橄欖石結構之磷酸鋰鐵材料(LiFePO4)，其能量密度高、熱穩定性好、環境友善以及低成本…等性質，是為極具應用潛力的鋰離子電池正極材料。但由於材料本質的限制，其電子導電率以及離子擴散速率皆不理想，而改善上述問題一直是鋰離子電池領域的研究重點。
本研究利用實驗室自行開發的製程可得之具獨特性的前驅物：類磷酸亞鐵，該項前驅物具有之結晶性質、元素比例，在經驗證後確定其特殊性並可以適洽的與另一項前驅物反應生成性質優良的磷酸鋰鐵材料，而合成出之奈米級磷酸鋰鐵粉末亦對於其形貌與結構進行分析，而經處裡後將磷酸鋰鐵粉末包覆碳膜，進而製備出性能卓越之電池，其在0.1 C 的定電流放電下，比電容量可達140.4 mAh/g。
實驗顯示，對於調整碳源之添加比例後，發現對於電池充放電時產生之極化現象可獲得相當大的減緩；實驗中，亦對於摻雜鈷及鋅元素了解其對於磷酸鋰鐵電池之影響，其中可以觀察到比電容值的提升以及極化現象的緩和，而摻雜鈷之電池在提升至0.2 C 的定電流放電下，比電容量仍可保有141.4 mAh/g。惟電池在快速充放電時之表現並不理想，因此關於在磷酸鋰鐵材料之表面改質上應為後續研究更須注重之要點，以求達到實用的目的。

Olivine lithium iron phosphate (LiFePO4) with the advantages of high energy density, good thermal stability, environmentally benign and low cost has been recognized as one of the most promising cathode materials candidates for rechargeable lithium ion batteries. However, because of its lattice structure, it has extremely low electronic conductivity and very low lithium-ion diffusion coefficient, which has greatly inhibited its commercial applications.
In this study, we used self-developed process to synthesize a unique precursor: quasi-iron phosphate hydrate. Its’ specificity of crystallinity and the relative elements ratio was confirmed. It was suitable for mixing with another Li precursor to synthesize LiFePO4. In order to have better conductivity, sucrose was applied as carbon source to get the LiFePO4/C composite. We also analyzed the morphology and crystallinity of the nanoscale LiFePO4/C composite powder. The battery fabricated with these composite powders has a specific capacity of 140.4 mAh/g at a 0.1 C discharge rate.
Experimental results showed that the polarization of the battery during charge and discharge can be reduced by adjusting carbon source ratio in the process. We also focused on doping modification of LiFePO4. The effect of Co–doping and Zn–doping on the electrochemical behavior of the battery was studied in detail. Doping was observed to enhance the capacity as well as the reduction of polarization. The 141.4 mAh/g battery capacity maintained up to a 0.2 C discharge rate for Co-doping. However, the high-rate charge/discharge property of the battery was not satisfactory. Further studies are needed to improve the electrochemical performance of LiFePO4.

摘要 I
Abstract II
致謝 III
目錄 IV
圖目錄 IX
表目錄 XII
第一章 緒論 13
1.1　前言 13
1.2　研究目的與動機 16
第二章 文獻回顧 18
2.1　鋰離子電池基本原理與運作概述 18
2.1.1　鋰離子電池工作原理 18
2.1.2　鋰離子電池構造概述 19
2.1.2.1　正極材料 20
2.1.2.2　負極材料 23
2.1.1.3　電解質 25
2.1.2.4　隔離膜 26
2.2　磷酸鋰鐵正極材料研究進展 26
2.2.1　磷酸鋰鐵材料結構 28
2.2.2　磷酸鋰鐵材料運作原理 29
2.2.2.1　磷酸鋰鐵材料充放電性質 29
2.2.2.2　磷酸鋰鐵中鋰離子嵌入與脫出理論 30
2.2.3　磷酸鋰鐵材料製備方法 36
2.2.3.1　固態法 36
2.2.3.2　共沉澱法 36
2.2.3.3　溶膠–凝膠法 37
2.2.3.4　水熱法 38
2.2.3.5　微波合成法 38
2.3　磷酸鋰鐵材料缺失與改質技術 39
2.3.1　磷酸鋰鐵材料研究存在問題與挑戰 39
2.3.2　磷酸鋰鐵材料改質技術 40
2.3.2.1　粒徑控制 40
2.3.2.2　表面包覆 41
2.3.2.3　形貌控制 42
2.3.2.4　摻雜 44
第三章 實驗方法與步驟 46
3.1　實驗內容 46
3.1.1　實驗藥品 47
3.1.2　實驗儀器 48
3.1.2.1　離心機 48
3.1.2.2　球磨機 48
3.1.2.3　熱處理管爐 48
3.1.2.4　真空烘箱 48
3.1.2.5　手套箱 48
3.2　磷酸鋰鐵粉末製備 49
3.2.1　前驅物製備 49
3.2.1.1　磷酸亞鐵製備 49
3.2.1.2　磷酸鋰製備 49
3.2.1.3　不同摻雜源之前驅物製備 49
3.2.2　球磨混和與表面處理 50
3.2.3　熱處理 50
3.3　磷酸鋰鐵電池製備 50
3.3.1　正極極片製備 50
3.3.1.1　漿料混和與塗佈 50
3.3.1.2　極片裁切與後處裡 51
3.3.2　CR2032硬幣型電池壓製 51
3.4　材料分析方法與儀器介紹 53
3.4.1　X-ray 繞射分析儀 53
3.4.2　感應耦合電漿質譜分析儀 53
3.4.3　掃描式電子顯微鏡 54
3.4.4　穿透式電子顯微鏡 55
3.4.5　拉曼光譜儀 56
3.4.6　電池充放電測試系統 56
第四章 結果與討論 57
4.1 標準製程 57
4.1.1 磷酸亞鐵前驅物分析 57
4.1.2 磷酸鋰前驅物分析 62
4.1.3 磷酸鋰鐵材料分析 64
4.1.4 添加碳源量製備之磷酸鋰鐵 70
4.1.5 磷酸鋰鐵材料碳包覆分析 72
4.2 鋰離子電池測試 75
4.3 含不同摻雜源之製程 80
4.3.1 不同摻雜源之磷酸亞鐵前驅物分析 81
4.3.2 不同摻雜源製程之磷酸鋰鐵材料分析 85
4.4 不同摻雜源之磷酸鋰鐵電池測試 91
4.5 電池製備之影響 97
第五章 結論 98
參考文獻 99

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