鋰離子混合式電容器搭配 LiTi1.5Zr0.5(PO4)3 LTZP或 LiSn2(PO4)3 LSP負極

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研究生：	彭建儒 Chien-ju Peng
論文名稱：	鋰離子混合式電容器搭配 LiTi1.5Zr0.5(PO4)3 LTZP或 LiSn2(PO4)3 LSP負極 Lithium ion hybrid capacitors equipped with LiTi1.5Zr0.5(PO4)3 LTZP or LiSn2(PO4)3 LSP negative electrode
指導教授：	蔡大翔 Dah-shyang Tsai
口試委員:	周振嘉 Chen-chia Chou 吳溪煌 She-huang Wu
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	143
中文關鍵詞：	混合式電容器、平行板電容器、鋰嵌入嵌出、負極材料、磷酸鋰鈦鋯、磷酸鋰錫、能量密度、鋰化程序、庫倫效率
外文關鍵詞：	Hybrid capacitor, Parallel-plate capacitors, Lithium intercalation/deintercalation, Negative electrode materials, Lithium titanium zicronium phosphate, Lithium tin phosphate, Energy density, Lithiation, Coulombic efficiency
相關次數：	點閱：320 下載：3
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上一筆

鋰離子混合式電容器為一種新型儲能元件，結合電池的高能量密度與電容器的高功率密度為其特色。本研究中，我們使用鋰離子混合式平行板電容器，搭配鋰嵌入負極及用於超高電容器的活性碳當正極材料。選用兩種負極材料，LiTi1.5Zr0.5(PO4)3 LTZP和LiSn2(PO4)3 LSP進行研究。透過X光繞射(XRD)、掃描式電子顯微鏡(SEM)、氣體吸附法(BET)量測電極材料之晶體結構、表面構形以及表面積。使用循環伏安法(CV)、恆電流充放電、循環壽命測試和電化學交流阻抗(EIS)測量單電極及電容器的電化學性質。
LTZP/AC(1:1)混合式電容器的放電曲線隨時間呈現指數型下降，在電位窗口3.4 V，放電得到能量密度46.7 Wh kg-1及功率密度80.3 W kg-1。當電流密度為0.07 A g-1時，得到極高的電容量，> 200 F g-1，而庫倫效率也高達90 %以上。
另一方面，LSP/AC(1:1.0)混合式電容器的放電曲線於高電壓範圍呈現駝背的特徵。在電位窗口3.6 V，搭載鋰化程度低的LSP電容器可以輸出能量密度23.2 Wh kg-1及功率密度41.7 W kg-1。而搭載鋰化程度高的LSP電容器，則能夠釋出更多的能量，能量密度達到28.7 Wh kg-1於功率密度37.9 W kg-1。但是循環測試中，鋰化程度較高的LSP電容器受鋰與錫金屬的電化學反應影響，庫倫效率僅70 %。

Lithium ion hybrid capacitor (LIHC) is a new type of energy storage device, featured with battery-like high energy density and capacitor-like high power density. In this study, we investigate the LIHCs of parallel-plate configuration, equipped with a negative electrode of lithium intercalation and a positive electrode of active carbon for regular ultracapacitor. Two negative electrodes are employed, one contains LiTi1.5Zr0.5 (PO4)3 LTZP and the other contains LiSn2(PO4)3 LSP. Crystal structure, morphology, and surface area of the electrode are examined with X-ray diffraction (XRD), scanning electron microscopy (SEM) and gas adsorption spectroscopy (BET). The electrochemical properties of single electrodes and capacitors are measured using cyclic voltammetry (CV), galvanostatic charge/ discharge, cycle life test, and electrochemical impedance spectroscopy (EIS).
Discharge of the hybrid capacitor of LTZP/AC(1:1) displays an exponentially decaying voltage with respect to time. In the potential window 3.4 V, this capacitor discharges with energy density 46.7 Wh kg-1 and power density 80.3 W kg-1. At current density 0.07 A g-1, the capacitance value is high, > 200 F g-1, so is coulombic efficiency, above 90%.
On the other hand, discharge of the LSP/AC(1:1.0) hybrid capacitor displays a decaying voltage curve with hunchbacked character in the high voltage region. In the potential window 3.6 V, this capacitor discharges with energy density 23.2 Wh kg-1 and power density 41.7 W kg-1 if the degree of lithiation is low in LSP. This capacitor is capable of discharging more energy, if the degree of lithiation is higher in LSP. The energy density reaches 28.7 Wh kg-1, with power density 37.9 W kg-1. But the capacitor of high lithiation in LSP also has a low coulombic efficiency  70 % in cycle life test due to the electrochemical reaction between lithium and tin metals.

摘要	I
ABSTRACT	III
目錄	V
圖目錄	X
表目錄	XVIII
第一章	序論	1
1	前言	1
2	研究動機	2
第二章	文獻回顧與理論基礎	3
1	電化學電容器(Electrochemical capacitors, EC)	3
2	電雙層電容器(Electrochemical Double-layer Capacitors, EDLC)	5
3	鋰離子混合式電容器 (Lithium-ion hybrid capacitors, LIHC)	7
3.1	鋰離子混合式電容器正極材料	8
3.2	鋰離子混合式電容器負極材料	9
3.3	鋰離子混合式電容器電解液[7]	15
第三章	實驗方法與步驟	17
1	實驗藥品耗材與儀器設備	17
1.1	實驗藥品及耗材	17
1.2	分析儀器	22
2	實驗流程	22
2.1	正極漿料製備	22
2.2	負極材料合成	23
2.3	負極漿料製備	25
2.4	鋰離子混合式電容器之電極準備	26
2.5	鋰離子混合式電容器組裝	27
2.6	電化學量測流程	27
3	實驗方法	28
4	電極材料鑑定與分析	35
4.1	X光繞射分析	35
4.2	比表面積與微孔徑分析	36
4.3	電化學特性分析	37
4.4	電化學計算分析	38
第四章	結果與討論	39
1	電極材料性質測試	39
1.1	活性碳正極材料	39
1.1.1	比表面積及微孔徑分析	39
1.1.2	循環伏安分析	44
1.2	LTZP負極材料	49
1.2.1	X光繞射分析	49
1.2.2	單電極充、放電行為	50
1.3	LSP負極材料	55
1.3.1	X光繞射分析	55
1.3.2	單電極充、放電行為	56
2	鋰離子混合式電容器性質測試	64
2.1	LTZP/AC(1:1)之鋰離子混合式電容器設計	64
2.1.1	恆電流充、放電分析	64
2.1.2	正、負極放電特性分析	66
2.1.3	比電量分析	69
2.1.4	功率損失分析	70
2.1.5	放電特性分析	72
2.1.6	循環壽命測試	73
2.2	LSP/AC(1:0.5)之鋰離子混合式電容器設計	76
2.2.1	恆電流充、放電分析	77
2.2.2	正、負極放電特性分析	78
2.2.3	比電量分析	82
2.2.4	功率損失分析	83
2.2.5	放電特性分析	84
2.2.6	循環壽命測試	86
2.3	LSP/AC(1:1.0)之鋰離子混合式電容器設計	90
2.3.1	恆電流充、放電分析	90
2.3.2	正、負極放電特性分析	92
2.3.3	比電量分析	95
2.3.4	功率損失分析	96
2.3.5	放電特性分析	97
2.3.6	循環壽命測試	99
2.4	LSP/AC(1:2.0)之鋰離子混合式電容器設計	103
2.4.1	恆電流充、放電分析	103
2.4.2	正、負極放電特性分析	105
2.4.3	比電量分析	108
2.4.4	功率損失分析	109
2.4.5	放電特性分析	110
2.4.6	循環壽命測試	112
2.5	不同重量比例之鋰離子混合式電容器比較	116
2.5.1	恆電流充、放電分析	116
2.5.2	正、負極放電特性分析	118
2.5.3	比電量分析	120
2.5.4	功率損失分析	121
2.5.5	放電特性分析	122
2.5.6	循環壽命測試	123
2.6	不同鋰化程序之鋰離子混合式電容器比較	125
2.6.1	恆電流充、放電分析	125
2.6.2	正、負極放電特性分析	126
2.6.3	比電量分析	127
2.6.4	放電特性分析	129
2.6.5	功率損失分析	130
2.6.6	循環壽命測試	131
2.6.7	電化學交流阻抗分析	133
第五章	結論	135
參考文獻	137
附錄	142

                                

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