臺灣博碩士論文加值系統

本研究以合成低成本之LiFePO4(LFP)及高能量密度之LiMn0.5Fe0.5PO4(LMFP)為目的。
以碳熱還原法作為低成本之合成方法，選用工業級Li2CO3和FePO4做為前驅物，並以不同含量之葡萄糖做為還原劑及碳源。藉此探討碳熱還原法之反應過程及碳含量最適化。同時以共沉澱法合成LMFP前驅物(Mn0.5Fe0.5)¬¬¬3(PO4)2 (MFP)，利用Mn原子取代橄欖石結構中部分Fe原子，藉此提高材料之能量密度。並藉由TGA、DSC、XRD、SEM及HR-TEM分析反應過程及材料鑑定。
根據研究結果，於氮氣氣氛下240℃恆溫四小時和650℃恆溫十五小時為本研究之較佳煅燒參數，此參數下0.1C充放電速率下電容量達118 mAh g-1，以1C速率下進行三十次充放電循環壽命測試庫倫效率仍然維持99.9 %以上且電容量保持率於5C下可達60%，此結果顯示材料除了擁有良好的晶體結構外也因於材料表面上披覆一層碳層，提供了一個良好的電子傳導路徑以及降低材料之極化現象。
在合成LMFP中，利用共沉澱法可合成具圓球狀之前驅物MFP，並且成功合成出LMFP。此合成方法於0.05C速率下電容量達113 mAh g-1，並且以1C速率下進行三十次充放電循環壽命測試庫倫效率仍然維持99.9 %以上顯示材料之穩定性，經由Ragone plots圖可證明LMFP於能量密度上高於LFP。

Recently, there has been considerable interest in preparing olivine LiMPO4 (M= Mn, Fe, Co, and Ni) as a cathode material for high-power and large-scale applications such as electric vehicles. This study focuses on the carbonthermal reduction method was first employed to prepare LiFePO4/C (LFP/C) cathode materials. The results demonstrated that the optimal calcination process for the synthesis of LFP/C composite material was set at 240°C for 4 h and 600°C for 15 h in N2 atmosphere with the addition of 18.9 wt.% glucose as carbon sources. The as-synthesized LFP/C, having a highly crystalline level, displays high specific capacity of 118 mAh g-1 at 0.1 C and good stability with almost no capacity fading after 30 cycles. The presence of carbon coating significantly is beneficial for rate capability (capacity retention: 60 % at 5C/0.1C) and high Coulombic efficiency (> 99.9%), showing excellent reversibility of insertion/de-insertion of Li ions. This can be ascribed to the fact that well dispersed carbon layer offers an electronic pathway over the LFP/C composite, thus imparting electronic conduction and reducing cell polarization. Accordingly, the deposition of carbon coating, prepared by the carbothermal reduction method, shows a positive effect on the rate-capability improvement of LFP/C cathodes.
As to the second part, one precursor, (Mn0.5Fe0.5)3(PO4)2 (MFP), was prepared by using ammonia as chelating agent and pH adjuster. The as-prepared LMFP was mixing the pre-calcined MFP with Li3PO4, followed by high-temperature calcination. A uniform carbon coating layers was found to coat over the surface of the spherical LMFP. The as-prepared LMFP cathode also exhibited excellent Li-storage performance and outstanding cycleability at 1 C (> 90%). The Ragone plot showed that the LMFP cathode is capable of retaining its higher energy-storage ability at high power density than commercial LFP.

目錄
中文摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VIII
表目錄 XII
第一章 1
緒論 1
1.1 前言 1
1.2 研究目的與動機 3
第二章 4
文獻回顧 4
2.1 鋰離子電池發展及簡介 4
2.2 鋰離子工作原理 7
2.2.1 鋰離子電池陰極材料 8
2.2.2 磷酸鐵鋰陰極材料性能指標 14
2.3 磷酸鐵鋰之介紹 16
2.4 磷酸鐵鋰之結構 17
2.5 磷酸鐵鋰之充放電模型 19
2.6 磷酸鐵鋰之合成方法 22
2.6.1 高溫固相合成法 23
2.6.2 碳熱還原法 25
2.6.3 水熱合成法 26
2.6.4 溶膠凝膠合成法 27
2.7 磷酸鐵鋰發展現況 29
2.8 磷酸鐵鋰未來發展方向 46
儀器分析原理 47
2.9.1 X-ray粉末分析儀 47
2.9.2 場發射掃描式電子顯微鏡 49
2.9.3 場發射穿透式電子顯微鏡 52
2.9.4 元素分析儀 53
2.9.5 熱重分析儀 54
2.9.6 微差掃描熱卡計 56
第三章 58
實驗方法與分析 58
3.1 實驗藥品 58
3.2 實驗儀器裝置 60
3.3 實驗架構 61
3.4 實驗步驟 62
3.5 材料鑑定分析 66
3.5.1 X-ray繞射粉末分析儀 66
3.5.2 場發射掃描式電子顯微鏡 67
3.5.3 場發射穿透式電子顯微鏡 68
3.5.4 熱重分析儀 69
3.5.5 元素分析儀 70
3.5.6 微差掃描熱卡計 71
3.6 電化學性能分析 72
3.6.1 陰極電極製備 72
3.6.2 鈕釦型電池組裝 74
3.6.3 定電流充放電 76
3.6.4 循環伏安法測試 77
第四章 78
結果與討論 78
4.1 前言 78
4.2 碳熱還原法合成LFP/C之分析及探討 79
4.2.1 LFP/C之製程探討 79
4.2.2 LFP/C之添加碳含量與披覆之碳含量探討 83
4.2.3 不同碳含量之LFP/C材料結構分析 85
4.2.4 不同碳含量之LFP/C表面形態之分析 89
4.2.5 不同碳含量之LFP/C表面形態之電池性能分析 91
4.3 商業化LFP之性能與結構分析 95
4.3.1 商業化LFP之材料結構分析 96
4.3.2 商業化LFP之表面型態分析 98
4.3.3 商業化LFP之電池性能分析 101
4.4 改善製程後之LFP/C之分析及探討 103
4.4.1 改善製程後之LFP/C之材料結構分析 103
4.4.2 改善製程後之LFP/C之表面形態分析 107
4.4.3 改善製程後之LFP/C之電池性能分析 108
4.5 合成LMFP之分析及探討 112
4.5.1 前驅物MFP之合成與結構分析 112
4.5.2 前驅物MFP之表面型態分析 116
4.5.3 LMFP之合成與結構分析 118
4.5.4 LMFP之表面型態分析 122
4.5.5 LMFP之循環伏安分析 124
4.5.6 LMFP之電池性能分析 126
第五章 132
結論與未來展望 132
5.1 結論 132
5.2 未來展望 134
參考文獻 135

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