本研究以多元醇回流法合成花瓣狀的纖薄LiFePO4前驅物，並以二茂鐵輔助蔗糖碳源進行包碳，於750~850℃的熱處理條件下製備LFP/fC陰極材料，以研究LFP/fC系統中，不同熱處理溫度對粉末的結晶性、粉末形貌、尺寸，以及碳膜石墨化程度的影響，並透過電池測試觀察其電化學表現。研究發現以750℃熱處理之LFP/fC陰極材料的粉末顆粒尺寸較小（定義詳第4.3.2節），且擁有較高之163.5 mAh/g的比電容。
LFP/fC陰極材料中，Fe2P導電相的含量可藉由改變熱處理之氣體流量及溫度調整。實驗結果顯示若熱處理溫度高於850℃且氣體流量較大時，便有機會生成Fe2P導電相。在850℃熱處理溫度下，氣體流量低至30 sccm時即不會生成Fe2P相。然而，於30 sccm之氣體流量下，當熱處理溫度高至900℃時便會導致Fe2P相的生成。
最後，我們藉由較低熱處理溫度製備粉末顆粒尺寸較小的LFP/fC陰極材料，再加熱至900℃以引入微量Fe2P導電相，藉以提升材料的電化學表現，於0.1 C放電時具有較高的3.32 V工作電壓，且當充放電速率由0.1 C提升至1 C時，其工作電壓衰減率較低，僅10.3%。但其比電容卻低於LFP/fC-750陰極材料。

In this work, polyol reflux method was applied to synthesize petal-like LiFePO4 precursors with 10 nm thickness. With the assistance of ferrocene catalyst, the precursours were mixed with sucrose, followed by sintering at various temperatures from 750~850℃ to obtain LFP/fC in order to study effects of annealing temperature on powders crystallinity, morphology, sizes as well as graphitization degree of carbon coating. Cell testing was also used to investigate their electrochemical performance. It showed that the LFP/fC annealed at 750℃ have smaller particle sizes and exhibit the highest discharge capacity 163.5 mAh/g at 0.1 C.
According to our investigation, the concentration of conductive Fe2P phase in LFP/fC can be controlled through adjusting the gas flow and the sintering temperatures during heat treatments. Fe2P phase may form if a sintering temperature higher than 850°C combined with a higher flow rate were applied. At 850℃, Fe2P was found exclusively if the flow rate was as low as 30 sccm. While Fe2P can still be observed in the sample heated at 900°C even with the low flow rate 30 sccm.
Finally, we promoted the electrochemical performance of LFP/fC cathode material by reducing grain sizes (Definition refers to chapter 4.3.2) with a lower sintering temperature, and introducing a slight amount of Fe2P by heating up to 900°C afterwards. The material delivers high operating voltage of 3.32 V at 0.1 C rate and demonstrates a lower voltage fading rate of 10.33% when the cycling rate raised from 0.1 C to 1 C. However, it was unable to reach the discharge capacity of LFP/fC-750 cathode material.

摘要 I
ABSTRACT II
致謝 III
目錄 IV
圖目錄 VIII
表目錄 X
第一章 緒論 1
第二章 文獻回顧 4
2.1 鋰離子電池之構造及其原理： 4
2.2 陽極材料 5
2.2.1 鋰金屬陽極材料 5
2.2.2 碳材陽極材料 6
2.2.3 陽極材料的改質 7
2.3電解質 8
2.4 隔離膜 9
2.5 陰極材料： 10
2.5.1 層狀結構之陰極材料 11
2.5.1.1 層狀結構之LiCoO2 11
2.5.1.2 層狀結構之LiNiO2 13
2.5.2 尖晶石結構之LiMn2O4 13
2.5.3 橄欖石結構之LiFePO4 14
2.6 LFP陰極材料的合成方法 19
2.6.1 固態反應法(Solid-State synthesis) 19
2.6.2 共沉澱法(Co-precipitation) 20
2.6.3 溶膠凝膠法(Sol-Gel synthesis) 21
2.6.4 水熱法(Hydrothermal synthesis) 22
2.6.5 溶劑熱法(Solvothermal synthesis) 23
2.6.6 多元醇回流法(Polyol Reflux method) 23
2.6.7 各合成方法流程簡圖 25
2.7 LFP陰極材料的改質 26
2.7.1 摻雜高價金屬離子(Supervalent ions doping) 26
2.7.2 包覆導電碳膜(Carbon Coating) 28
2.7.2.1 二茂鐵簡介 31
2.7.3 縮小晶粒尺寸(Size Reduction) 33
2.7.4 引入導電相Fe2P 34
2.8 研究動機與目的 37
第三章 實驗方法與步驟 39
3.1 實驗藥品 39
3.2 實驗用儀器 40
3.3 多元醇迴流法合成LFP前驅物 41
3.3.1 前置步驟 41
3.3.2 合成暨粉末收集實驗步驟 41
3.4 包覆導電碳膜 42
3.4.1 以蔗糖作為碳源進行包碳 42
3.4.2 以二茂鐵輔助蔗糖碳源進行包碳 42
3.5 電池製作 42
3.5.1 陰極極片製作 42
3.5.2 鈕扣電池組裝 43
3.6 電池充放電測試 44
3.7 實驗用儀器介紹 45
3.7.1 X-射線繞射分析儀 45
3.7.2 場發射掃描式電子顯微鏡 45
3.7.3 場發射掃描穿透式球差修正電子顯微鏡 46
3.7.4 感應耦合電漿放射光譜儀 47
3.7.5 拉曼光譜儀 48
3.8 實驗流程圖 49
第四章 結果與討論 50
4.1改變定氣流熱處理參數以控制Fe2P相的生成 51
4.1.1改變定氣流熱處理之氣體流量以控制Fe2P相的生成 51
4.1.1.1改變熱處理氣體流量以控制LFP/C中Fe2P相的生成 52
4.1.1.2 改變熱處理氣體流量及種類以控制LFP/fC中Fe2P相的生成 53
4.1.2 改變定氣流熱處理溫度以控制Fe2P相的生成 54
4.2 Fe2P相對於LFP/fC陰極材料的影響 55
4.2.1 XRD繞射分析 55
4.2.2 SEM分析 57
4.2.3 拉曼分析 60
4.2.4 TEM分析 63
4.2.5 電池充放電測試與分析 67
4.2.5.1 LFP/fC-850F電池充放電測試 67
4.2.5.2 LFP/fC-850電池充放電測試 70
4.2.5.3 LFP/fC-850F與LFP/fC-850充放電分析 73
4.3 降低LFP/fC熱處理溫度產生的影響 76
4.3.1 XRD繞射分析 77
4.3.2 SEM分析 78
4.3.3 拉曼分析 81
4.3.4 電池充放電測試與分析 84
4.3.4.1 LFP/fC-750電池充放電測試 84
4.3.4.2 LFP/fC-800電池充放電測試 87
4.3.4.3 LFP/fC-750、LFP/fC-800與LFP/fC-850充放電分析 90
4.4 縮小LFP/fC粉末顆粒尺寸並引入微量Fe2P相 95
4.4.1 XRD繞射分析 96
4.4.2 SEM分析 97
4.4.3 拉曼分析 101
4.4.4 電池充放電測試與分析 104
4.4.4.1 LFP/fC-800-900F電池充放電測試與分析 104
4.4.4.2 LFP/fC-850-900F電池充放電測試與分析 107
4.4.4.3 LFP/fC-800-900F與LFP/fC-850-900F充放電分析 110
第五章 結論 115
參考文獻 116

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