以金屬氧化物NiO和Mn3O4摻入有序中孔洞碳材作為鋰離子電池負極材料之應用

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姓名

陳秀真(Hsiu-Chen, Chen) 查詢紙本館藏

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化學學系

論文名稱

以金屬氧化物NiO和Mn3O4摻入有序中孔洞碳材作為鋰離子電池負極材料之應用
(Electrochemical Performance of Lithium Ion Batteries with Anode-based NiO and Mn3O4 nanoparticles confined in Ordered Mesoporous Carbons)

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摘要(中)

本論文主要探討利用含高理論電容氧化金屬參雜在有序結構規則中孔洞奈米碳材CMK-8用用至鋰離子二次電池負極材料上的複合材料，起初利用高分子界面活性劑P123做為軟性模板並以矽酸乙脂(Tetraethyl orthosilicate，簡稱為 TEOS)作為矽的來源，合成出有序的Ia3 ̅d特性的Cubic KIT-6 矽材，接著將矽材碳化之後得到CMK-8，再利用含浸法將金屬氧化物至入CMK-8孔洞中，利用XRD、BET、TEM來鑑定其結構是高表面積且規則的中孔洞碳才。
　　本論文金屬氧化物包含兩種，分別是Mn3O4和NiO，利用硝酸鎳和硝酸錳作為含浸金屬氧化物的前驅物，依據不同濃度，0.25 M、0.1 M、0.05 M含浸到CMK-8的中孔洞及孔道當中，從XRD估算金屬氧化物顆粒大小，且以TEM來觀測，與之相符合，可以觀察到粒子大小會隨著濃度改變，電性表現也會因為顆粒的大小有所不同，比原本基材CMK-8的電性表現會提高，本篇論文會針對不同濃度及金屬氧化物顆粒大小利用做比較和結論。

摘要(英)

Lithium-ion batteries (LIBs) have been commonly used as power sources in portable electronics. Although ordered mesoporous carbon CMK-8 has been used as an anode for lithium-ion batteries, its theoretical capacity is only 372 mA h g-1. To improve the reversible capacity, cycling stability, and electrochemical performance of CMK-8 based anodes for applications in LIBs, two types of metal oxides such as NiO (theoretical capacity = 718 mA h g-1) and Mn3O4 (theoretical capacity = 937 mA h g-1) were chosen to embed into the mesopores of CMK-8 separately in this study. The mesopores of CMK-8 can effectively limit the particle growth of metal oxide and accommodate the volume variation of metal oxides during charge-discharge. Metal oxide@CMK-8 can also improve electronic conductivity. The metal oxide@CMK-8 materials were characterized by SEM, TEM, powder X-ray diffraction, and nitrogen adsorption-desorption measurements. The electrodes for LIBs were fabricated using a mixture of the active materials, namely metal oxide@CMK-8 materials (80 wt.%), carbon black (10 wt.%), and polyvinylidene fluoride (PVDF, 10 wt.%) in N-methyl-2-pyrrolidone (NMP) , The electrochemical performance was tested by assembling CR2032 coin cell.

關鍵字(中)

★ 鋰離子電池
★ 中孔洞碳材
★ 氧化金屬
★ 負極

關鍵字(英)

★ Lithium Ion Batteries
★ Mesoporous Carbons
★ Anode

論文目次

中文摘要 i
Abstract vi
目錄 viii
圖目錄 xii
表目錄 xvi
第一章緒論 1
1-1 鋰離子電池簡介 1
1-2 研究目的 5
1-3 研究架構 7
第二章文獻回顧 8
2-1 中孔洞碳材 8
2-1-1 奈米模鑄法 (Nanocasting) 11
2-2 負極材料 20
2-2-1 非碳材 20
2-2-1-1 鎳氧化物 20
2-2-1-2 錳氧化物 28
2-3 金屬氧化物在碳材改質方法 30
2-3-1 NiO@碳材改質法 30
2-3-2 Mn3O4@碳材改質法 37
第三章實驗方法 42
3-1 藥品 42
3-2 奈米模鑄法合成三維孔道結構 (Ia3 ̅d)中孔洞碳材 44
3-2-1 三維立方體Ia3 ̅d中孔洞矽材模板KIT-6合成 44
3-2-2 三維立方體Ia3 ̅d中孔洞矽材模板CMK-8合成 44
3-3 含浸法合成NiO@CMK8負極複合物 46
3-4 含浸法合成Mn3O4@CMK8負極複合物 46
3-5 材料電化學測試 47
3-5-1 負極極片製作 47
3-5-2 硬幣型電池組裝 47
3-5-3 電池性能測試方法 49
3-5-4 定(變)電流充放電循環測試 49
3-5-4-1 電化學阻抗分析 (EIS) 49
3-5-4-2 循環伏安法 (CV) 49
3-6 實驗鑑定儀器 50
3-7 鑑定儀器之原理 51
3-7-1 同步輻射光束線54 51
3-7-2 X射線粉末繞射 (Powder X-Ray Diffractometer, XRD) 53
3-7-3 氮氣等溫吸脫附曲線、表面積與孔洞特性鑑定 55
3-7-4 穿透式電子顯微鏡 (Transmission Electron Microscope, TEM)61 60
3-7-5 掃描式電子顯微鏡 (Scanning Electron Microscope, SEM)63 62
第四章結果與討論 64
4-1 含浸法合成NiO@CMK8負極奈米複合物 64
4-1-1 低角度XRD 結果分析 64
4-1-2 高角度XRD 結果分析 66
4-1-3 氮氣等溫吸附/脫附結果分析 69
4-1-4 充放電前後SEM結果分析 72
4-1-5 TEM結果分析 74
4-1-6 XPS結果分析 77
4-1-7 固定電流下循環壽命 78
4-1-8 不同電流密度放電 85
4-1-9 循環伏安法分析 86
4-1-10 交流阻抗分析 88
4-1-11 充放電後SEM結果分析 90
4-2 含浸法合成Mn3O4@CMK8負極奈米複合物 92
4-2-1 低角度XRD 結果分析 92
4-2-2 高角度XRD 結果分析 94
4-2-3 氮氣等溫吸附/脫附結果分析 97
4-2-4 充放電前SEM結果分析 100
4-2-5 TEM結果分析 102
4-2-6 XPS 105
4-2-7 固定電流下循環壽命 106
4-2-8 不同電流密度放電 113
4-2-9 循環伏安法分析 114
4-2-10 交流阻抗分析 116
4-2-11 充放電後SEM結果分析 118
第五章結論 120
第六章參考文獻 121

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指導教授

高憲明(Hsien-Chen, Chen)

審核日期

2017-7-18

推文