以金屬氧化物ZnO及MgO修飾有序中孔洞碳材CMK-8於高效能鋰離子電池之應用

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張文瑄(Wen-Hsuan Chang) 查詢紙本館藏

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論文名稱

以金屬氧化物ZnO及MgO修飾有序中孔洞碳材CMK-8於高效能鋰離子電池之應用
(ZnO and MgO nanoparticles confined in 3D mesoporous carbon as efficient nanocomposite anodes for lithium-ion batteries)

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摘要(中)

本論文主要是在研究中孔有序碳材CMK-8，進行金屬氧化物的複合修飾，應用在鋰離子電極當中，利用介面活性劑P123，為三嵌段共聚型的高分子，與矽源TEOS (Tetraethyl orthosilicate) 在酸性的條件下進行合成，得到其對稱性為Ia3 ̅d 構型為Cubic的矽材KIT-6，接著將KIT-6進行高溫斷燒碳化，以奈米膜鑄法得到相同對稱性的碳材CMK-8，透過SAXRD、 XRD、BET、TEM等儀器鑑定後，應證為具規則結構的中孔洞碳材，並具有高表面積。
在許多金屬氧化物當中，ZnO具有高理論電容(978 mAh/g)，電化學形質活潑的特性，應用相當廣泛，而MgO雖然電性不高，卻有相當高的熱穩定性，在許多文獻當中，作為保護層應用到鋰離子電池當中，因此在本篇論文當中，將金屬氧化物ZnO及MgO含浸進入到CMK-8 當中，透過一系列儀器的鑑定可以驗證知道金屬氧化物是否成功被含浸，經由調整含浸的濃度大小，成功的合成出不同尺寸的金屬氧化物奈米粒子。將材料應用到鋰離子電池當中，在1C的循環電性當中，樣品ZnO@CMK-8-0.5的初始電容達到2214 mAh/g，而MgO@CMK-8-10wt%的初始電容也達到744 mAh/g，都遠遠大於金屬氧化物本身的理論電容。

摘要(英)

Trainsition metal oxide as anode materials in lithium ion batteries have attracted tremendous attention in the past few years because of their characterstics.ZnO is regarded as one of the most promising anode material for lithium ion batteries (LIBs), due to its high theoretical capacity (978 mAh/g), natural abundance, and low cost. Although MgO is electrochemically inactive, its adsorption capacity towards liquid electrolyte functioning as a protective coating and enhancement in ionic conductivity encourages the use of a MgO-decorated composite as an anode for LIBs.
The ZnO@CMK-8 and MgO@CMK-8 nanocomposites, composed of ultrafine ZnO and MgO nanoparticles encapsulated in three dimensional (3D) ordered mesoporous carbon CMK-8, has been successfully synthesized and served as promising anode materials in lithium-ion batteries (LIBs) with different concertration, separately. The prepared ZnO@CMK-8 and MgO@CMK-8 have been characterized by various techniques, such as XRD, nitrogen adsorption-desorption, high-resolution TEM, and SEM measurements. Our characterization results demonstrates that both ZnO and MgO nanoparticles can be incorporated into the mesopores of CMK-8 with high dispersion and small particle sizes.
As anode materials in lithium ion batteries the composites ZnO@CMK-8-0.5M displays higher initial discharge capacity(2214 mAh/g) than bulk ZnO. MgO@CMK-8-10wt% also demonstrates the better results(744 mAh/g) than rude MgO.

關鍵字(中)

★ 鋰離子電池
★ 陽極
★ 中孔有序碳材

關鍵字(英)

★ Lithium ion batteries
★ anode
★ ordered mesoporous carbon material

論文目次

中文摘要 i
Abstract ii
謝誌 iii
目錄 iv
圖目錄 vii
表目錄 xi
第一章前言 - 1 -
第二章文獻回顧 - 7 -
2-1 中孔洞有序碳材 (Mesoporous ordered carbon materials) - 7 -
2-2 陽極材料 - 18 -
2-2-1 碳材 - 18 -
2-2-2 非碳材 - 21 -
2-2-3 以金屬氧化物修飾上碳材的陽極材料 - 23 -
2-2-3-1 氧化鋅修飾碳材的陽極材料 - 25 -
2-2-3-2 氧化鎂修飾碳材的陽極材料 - 33 -
第三章實驗方法 - 40 -
3-1 藥品 - 40 -
3-2 奈米模鑄法合成三維孔道結構 (Ia3 ̅d) 中孔洞碳材 - 42 -
3-2-1 三維立方體Ia3 ̅d中孔洞矽材模板KIT-6合成 - 42 -
3-2-2 三維立方體 Ia3 ̅d 中孔洞碳材 CMK-8合成 - 42 -
3-3 含浸法合成ZnO@CMK8陽極複合物 - 43 -
3-4 含浸法合成MgO@CMK8陽極複合物 - 44 -
3-5 材料電化學性能測試 - 44 -
3-5-1 陽極極片製作 - 44 -
3-5-2 硬幣型電池組裝 - 45 -
3-5-3 電池性能測試方法 - 46 -
3-6 實驗鑑定儀器 - 47 -
3-7 鑑定儀器之原理 - 48 -
3-7-1 同步輻射光束線 - 48 -
3-7-2 X射線粉末繞射 (Powder X-Ray Diffractometer, XRD) - 51 -
3-7-3 氮氣等溫吸脫附曲線、表面積與孔洞特性鑑定 - 52 -
3-7-4 熱重分析儀 (Thermogravimetric Analyzer, TGA)56 - 56 -
3-7-5 穿透式電子顯微鏡(Transmission Electron Microscope, TEM)57- 57 -
3-7-6 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)58 - 59 -
第四章結果與討論 - 60 -
4-1 奈米模鑄法合成Ia3 ̅d 規則中孔洞碳材及ZnO@CMK-8陽極奈米複合物 - 60 -
4-1-1 低角度XRD結果分析 - 60 -
4-1-2 高角度XRD 結果分析 - 63 -
4-1-3 氮氣等溫吸脫附結果分析 - 66 -
4-1-4 熱重分析 - 69 -
4-1-5 SEM結果分析 - 71 -
4-1-6 TEM結果分析 - 73 -
4-1-7 XPS結果分析 - 75 -
4-1-8 循環伏安法分析 - 77 -
4-1-9 ZnO@CMK-8的電性表現 - 79 -
4-1-10 交流阻抗分析 - 84 -
4-1-11 充放電後的SEM結果分析 - 86 -
4-2 MgO@CMK8陽極奈米複合物 - 87 -
4-2-1 低角度XRD結果分析 - 87 -
4-2-2 高角度XRD結果分析 - 89 -
4-2-3 氮氣等溫吸附/脫附結果分析 - 91 -
4-2-4 熱重分析 - 93 -
4-2-5 SEM結果分析 - 95 -
4-2-6 TEM結果分析 - 97 -
4-2-7 XPS結果分析 - 99 -
4-2-8 循環伏安法分析 - 101 -
4-2-9 MgO@CMK-8電性表現 - 103 -
4-2-10 交流阻抗分析 - 107 -
4-2-11 充放電後的SEM結果分析 - 109 -
第五章結論 - 110 -
參考文獻 - 112 -

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指導教授

高憲明(Hsien-Ming Kao)

審核日期

2017-7-18

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