臺灣博碩士論文加值系統

鋰空氣電池使用鋰金屬陽極，陰極反應所需的氧氣擷取自外界空氣中，因此減少電池本身的重量，提升電池的重量能量密度，為目前理論能量密度最接近石油的替代性能源，在越來越依賴石油能源的世代，需要一個潔淨的替代性能源載體。
本研究中使用非質子型系統(aprotic system)來研究，含PTFE疏水層的碳布作為陰極基材，配合白金觸媒及1 M LiTFSI(tetaglyme)作為電解液，比較不同操作電流對電池性能的影響並進行電化學性質的檢測分析及陰極沉積物分析，首先研究PTFE疏水層不同分佈方式之影響，其中以疏水層位於鋰金屬端而白金觸媒分佈於空氣端較佳的組裝方式，在0.2 mA電流下能達到28個放電電容量2000 mAh/g-catalyst的循環且能量效率在28個循環中皆維持在64 %以上;長期放電測試，在0.2 mA電流下，放電時間為98小時，放電電容量為37886 mAh/g-catalyst，鋰金屬的利用率為24%。陰極主要放電沉積物為碳酸鋰(Li2CO3)，且放電沉積物會隨著操作時間增加而增加，其形狀大小會隨著電流的增加而變小。

Lithium-air battery is a good potential energy storage devices that uses oxidation of lithium at the anode and reduction of oxygen at the cathode. A high energy density is achieved by utilizing the oxygen in air, reducing the weight of the battery. The theoretical specific energy densities for lithium-air batteries are closest to gasoline.
This study uses the lithium-air battery aprotic system to test electrochemical performance of primary and rechargeable batteries at different operating currents. We compare the configuration of MPL coated cathode. The results suggested that the MPL adjacent to Li side and catalyst facing air side has best performance. It can achieve 28 cycles and 2000 mAh/g-catalyst+C at 0.2mA current. At the current of 0.2mA results in 98 hours in long-term discharge test, It achieves discharge capacity of 37886 mAh/g-catalyst+C. The main discharge deposits on cathode consist of Li2CO3. The discharge Li2CO3 deposits increased with operating time. The deposits shape varies with the discharge current and decreases with higher current.

目錄
指導教授推薦書
論文口試委員會審定書
致謝 iii
中文摘要 iv
Abstract v
目錄 vi
圖目錄 viii
表目錄 xiii
第一章 前言 1
第二章 文獻回顧 2
2.1 能源與儲能 2
2.2 儲能技術簡介 4
2.3 鋰空氣電池 7
2.3.1 非質子系統(aprotic electrolyte system) 10
2.3.2 水相系統(aqueous electrolyte system) 11
2.3.3 固態系統(solid electrolyte system) 12
2.3.4 混合系統(mixed aprotic/aqueous electrolyte system) 12
2.4 非質子鋰空氣電池結構 14
2.4.1空氣電極與觸媒 15
2.4.2非質子電解液 19
2.5 影響鋰空氣電池性能的因素 21
2.6 研究目標 23
第三章 實驗方法 24
3.1 實驗藥品 24
3.2 儀器與設備 25
3.3 電池各組成製備 27
3.3.1 空氣陰極製備 27
3.3.2 非質子電解液製備 27
3.4電池封裝與電池測試 28
3.5 電池陰極之分析 30
第四章 結果與討論 31
4.1 電池再現性之測試 31
4.2 電池性能分析 39
4.2.1 空氣陰極中MPL位置對循環充放電性能的影響 39
4.2.2 一次放電的電池性能 57
4.2.3 不同電流下的陰極沉積物分析 68
第五章 結論 81
參考文獻 83


圖目錄
圖 1:世界主要能源市場需求趨勢圖[1] 3
圖 2：各類電池與汽油的能量密度比較圖[22] 8
圖 3：四種不同類型之鋰空氣電池系統示意圖。(a)水相(b)非質子(c)混合(d)固態電解質[23] 9
圖 4:IBM開發的鋰空氣電池結構圖[43] 14
圖 5:鋰空氣電池充放電示意圖[44] 15
圖 6: 鈀、白金、釕、金和玻璃碳對氧還原反應曲線[62] 18
圖 7:使用等效電路擬合之Nyquist圖[89] 29
圖 8:電池功率密度分析比較[41] 30
圖 9：不同日期製作的電池充放電測試前阻抗之再現性:(a)MPL-Li片 (b) MPL-air 33
圖 10：不同日期製作的電池放電電壓曲線之再現性:(a)MPL-Li片 (b) MPL-air 35
圖 11：不同日期製作的電池功率密度曲線之再現性:(a)MPL-Li片 (b) MPL-air 37
圖 12:用0.2 mA充放電測試前交流阻抗分析圖:(a)MPL-Li片 (b) MPL-air 39
圖 13:用0.2 mA充放電測試前放電電壓和功率密度曲線圖:(a)MPL-Li片 (b) MPL-air 40
圖 14:用0.2 mA對不同MPL位置的電池循環壽命及電池放電容量分析圖: (a)MPL-Li片 (b) MPL-air 42
圖 15:用0.2 mA對不同MPL位置的電池充放電曲線圖及能量效率分析圖: (a)MPL-Li片 (b) MPL-air 43
圖 16:用0.2 mA充放電測試後交流阻抗對時間變化分析圖(左)Rb阻抗對時間變化(右)Rct阻抗對時間變化:(a)MPL-Li片 (b) MPL-air 44
圖 17:用0.2 mA充放電測試後放電電壓和功率密度曲線圖:(a)MPL-Li片 (b) MPL-air 45
圖 18:用0.1 mA充放電測試前交流阻抗分析圖:(a)MPL-Li片 (b) MPL-air 46
圖 19:用0.1 mA充放電測試前放電電壓和功率密度曲線圖:(a)MPL-Li片 (b) MPL-air 47
圖 20:用0.1 mA電池循環壽命及電池放電容量分析圖: (a)MPL-Li片 (b)MPL-air 49
圖 21:用0.1 mA對不同MPL位置的電池充放電曲線圖及能量效率分析圖: (a)MPL-Li片 (b) MPL-air 51
圖 22:用0.1 mA充放電測試後交流阻抗對時間變化分析圖(左)Rb阻抗對時間變化(右)Rct阻抗對時間變化: (a)MPL-Li片 (b) MPL-air 53
圖 23:用0.1 mA充放電測試後放電電壓和功率密度曲線圖:(a)MPL-Li片 (b) MPL-air 54
圖 24:電池陰極充放電循環測試後之顯微拉曼光譜分析:(a)近空氣端-碳布(b)近鋰片端-MPL 56
圖 25:陰極組態(a)的鋰空氣電池用0.2 mA充放電測試前之(a)交流阻抗分析圖及(b)放電電壓和功率密度曲線圖 57
圖 26:陰極組態(a)的鋰空氣電池用0.2 mA連續長期放電及充電至4.5 V分析圖 58
圖 27:陰極組態(a)的鋰空氣電池用0.2 mA長期放電測試之交流阻抗對時間變化分析圖 59
圖 28:陰極組態(a)的鋰空氣電池用0.2 mA初始長期放電86小時及回充1.5小時測試之放電電壓和功率密度曲線圖 60
圖 29:重覆測試陰極組態(a)的鋰空氣電池用0.2 mA充放電測試前之(a)交流阻抗分析圖及(b)放電電壓和功率密度曲線圖 60
圖 30:重覆測試陰極組態(a)的鋰空氣電池用0.2 mA連續長期放電及充電至4.5 V分析圖 61
圖 31:重覆測試陰極組態(a)的鋰空氣電池用0.2 mA長期放電測試之交流阻抗對時間變化分析圖 62
圖 32:重覆測試陰極組態(a)的鋰空氣電池用0.2 mA長期放電測試之放電電壓和功率密度曲線圖 63
圖 33:陰極組態(a)的鋰空氣用0.1 mA充放電測試前之(a)交流阻抗分析圖及(b)放電電壓和功率密度曲線圖 64
圖 34:陰極組態(a)的鋰空氣電池用0.1 mA連續長期放電及充電至4.5 V分析圖 65
圖 35:陰極組態(a)的鋰空氣電池用0.1 mA長期放電測試之交流阻抗對時間變化分析圖 67
圖 36:陰極組態(a)的鋰空氣電池用0.1 mA長期放電測試之放電電壓和功率密度曲線圖 67
圖 37:陰極組態(a)的鋰空氣電池測試前之(a)交流阻抗分析圖及(b)放電電壓和功率密度曲線圖: MPL-Li片 68
圖 38:陰極組態(a)的鋰空氣電池之不同電流連續放電分析圖 69
圖 39:陰極組態(a)的鋰空氣電池不同電流連續放電後之交流阻抗對時間變化分析圖 70
圖 40:陰極組態(a)的鋰空氣電池不同電流連續放電後之放電電壓和功率密度曲線圖 71
圖 41:陰極組態(a)的鋰空氣電池不同電流在不同操作時間下之連續放電分析圖:(a) 0.1 mA (b) 0.2 mA (c) 0.5 mA; (d)不同電流之電壓對放電容量圖 72
圖 42:MPL面向鋰片端而觸媒分布於空氣端之電池陰極測試前表面形貌:(a)鋰片端100倍 (b)鋰片端1000倍 (c)鋰片端5000倍 (d)有觸媒空氣端100倍 (e)空氣端1000倍 (f)空氣端5000倍 (g)無觸媒空氣端100倍 (h)無觸媒空氣端1000倍 (i)無觸媒空氣端5000倍 74
圖 43:不同電流採取放電容量1000 mAhg-1-catalyst之電池陰極空氣端測試後:(a)0.1 mA鋰片端1000倍，插圖5000倍 (b)0.2 mA鋰片端1000倍，插圖5000倍 (c)0.5 mA鋰片端1000倍，插圖5000倍 (d)0.1 mA空氣端1000倍，插圖5000倍 (e)0.2 mA空氣端1000倍，插圖5000倍 (f)0.5 mA空氣端1000倍，插圖5000倍 75
圖 44:不同電流採取放電容量5000 mAhg-1-catalyst之電池陰極鋰片端測試後:(a)0.1 mA鋰片端1000倍，插圖5000倍 (b)0.2 mA鋰片端1000倍，插圖5000倍 (c)0.5 mA鋰片端1000倍，插圖5000倍 (d)0.1 mA空氣端1000倍，插圖5000倍 (e)0.2 mA空氣端1000倍，插圖5000倍 (f)0.5 mA空氣端1000倍，插圖5000倍 77
圖 45:不同電流採取放電容量10000 mAhg-1-catalyst之電池陰極鋰片端測試後:(a)0.1 mA鋰片端1000倍，插圖5000倍 (b)0.2 mA鋰片端1000倍，插圖5000倍 (c)0.5 mA鋰片端1000倍，插圖5000倍 (d)0.1 mA空氣端1000倍，插圖5000倍 (e)0.2 mA空氣端1000倍，插圖5000倍 (f)0.5 mA空氣端1000倍，插圖5000倍 79
圖 46:不同電流採取不同放電電容量之XRD分析圖:(a) 1000 mAhg-1-catalyst (b)5000 mAhg-1-catalyst (c)10000 mAhg-1-catalyst 80
表目錄
表1：各類金屬空氣電池之特性比較[18] 7
表2:各類電解液之優缺點[81,82] 20
表 3:充放電測試前之交流阻抗和功率密度分析結果:(a)MPL-Li片 (b) MPL-air 38

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