particle size and cycleability can be improved by adding acetylene black in precursor for heat-treatment, CoCx phase forms in the prepared powder. The addition of PEG into the transition metal ion solution before co-precipitation shows negative effects on particle reduction and cycleability.

ABSTRACT.............................................................................................. I
摘要...........................................................................................................II
CONTENTS...........................................................................................III
TABLES LIST......................................................................................VII
FIGURES LIST..................................................................................VIII
Chapter 1 Introduction………..........…………..…..…………………. 1
Chapter 2 Literature Review...........................................................…... 3
2.1 Cathode Materials for Lithium Batteries…………………..….… 3
2.1.1 LiCoO2 cathode material……………………...........………3
2.1.2 LiNiO2 cathode material...............................................….....4
2.1.3 LiMn2O4 cathode material.............................................…... 5
2.1.4 LiMnO2 cathode material…………………….……….…....5
2.1.5 LiFePO4 cathode material…………….…….…………….. 6
2.1.6 Li-Ni-Co-Mn-O based cathode material…….…………..... 6
2.2 The properties of Li(Ni1/3Co1/3Mn1/3)O2…………………….…...7
2.3 Electrochemical Methods………………………………….…… 8
2.3.1 Potential step chronoamperomtry method, PSCA…….…. 8
2.3.2 Cyclic voltammetry, CV………………………….……… 9
2.3.3 Capacity retention study……..……………….….………10
Chapter 3 Experimental…………………………………………….... 12
3.1 Powder preparation……………………………………………. 12
3.1.1 Hydroxide co-precipitation method….……...….……… 12
3.1.2 Hydroxide co-precipitation with acetylene black added before calcined ……………………..…….………… 13
3.1.3 Hydroxide co-precipitation with PEG added before precipitation..................................................................... 13
3.1.4 Hydroxide co-precipitation with sucrose added before precipitation……………………………………………..13
3.2 Powder Characterization………………………………………. 14
3.2.1 XRD studies…………………………………………….. 14
3.2.2 Thermal analysis……………………………………....... 14
3.2.3 SEM observation…………………………………….... 15
3.2.4 Composition determination……………………………... 15
3.3 Cell Assembly Test…………………………………………….. 16
3.3.1 Electrode preparation……………….…………………… 16
3.3.2 Coin-type cell assemblage....……………………….…… 17
3.3.3 Three-electrode cell assemblage...……………………..... 17
3.4 Electrochemical Analysis……………………………………… 18
3.4.1 Capacity retention studies………………….…………… 18
3.4.2 Cyclic voltammetry………………………………….….. 18
Chapter 4 Results and Discussions………………………..………… 20
4.1 Characteristics of LiNi1/3Co1/3Mn1/3O2 Powders…………….… 20
4.1.1 Thermal analysis for LiNi1/3Co1/3Mn1/3O2 precursors….... 20
4.1.2 Composition determination……….……………………... 20
4.1.3 Crystalline structure of the prepared powders….…….…. 21
4.1.4 SEM observation………………………………….….... 22
4.1.5 Specific discharge capacity of the prepared powders....… 23
4.2 Preparation and characterization of LiNi1/3Co1/3Mn1/3O2 with 10 wt% acetylene Black added into Precursor…………... 24
4.2.1 Crystalline Structure of Prepared Powders……………… 24
4.2.2 Particle sizes and morphology of prepared powders…..... 25
4.2.3 Thermal analysis for LiNi1/3Co1/3Mn1/3O2 precursors with
adding 10 wt% acetylene black……………………. 26
4.2.4 Specific discharge capacity of the prepared powders……26
4.3 Characteristics of Li(Ni1/3Co1/3Mn1/3)O2 precursor with various
concentration of PEG and 1 wt% sucrose………………….27

4.3.1 Crystalline Structure of Prepared Powders……………… 27
4.3.2 SEM observation………………………………………...28
4.3.4 Specific Discharge Capacity of the Prepared Powders….. 28
4.4 Characteristics of Li(Ni1/3Co1/3Mn1/3)O2 precursor with various
concentration of sucrose and 1 wt% sucrose………………….29
4.4.1 Thermal analysis for various amounts of sucrose……..….29
4.4.2 Crystalline structure of prepared powders…………...……30
4.4.3 SEM observation.................................................................30
4.4.4 Surface area result of the prepared powders……………....31
4.4.5 Specific discharge capacity of the prepared powders……..32
Chapter 5 Conclusion………………………………………………… 34
Chapter 6 Reference………………………………………………….. 36

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