本研究以共沉澱法結合金屬有機骨架合成出多孔奈米柱狀ZnFe2O4。燒結溫度會影響多孔結構內部的顆粒大小，而顆粒大小影響嵌入式反應的可逆性。350°C燒結所生成的多孔結構內部顆粒大小介於10到20 nm，並在0.1 C定速率充放電50圈後貢獻1273 mAh/g的可逆電容量。
摻雜用離子依電化學活性及價數分為三組，並分別以Sn2+、Mg2+、Al3+為代表。除合金化反應外，Sn2+亦以部份不可逆的氧化還原反應儲存鋰離子，而微量摻雜Sn0.05Zn0.95Fe2O4以0.1 C定速率充放電60圈後1318 mAh/g的可逆電容量，與88.6 %的電容量保留率為最佳Sn2+摻雜量。由不參與電化學反應的Mg2+取代因合金化反應體積變化較大的Zn2+，能減緩因重複體積變化使SEI不斷增厚的現象，同時避免活物不必要的損耗而穩定電性表現，其中Mg0.9Zn0.1Fe2O4以1 C定速率充放電250圈後811 mAh/g的可逆電容量，與82.1 %的電容量保留率(capacity retention rate)為最佳Mg2+摻雜量。
Al3+未成功摻雜至ZnFe2O4中，而可能是由非晶相包覆於粉末表面，因此添加Al3+後Zn2+量減少，能貢獻的電容量隨之減少，不過高充放電速率與長圈數下微幅減弱因體積變化大所導致電性衰退的現象，其中鋁摻雜量0.1的例子以250圈後429 mAh/g的可逆電容量與41.7 %電容量保留率表現最為明顯。

ZnFe2O4 and MxZn1-xFe2O4 (M=Sn, Mg and Al) were synthesized by a facile and high-yield co-precipitation method followed by thermal treatment of the metal-organic frameworks (MOFs) in air to form mesoporous structure. Temperatures of thermal treatment affected the porous structure of the material and also influenced charge/discharge process of ZnFe2O4.
From the electrochemical performance, we have found that doping Sn which is electrochemically active would raise the voltage plateau corresponding to the reaction peaks of the doping elements, and Sn0.05Zn0.95Fe2O4 demonstrated the highest capacity of 1318 mAh/g after 50 cycles at 0.1 C. In contrast, doping Mg which is electrochemically inactive would inhibit volume change and stabilize structure during lithiation-delithiation. Mg0.9Zn0.1Fe2O4 showed an excellent reversible capacity of 811 mAh/g with a capacity retention rate of 82.1% after 250 cycles at 1 C, while the pristine ZnFe2O4 only remained 382 mAh/g with a capacity retention rate of 32%. Al3+ failed to dope into the structure, instead, probably formed an amorphous layer outside the ZnFe2O4 particles. Therefore, the sample with Al doping amount equal to 0.1 showed slightly slow decay in cycle performance with a capacity retention rate of 41.7% after 250 cycles at 1 C, owing to decreased Zn whose volume change is larger, rather than increased Al.

Abstract III
摘要 IV
誌謝 V
目錄 VI
圖目錄 VIII
表目錄 XI
第一章 緒論 1
1.1 鋰離子電池產業概況 1
1.2 鋰離子電池原理 5
1.3 鋰離子電池組成 6
1.4 陽極材料 7
第二章 文獻回顧 9
2.1 尺寸奈米化 9
2.2 形貌改質 10
2.2.1 多孔結構 10
2.2.2 中空結構 12
2.3 離子取代與摻雜 14
第三章 實驗步驟 18
3.1 實驗藥品 18
3.2 多孔奈米柱狀氧化鐵鋅之製備 19
3.3 氧化鐵鋅摻雜亞錫離子/鎂離子/鋁離子之製備 20
3.4 陽極製備 20
3.5 電池組裝 21
3.6 材料分析 22
3.6.1 場發射掃式描電子顯微鏡 22
3.6.2 X光粉末繞射儀 22
3.6.3 熱重分析 22
3.6.4 循環伏安法 23
3.6.5 交流阻抗分析 23
3.6.6 電池循環壽命測試 23
3.6.7 X射線光電子能譜分析 23
第四章 結果與討論 24
4.1 共沉澱法製備ZnFe2O4之燒結溫度探討 24
4.1.1 表面形貌 25
4.1.2 電性結果 27
4.2 亞錫離子摻雜 31
4.2.1 形貌與晶格影響 31
4.2.2 電性表現影響 35
4.3 鎂離子摻雜 42
4.3.1 形貌與晶格影響 42
4.3.2 電性表現影響 46
4.4 鋁離子摻雜 54
4.4.1 形貌與晶格影響 54
4.4.2 電性表現影響 57
第五章 結論 61
第六章 參考文獻 63

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