二維材料 MXene 結合二硫化鉬與硫化錳及雙金屬鋅錳氧化物 ZnMn2O4 之複合材作為鋰(鈉)離子電池負極材料之應用

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莊才俊(Tsai-Chun Chuang) 查詢紙本館藏

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二維材料 MXene 結合二硫化鉬與硫化錳及雙金屬鋅錳氧化物 ZnMn2O4 之複合材作為鋰(鈉)離子電池負極材料之應用

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至系統瀏覽論文 (2029-6-30以後開放)

摘要(中)

本論文分為兩部分，首先在第一部分中，二維/二維異質結構能夠充分發揮每種二維材料的優勢，甚至通過協同效應展現出更好的性能。二維過渡金屬碳化物Ti3C2Tx (MXene) 具有優異的金屬導電性，但易發生重新堆疊；而二維MoS2則具有鬆散的空間，但導電性較差。兩者結合後能夠彌補彼此的不足。此外，將二維MoS2與其他過渡金屬硫化物結合是提高其電化學性能的有前途的策略。在這個研究中，利用一步水熱法合成了一種異質結構，其中MnS納米顆粒嵌入生長在MXene上的MoS2納米片層與層中 (稱為MXene@MnS-MoS2，簡稱為M-MMS)，作為鋰離子電池的負極材料。異質結構帶來的相變和內建電場提高了鋰(鈉)離子的插層動力學，促進了電荷傳遞，並且能夠應對體積膨脹。在鋰離子半電池中，M-MMS電極展現出良好的比容量、出色的倍率性能和穩定的循環穩定性。在鈉離子半電池及鋰離子全電池測試中也表現出不錯的比容量。
第二部分以第一部分的水熱合成為基礎，嘗試將MXene與ZnMn2O4結合在一起，並期許也發揮協同效應，使其能作為鋰離子電池負極進行應用。

摘要(英)

In the first part, two-dimensional/two-dimensional heterostructures can leverage the strengths of each constituent 2D material and even demonstrate enhanced performance through synergistic effects. Two-dimensional transition metal carbide Ti3C2Tx (MXene) boasts excellent metallic conductivity, but, is prone to restacking, whereas two-dimensional MoS2 offers loose space but lacks in conductivity. Therefore, combining the Ti3C2Tx and MoS2 can complement each other′s weaknesses. Additionally, merging of 2D MoS2 with other transition metal sulfides represents a promising strategy for enhancing its electrochemical performances. Herein, a heterostructure composed of MnS nanoparticles embedded in MoS2 nanosheets grown on MXene (referred to as MXene@MnS-MoS2, abbreviated as M-MMS) was designed and synthesized as an anode material for lithium-ion batteries using a one-step hydrothermal method. The heterostructure-induced phase transition and built-in electric field enhance the intercalation kinetics of Li-ions, facilitate charge transfer, and accommodate volume expansion. Among the M-MMSs, the 0.26M-MMS exhibited the best performance, with a capacity of 818 mAh g-1 after 200 cycles at a current density of 100 mA g-1. The results indicate that M-MMS is a promising high-performance anode material for lithium-ion batteries demonstrating remarkable cycling performance, outstanding rate performance and good stability. The second part attempts to combine MXene with ZnMn2O4, aiming to enhance its performance as a lithium-ion battery anode.

關鍵字(中)

★ 過度金屬碳氮化物
★ 過渡金屬二硫屬化物
★ 鋰離子電池
★ 鈉離子電池

關鍵字(英)

★ MXene
★ TMD
★ LIB
★ SIB

論文目次

摘要 II
Abstract III
謝誌 IV
目錄 VI
圖目錄 XII
表目錄 XIX
第一章序論 1
1-1 鋰離子電池 (LIBs) 1
1-1-1 鋰離子電池簡介 1
1-1-2 鋰離子電池正極材料 3
1-1-3 鋰離子電池負極材料 7
1-2 鈉離子電池 (SIBs) 10
1-2-1 鈉離子電池簡介 10
1-2-2 鈉離子電池正極材料 12
1-2-3 鈉離子電池負極材料 14
1-3 電解液 16
1-3-1 電解液簡介 16
1-3-2 有機溶劑 17
1-3-3 金屬鹽 18
1-3-4 添加劑 19
1-3-5 固態電解質界面 21
1-4 過渡金屬二硫屬化物 (TMDs) 22
1-4-1 過渡金屬二硫屬化物簡介 22
1-4-2 過渡金屬二硫屬化物製備方式 24
1-4-3 在鋰/鈉離子電池負極的應用 26
1-5 過渡金屬碳/氮化物 (MXenes) 29
1-5-1 過渡金屬碳/氮化物簡介 29
1-5-2 MAX phase製備方式 31
1-5-3 合成MXene的蝕刻方式 37
1-5-4 插層劑 41
1-5-5 在鋰/鈉離子電池負極的應用 42
1-6 研究動機與目的 45
第二章實驗方法與鑑定 46
2-1 實驗藥品 46
2-2 實驗步驟 48
第壹部分二維材料MXene結合二硫化鉬與硫化錳之複合材作為鋰(鈉)離子電池負極材料之應用 48
2-2-1 合成多層Ti3C2Tx (m-MXene) 48
2-2-2 合成少層Ti3C2Tx (f-MXene) 49
2-2-3 合成MnMoO4奈米棒 (MMO) 50
2-2-4 合成MXene@MnS-MoS2 (M-MMS) 51
第貳部分二維材料MXene結合鋅錳氧化物ZnMn2O4之複合材作為鋰離子電池負極材料之應用 52
2-2-5 合成MXene@ZnMn2O4 (M-ZMO) 52
2-3 電極製備及電化學測試方法 53
2-3-1 負極極片製作 53
2-3-2 正極極片製作 53
2-3-3 硬幣型2032型電池組裝 54
2-3-4 定(變)電流充放電循環穩定性測試 55
2-3-5 循環伏安法 (CV) 56
2-3-6 電化學阻抗分析 (EIS) 56
2-4 實驗合成及鑑定儀器 57
2-4-1 實驗合成設備 57
2-4-2 實驗鑑定儀器 58
2-5 儀器鑑定之原理 59
2-5-1 粉末X光繞射儀 (PXRD) 59
2-5-2 掃描式電子顯微鏡 (SEM) 60
2-5-3 穿透式電子顯微鏡 (TEM) 61
2-5-4 拉曼光譜分析儀 (Raman Spectroscopy) 62
2-5-5 熱重分析儀 (TGA) 63
2-5-6 高解析感應耦合電將質譜分析 (ICP-MS) 64
2-5-7 元素分析儀 (EA) 65
2-5-8 光電子能譜 (XPS) 66
2-5-9 電化學阻抗譜 (EIS) 67
2-5-10 循環伏安法 (CV) 68
第三章結果與討論 70
第壹部分二維材料MXene結合二硫化鉬與硫化錳之複合材作為鋰(鈉)離子電池負極材料之應用 70
3-1 材料鑑定 70
3-1-1 大角度X光繞射分析 (WXRD) 70
3-1-2 掃描式電子顯微鏡 (SEM) 形貌鑑定 73
3-1-3 穿透式電子顯微鏡 (TEM) 結果分析 80
3-1-4 拉曼光譜分析 (Raman) 87
3-1-5 熱重分析 (TGA) 90
3-1-6 感應電漿耦合質譜 (ICP-MS) 分析及元素分析 (EA) 91
3-1-7 X光電子能譜 (XPS) 分析 92
3-2 材料於鋰離子半電池之電化學測試 97
3-2-1 循環伏安曲線及充放電曲線之分析 97
3-2-2 循環穩定性及倍率性測試 102
3-2-3 交流阻抗分析 108
3-2-4 電容貢獻度計算 111
3-3 充放電循環後之鑑定 116
3-4 材料於鈉離子半電池之電化學測試 119
3-4-1 循環伏安曲線及充放電曲線之分析 119
3-4-2 循環穩定性及倍率性測試 121
3-4-3 交流阻抗分析 124
3-4-4 電容貢獻度計算 126
3-5 實際應用及相關文獻比較 130
第四章結果與討論 133
第貳部分二維材料MXene結合鋅錳氧化物ZnMn2O4之複合材作為鋰離子電池負極材料之應用 133
4-1 材料鑑定 133
4-1-1 大角度X光繞射分析 (WXRD) 133
4-1-2 掃描式電子顯微鏡 (SEM) 形貌鑑定 134
4-1-3 穿透式電子顯微鏡 (TEM) 結果分析 137
4-2 材料於鋰離子半電池之電化學測試 139
4-2-1 循環伏安曲線及充放電曲線之分析 139
4-2-2 循環穩定性及倍率性測試 141
第五章結論 144
參考文獻 146

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指導教授

高憲明(Hsien-Ming Kao)

審核日期

2024-7-11

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