臺灣博碩士論文加值系統

本論文以乳膠法合成鋰離子二次電池的陰極材料-LiCoO2。並以固相法探討LiCoO2粉體合成的反應模型與求解反應的活化能。另外，改變Li/Co的計量比以合成Li(LixCo1-x)O2單相粉體，探討合成粉體的結構並粉體型態，以了解電池的電性表現與結構間的關係。
單相的LiCoO2可藉由乳膠的製程經900℃急冷不須持溫煆燒合成，證明乳膠法的製程可增加先驅粉體的反應活性，粉體粒徑約0.2~0.3μm，小於以固相法合成之商業化粉體。於3.0~4.2V間的第一次放電電容量為130.1 mAh/g，經五次循環後放電容量僅衰退5%。
乳膠製備先驅粉體經700℃以上煆燒1小時可合成單相的LiCoO2。粉體的結晶性、粒徑大小、結晶子大小(crystallite)隨煆燒溫度的增加而提高。800℃煆燒1小時的粉體為平均粒徑1.464μm的單顆粒。粉體的成長是由大小約80~100 nm的片狀結晶子聚集之後而致。高溫度煆燒的試樣，其充、放電電容量高且效率佳。經10次循環充放電之後仍保有90%的電容量，充放電效率則達0.95以上。
反應動力方面，以Li2CO3、Co3O4為先驅物來合成LiCoO2層狀氧化物。採微分法、積分法並用的優點，決定擴散控制過程為反應控制步驟，並解得反應活化能為163.62 KJ/mole。
以不同Li2CO3與Co3O4計量比合成單相鋰鈷氧時，惟有Li/Co大於1時，可合成單相的Li(LixCo1-x)O2。先驅粉體Li/Co計量比越高，合成粉體的I(104)/I(003)比值大，表示過多的Li離子佔據結構中的Co層位置。同時，LiCoO2的c軸因Co氧化數的增加而變小，並具較大的粒徑。發現Li/Co的計量比高的試樣，第一次放電電容量最大，達146.34 mAh/g，但經30次循環充放電之後，因結構不穩定，電容量衰退最嚴重，僅剩原來的64.83%。

Cathode materials, LiCoO2 was synthesized through the emulsion process. The single phase Li(LixCo1-x)O2 powders were formed when Li/Co≧1. In order to research the relationship between structure and electrochemical properties, the morphology and distribution of cations in the structure of LiCoO2 are also discussed.
In the emulsion process, the single phase of LiCoO2 powders was prepared by quenching at 900℃without calcination. The diameter of particles are 0.2~0.3μm. In the first cycle of discharge, the capacity of the battery attains 130.1 mAh/g from 3.0 to 4.2V. After 5 cycles, the fading ratio is only 5%. LiCoO2 powders were also synthesized by calcining at 700℃. With an increase in temperature, the crystalline size and the diameter of particles are increased. They are 167 nm and 1.5μm at 800℃ respectively. Well-crystallized powders have better capacity and efficiency.
In the analysis of kinetics of reaction, Li2CO3 and Co3O4 were used as starting materials. Through integral and differential methods, the mechanism of the reaction was decided. In this reaction, the rate determinate step is the diffusion of Li2CO3 through LiCoO2. The activated energy of this reaction is calculated to be 163.62 KJ/mole.
When the Li to Co ratio is larger than 1, the Li(LixCo1-x)O2 single phase is formed. Increasing the Li/Co ratio results in an increase in lattice constant c, and an increase in particles size. In addition, the high Li/Co ratio results in the high capacity of the first cycle.

摘要 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ Ⅰ
英文摘要 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ Ⅱ
目次 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ Ⅲ
圖表說明 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ Ⅵ
第一章 緒論 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 1
1-1 前言 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 1
1-2 二次鋰電池的工作原理及發展趨勢 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 2
1-2-1 工作原理 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 2
1-2-2 發展趨勢 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 3
1-3 鋰離子二次電池之陰極材料簡介 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 4
1-3-1 LiCoO2 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 4
1-3-2 LiNiO2 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 5
1-3-3 LiMn2O4 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 6
1-3-4 其他陰極材料 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 8
1-4 LiCoO2的文獻回顧 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 9
1-4-1 晶相合成、結構探討與電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 9
1-4-2 合成方法 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 10
1-4-3 理論計算 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 11
1-4-4 LiCoO2電性改良 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 13
1-5 乳膠法簡介 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 15
1-6 動力分析的理論推導 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 16
1-6-1 理論推導 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 16
1-6-2 反應動力模型簡介 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 19
1-7 研究目的 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 20
第二章 研究步驟與實驗方法 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 36
2-1 LiCoO2乳膠法合成 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 36
2-2 LiCoO2固相法合成 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 37
2-2-1 LiCoO2固相反應機制與動力分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 37
2-2-2 不同Li/Co計量比的粉體合成 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 37
2-3 LiCoO2電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 38
第三章 LiCoO2的乳膠法合成與電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 39
3-1 乳膠法急冷合成LiCoO2及反應機制與電性分析 ﹍﹍﹍﹍﹍﹍﹍ 39
3-1-1 LiCoO2合成及反應機制 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 39
3-1-2 微結構 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 42
3-1-3 電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 42
3-2 乳膠法煆燒合成LiCoO2與電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 44
3-2-1 LiCoO2的煆燒與微結構 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 44
3-2-2 煆燒LiCoO2細微結構與晶相探討 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 45
3-3 煆燒合成LiCoO2之電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 47
3-4 結論 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 50
第四章 LiCoO2的生成反應動力 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 66
4-1 LiCoO2之固相反應機制 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 66
4-1-1 熱分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 66
4-1-2 反應溫度區段的選擇 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 66
4-2 以微分法判斷反應模型 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 69
4-2-1 轉化率的計算 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 69
4-2-2 模型的選擇 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 70
4-3 以積分法計算反應動力參數 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 72
4-4 結論 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 75
第五章 不同Li/Co計量比的粉體合成與電性分析 ﹍﹍﹍﹍﹍﹍﹍ 88
5-1 不同Li/Co計量比的粉體合成 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 88
5-1-1 單相合成與微結構 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 88
5-1-2 不同Li/Co之單相結構的探討 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 89
5-2 不同Li/Co計量比粉體的電性分析 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 91
5-2-1 定電流之充放電特性 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 91
5-3 結論 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 95
第六章 結論 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 111
參考文獻 ﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍﹍ 113

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