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研究生:王騰輝
研究生(外文):Teng-Hui Wang
論文名稱:電場排列電極材料於高能鋰離子電池之研究
論文名稱(外文):Using electric field arrange electrode materials for lithium ion batteries
指導教授:諸柏仁
指導教授(外文):Peter Po-Jen Chu
學位類別:碩士
校院名稱:國立中央大學
系所名稱:化學學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2018
畢業學年度:106
語文別:中文
論文頁數:120
中文關鍵詞:尖晶石LTOLi4Ti5O12電場誘導
外文關鍵詞:SpinelLTOLi4Ti5O12Electric field induction
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隨著3C產品的使用以及電動車的發展,下一代鋰離子電池需要高的能量密度以及高的功率密度,新的正極材料開發以及負極材料的包覆是近幾年來可以增加能量密度的方式。製造低曲折率(Tortuosity)、高孔洞性(Pores)、高電解液滲透率(Permeability)、低阻抗值(Impedance)的極片將是下一代鋰離子電池開發高能量密度以及高功率密度的新方向。
在此篇研究中,使用電場施加極片的方式來製造出低曲折率的極片。當鋰離子在極片中移動的路徑減小,則鋰離子移動的速度增加,電阻抗就會降低,這是一種可以提升功率密度又不會降低能量密度的做法。本研究使用穩定的尖晶石(Spinel)結構鋰鈦氧(Li4Ti5O12 [LTO])來做活性材料,並使用外加電場可以排列無機物的概念誘導陰極漿料(LTO、導電碳黑[Super-P]、黏著劑[PVdF])排列。由表面AFM、表面SEM、還有斷面SEM結果可以表明電極材料形成孔隙結構、低的曲折率、以及高的孔洞半徑。由離子導電度測試可以發現導電度有增加(由1.32×10-3 S cm-1 提升到4.45×10-3 S cm-1 ),交流阻抗測試可以發現電荷轉移阻抗(Charge transfer Resistant [Rct])有降低的情形(由 164.0Ω 降低到 80.1Ω ),這些數據可以表明使用電場施加的極片是可以提升電解液的穿透率以及降低極片的阻抗值。
最後,以不同電壓範圍以及不同速率充放電測試並且使用拉格圖(Ragone Plot)來找能量密度以及功率密度的關係圖譜。發現到經過電場施加的極片可以有效提升能量密度以及功率密度。功率密度從545.3增加至660.4 W kg-1,而能量密度從57.1增加至105.3 Wh kg-1。而高的孔隙結構也可以增加極片的比電容數值(specific capacity)而展現擬電容器(Pseudocapacitance)的現象。
New materials are being developed for next generation of lithium battery with higher energy and power density. Making low tortuosity and more porosity electrode has the potential to deliver high permeability of electrolytes and lower ion transport resistance. These features are essential to raise the power and energy density for next generation lithium ion batteries.
In present work, we report a novel approach by architecting lower tortuosity electrode structure with the use of electric field poling technique. The straightforward ion transfer path established fluent electrolyte permeation and faster ion transport with the voids in electrode, and maintains high power density without sacrificing energy density. This approach is demonstrated with the stable spinel structure Li4Ti5O12 (LTO) as an active material. The external electric force induced instantaneous dipole interaction which served to arrange the anode components (carbon black, binder) containing LTO with preferentially ordered alignment. Surface AFM, surface SEM and cross-section SEM results shows the electrode developed a pore structure with lower degree of tortuosity, and larger pore size. Ion conductivity is found to be increased (from 1.32×10-3 to 4.45×10-3 S/cm) and AC-impedance analysis shows the Rct, is reduced (from 164.0 to 80.1Ω). This confirms that E-F poling has developed benign electrode pore structure for better electrolyte permeation which shows lower ion transport resistance.
Finally, different voltage range and variable charge-discharge rate test revealed the relationship of power and energy density with Ragone Plot which suggested that the electric field-induced inorganic alignment is able to elevated both power and energy densities. On average, power density is increased from 545.3 to 660.4 W/kg, and energy density from 57.1 to 105.3 Wh/kg. The larger pore structure also allows for more complete access to active electrode materials, thus improves the specific capacitance, as well.
摘要 i
Abstract ii
致謝辭 iv
目錄 v
圖目錄 viii
表目錄 xiii
第一章 介紹 1
1-1 前言 1
1-2 電池儲能裝置 3
1-3 鋰離子電池與其工作原理 5
第二章 文獻回顧 7
2-1 電解液進入極片的因素 7
2-1-1 曲折率 7
2-1-2 有效的擴散係數 8
2-1-3 探討正極材料的厚度以及電解液之間的關係 9
2-2 如何增加鋰離子電池的效能(能量密度以及功率密度) 11
2-2-1 摻入碳材 12
2-2-2 改變活性材料—晶格組成改變 15
2-2-3 增加或製造表面積 18
2-2-4 使用犧牲劑來做孔洞結構 28
2-3 鋰鈦氧(LTO)負極材料 30
2-4 超級電容(電雙層電容器) 30
2-5 使用電流密度法測量電池與電容器的效能 33
2-5-1 循環壽命測試 34
2-5-2 變速率充放電測試 36
第三章 藥品儀器以及實驗介紹 38
3-1 實驗藥品與器材以及實驗設備儀器 38
3-1-1 實驗藥品 38
3-1-2 實驗器材 40
3-1-3 實驗設備儀器 40
3-2 實驗方法與步驟 43
3-2-1 正常極片的製作方法(沒有通入電場的極片) 44
3-2-2 電場的施加方法(通入電場的極片) 44
3-2-3 半電池的製作方法 45
3-3 氮氣吸脫附儀(N2 Adsorption Desorption Isotherm) 47
3-4 交流阻抗儀 48
第四章 結果與討論 49
4-1 極片的形貌 49
4-1-1 AFM表面鑑定 50
4-1-2 SEM表面鑑定 51
4-1-3 SEM斷面鑑定 52
4-1-4 BET孔徑度測試 53
4-1-5 電解液的擴散時間 55
4-2 使用交流阻抗測量極片的電阻以及半電池的阻抗 56
4-2-1 極片導電度測試 56
4-2-2 半電池交流阻抗測試 58
4-3 電化學性能測試 60
4-3-1 電池性能測試 (Capacity) [正常電壓充放電測試 (1.0~2.5V)] 61
4-3-2 電池性能測試 (Capacity) [過充電壓充放電測試 (0.1~2.5V)] 68
4-3-3 電容性能測試 (Faraday) 78
4-4 化成三圈後的EDX元素鑑定 86
4-5 電場對無機物的影響 88
第五章 結論與未來展望 93
參考文獻 97
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