鋰離子電池因為具有高能量密度、大電流輸出以及循環壽命長等優點，在現今已被廣泛應用在許多儲能設備及系統上，並且大大提升了科技的發展。而有機材料所形成之電極在近期吸引相當多的關注，其擁有低重量、低毒性、低成本等優點。然而，需要解決的是有機材料在電解液中的高溶解度，因此將有機單體合成聚合物以降低溶解度來維持電池之效率。
    利用具有氧化還原活性之醌類似物做為配位聚合物的建構組元。因此我們設計了1,4-二氰基-2,3,5,6-四羥基苯 (LH4)做為有機配位基，再與銅二價離子、鈷二價離子以及鋅二價離子配位形成線性配位聚合物，抑或是三維的金屬有機骨架。此些金屬有機材料被做為鋰離子電池之陰極，並具有高循環壽命及可逆之充放電表現。

Lithium-ion batteries (LIBs) have been employed in a wide range of energy-storage applications and they also improve the technological development greatly. They have been used in our daily life because of their high energy density, large output current, and long cycle life. Organic electrode materials, which feature lightweight, low cost, and low environmental impact, are attracting more and more attention. However, the high solubility of organic compounds in electrolytes is a significant issue to be solved. It is an operative strategy to polymerize redox-active monomers to decrease the solubility and maintain the high capacity of organic electrodes.
  Hydroquinone derivatives may be used as building blocks for coordination polymers to perform multielectron-transfer processes. Herein, we synthesized a quinone-based ligand 1,4-dicyano-2,3,5,6-tetrahydroxybenzene (LH4) which was used to connected to copper(II), cobalt(II) and zinc(II) to form one-dimensional coordination polymers (CPs) or metal-organic frameworks (MOFs). These materials were employed as cathode for LIBs and the results displayed high cycling stability and reversible charge-discharge behaviors.

目錄
第一章 緒論	1
1.1 配位聚合物簡介	1
1.2 鋰離子電池的簡介	4
1.3 研究動機	5
1.4 合成策略	6
第二章 實驗儀器與藥品	8
2.1 核磁共振光譜儀（Nuclear Magnetic Resonance Spectrometer）：	8
2.2 粉末繞射儀（Powder X-ray Diffractometer）：	8
2.3 單晶繞射儀（Single-Crystal X-ray Diffractometer）：	8
2.4 傅立葉紅外線光譜儀（Fourier-Transform Infrared Spectrometer）：	9
2.5 熱重分析儀（Thermogravimetric Analyzer）：	9
2.6 循環伏安儀（Cyclic Voltammeter）：	9
2.7 質譜儀（Mass Spectrometer）：	9
2.8 溶劑及藥品	10
第三章 實驗步驟	12
3.1 有機配位基的製備	12
3.2 配位聚合物的製備	14
[CuL(DMF)2]n	14
[CuL(Py)2]n	14
[Co2L2(Py)4]n	15
Zn+LH4+Pyridine	15
3.3 金屬有機骨架的製備	16
[Cu4L3]n	16
[Cu5L3(iq)3]n	16
第四章 結果與討論	17
4.1 養晶條件	17
4.1.1 [CuL(DMF)2]n	17
4.1.2 [CuL(Py)2]n	19
4.1.3 [Co2L2(Py)4]n	22
4.1.4 Zn+LH4+Pyridine	24
4.1.5 [Cu4L3]n	26
4.1.6 [Cu5L3(iq)3]n	29
4.2 結構分析	31
4.2.1 [CuL(DMF)2]n	31
4.2.2 [CuL(Py)2]n	39
4.2.3 [Co2L2(Py)4]n	43
4.2.4 Zn+LH4+Pyridine	47
4.2.5 [Cu4L3]n	51
4.2.6 [Cu5L3(iq)3]n	56
4.3 電化學測試	61
4.3.1 有機配位基－LH4	61
4.3.2 [CuL(DMF)2]n	63
4.3.3 [CuL(Py)2]n	66
結論	68
參考文獻	69
附錄	72

圖目錄
圖 1 對苯二酚／1,4－苯醌氧化還原反應	7
圖 2 1,4-dicyano-2,3,5,6-tetrahydroxybenzene, LH4結構式	7
圖 3 [CuL(DMF)2]n結構	32
圖 4 CuL(DMF)2]n層與層之間緊密排列且無溶劑分子	32
圖 5 C≣N…π（橘線）以及C≣N…H（綠線）弱交互作用力	33
圖 6 產物之粉末繞射訊號與電腦計算不符	33
圖 7 [CuL(DMF)2]n在液氮溫度及常溫狀況下單元晶格的長度、角度不同，造成彼此之間粉末繞射圖不同	34
圖 8 將產物置於液氮溫度下即可與電腦計算相符	35
圖 9 [CuL(DMF)2]n浸置於不同溶劑中1天的穩定度測試	35
圖 10 [CuL(DMF)2]n紅外線光譜	36
圖 11 [CuL(DMF)2]n熱重分析	37
圖 12 LH4與[CuL(DMF)2]n之溶解度比較a	38
圖 13 [CuL(Py)2]n結構	39
圖 14 產物之粉末繞射訊號與電腦計算相符	40
圖 15 [CuL(Py)2]n浸置於不同溶劑中1天的穩定度測試	40
圖 16 [CuL(Py)2]n紅外線光譜	41
圖 17 [CuL(Py)2]n熱重分析	42
圖 18 [Co2L2(Py)4]n結構	43
圖 19 [Co2L2(Py)4]n為一維線性結構	44
圖 20 產物之粉末繞射圖與電腦計算相符	44
圖 21 浸置於乙醇中1天的穩定度測試	45
圖 22 [Co2L2(Py)4]n紅外線光譜	45
圖 23 [Co2L2(Py)4]n熱重分析	46
圖 24 以粉末繞射圖證明Zn+LH4+Pyridine非金屬鹽類或配位基再結晶	47
圖 25 以紅外線光譜證明Zn+LH4+Pyridine中確實含有LH4	48
圖 26 以氫譜證明Zn+LH4+Pyridine中確實含有吡啶	48
圖 27 Zn+LH4+Pyridine浸置於不同溶劑中1天的穩定度測試	49
圖 28 Zn+LH4+Pyridine熱重分析	50
圖 29 [Cu4L3]n結構	51
圖 30 一價銅由兩個氰基及C─O－、C＝O嵌合	52
圖 31 三價銅由三對C─O－、C＝O嵌合	52
圖 32 產物之粉末繞射訊號與電腦計算相符	53
圖 33 [Cu4L3]n浸置於不同溶劑中1天的穩定度測試	53
圖 34 [Cu4L3]n紅外線光譜	54
圖 35 [Cu4L3]n熱重分析	55
圖 36 [Cu5L3(iq)3]n結構	56
圖 37 孔洞中嵌入了Cu(iq)3	57
圖 38 Cu(iq)3結構	57
圖 39 產物之粉末繞射訊號與電腦計算相符	58
圖 40 [Cu5L3(iq)3]n浸置於不同溶劑中1天的穩定度測試	58
圖 41 [Cu5L3(iq)3]n紅外線光譜	59
圖 42 [Cu5L3(iq)3]n熱重分析	60
圖 43 LH4之充放電測試a	61
圖 44 LH4之電容壽命測試a	62
圖 45 [CuL(DMF)2]n充放電測試a	64
圖 46 [CuL(DMF)2]n固態循環伏安測試a	64
圖 47 [CuL(DMF)2]n之電容壽命測試a	65
圖 48 [CuL(Py)2]n充放電測試a	66
圖 49 [CuL(Py)2]n之電容壽命測試a	67
圖 50 [CuL(Py)2]n之電容壽命測試a	67

表目錄
表1 [CuL(DMF)2]n單晶最佳化條件a	17
表2 [CuL(DMF)2]n大量化最佳條件	18
表3 [CuL(Py)2]n單晶最佳化條件a	19
表4 [CuL(Py)2]n大量化最佳條件	21
表5 [CoL(Py)2]n單晶最佳化條件a	22
表6 [ZnL(Py)2]n單晶最佳化條件a	24
表7 Cu4L3單晶最佳化條件a	26
表8 Cu4L3大量化最佳條件	27
表9 [CuL(iq)2]n單晶最佳化條件a	29
表10 [CuL(DMF)2]n在液氮溫度及常溫狀況下單元晶格不同	34

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