研究目的為探討微波輔助法對磷酸鋰鐵(LFP)陰極材料表面進行銅修飾以及鋅修飾之改質效果。銅披覆與鋅披覆LFP之改質在1C電容量，分別提升30%及5%以上，在1C下50圈循環壽命試驗，庫倫效率分別維持在94%及99%。其中銅表面修飾LFP的整體電性最好，其歸因於銅在LFP表面形成Cu0與Cu2+，Cu0良好的導電性帶動電子遷移的同時也同時帶動Li+的遷移速率，亦使得充放電過程中堆積在LFP表面的Li+能夠迅速的崁入/崁出，緩解材料崩解、降低LFP表面阻抗，進而提升其電性效能。而微波能具有良好熱傳導性及質傳特性，更可大幅節省製程時間，未來亦可研擬以微波輔助法對其他陰極材料進行表面改質，增加研究速率、減少工時、提升經濟效益。

his thesis proposed an efficient microwave-assisted approach to prepare metal-coated lithium iron phosphate (LFP) cathode materials for improving electrochemical performance of Li-ion batteries. Two kinds of metallic ions, Cu and Zn, were employed as conductive layer over the surface of LFP powders through the microwave deposition method. The as-prepared LFP powders still kept their original morphology after the metallic coatings. Based on the micro-structural observation, the presence of metallic layers induces not only a decrease of interfacial resistance but also a remarkable increase of rate capability. Experimental results indicated that the Cu-coated LFP cathode displayed the maximal cell performance, i.e., the specific capacity of 146 mAh g-1 at 0.1 C and the enhanced cyclic stability of 6% capacity fading after 50 cycles. This enhanced performance could be attributed to the fact that the Cu thin layer enables the repairing of incomplete original carbon network, showing a completed electronic circuit onto the LFP powders. The Cu-coated LFP, thus, leads to faster kinetics of electrons and better reversibility of Li ions in the olivine crystals. Accordingly, the microwave-assisted approach offers a great potential in modifying cathode materials due to its short synthesis time, low-temperature operation, and energy-saving.

中文摘要 III
Abstract IV
誌謝 V
目錄 VI
圖目錄 IX
表目錄 XII
第一章 1
緒論 1
1.1研究源起及目的 1
1.2研究目的與動機 4
第二章 6
文獻回顧 6
2.1鋰離子電池簡介 6
2.1.1鋰離子電池的發展 6
2.1.2鋰離子工作原理 9
2.2鋰離子電池陰極材料 11
2.2.1 LiCoO2陰極材料 13
2.2.2 LiNiO2陰極材料 14
2.2.3 LiMn2O4陰極材料 16
2.3 LFP介紹 18
2.3.1 LFP陰極材料性能指標 21
2.4磷酸鋰鐵材料製備合成方法 23
2.4.1固相合成法 (Solid-state method) 23
2.4.2碳熱還原法(Carbon-thermal reduction method) 24
2.4.3溶膠凝膠法(Sol-gel method) 25
2.4.4水熱法(Hydrothermal method) 26
2.4.5噴霧熱解法(Spray pyrolysis method) 27
2.4.6機械合金法(Mechanical alloying method) 28
2.4.7液相共沉澱法(Co-precipitation method) 29
2.4.8微波法(Microwave heating method) 30
2.5 LFP之發展與應用 34
2.6 LFP之改質方向 36
2.6.1材料奈米化 37
2.6.2摻雜高價金屬離子 39
2.6.3材料表面改質 41
2.7儀器分析原理 45
2.7.1 X-ray粉末分析儀 45
2.7.2場發射掃描式電子顯微鏡 48
2.7.3場發射穿透式電子顯微鏡 51
2.7.4熱重分析儀 52
2.7.5化學分析電子能譜儀 53
第三章 54
實驗方法與分析 54
3.1實驗藥品 54
3.2實驗儀器裝置 55
3.3實驗流程圖 56
3.4實驗步驟 57
3.5材料鑑定分析 59
3.5.1 X-ray繞射粉末分析儀 59
3.5.2 場發射掃描式電子顯微鏡 60
3.6電化學性能分析 61
3.6.1陰極電極製備 61
3.6.2鈕扣型電池組裝 63
3.6.3定電流充放電 65
3.6.4交流阻抗分析 66
第四章 68
結果與討論 68
4.1銅披覆表面改質 68
4.1.1晶體表面分析 68
4.1.2晶體型態分析 73
4.1.3電性分析 74
4.2鋅披覆表面改質 82
4.2.1晶體表面分析 82
4.2.2晶體型態分析 84
4.2.3電性分析 85
4.3電性分析比較 89
第五章 93
結論與未來展望 93
5.1結論 93
5.2未來展望 95
參考文獻 96

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