本研究利用超臨界流體合成法(SFLS)合成出高品質的磷化銅(CuP2)奈米線，並且應用在鋰、鈉離子電池(lithium/sodium ion batteries)以及電晶體元件上面。於鋰離子電池，經碳化燒結處理的磷化銅奈米線所製備的陽極電極，第一圈充、放電比電容量(charge /discharge specific capacity) 擁有1689和1075 mA h g-1，庫倫效率(coulombic efficiency) 為64%。再經過100次充放電循環後的比電容量維持945 mA h/g，電容量保持率(capacity retention)維持在88％。即使是在電流密度(current density) 6C，電極仍具有突出的表現，比電容量約〜700 mA h g-1，遠高於一般商業負極材料-石墨比電容量(372 mA h g-1)。最後，我們將負極材料磷化銅奈米線搭配業界常用的正極材料磷酸鋰鐵(LiFePO4)，以疊片式組成鈕釦型(coin cell)以及軟包式全電池，進行概念性運用。
由於鋰離子電池的需求量逐年增加，導致鋰金屬原料供不應求，價格急遽上漲。未來方向必定是找尋高富含量(earth abundance)的替代材料作為電池中傳導的離子。鈉離子電池是目前最為可行性的選項之一。同樣，我們將先前碳化燒結處理的磷化銅奈米線製備成負極電極並運用於其中，經過100次充放電循環後比電容量維持在975 mA h g-1，比電容量維持率為95%。表現出不輸給鋰離子電池的電化學特性。
在電晶體元件測試中，透過電流-電壓曲線圖我們計算出磷化銅奈米線電阻率(resistivity)為7.9×10-3 Ω*m。同時利用單根磷化銅奈米線場效電晶體(field effect transistor)測試，結果顯示具有p型行為，開/關比(on/off ratio)大於104。

Phosphorus-rich transition metal phosphide CuP2 nanowires were synthesized with high quality and high yield (∼60%) via the supercritical fluid−liquid−solid (SFLS) growth at 410 °C and 10.2 MPa. The obtained CuP2 nanowires have a high aspect ratio and exhibit a single crystal structure of monoclinic CuP2 without any impurity phase. CuP2 nanowires have progressive improvement for semiconductors and energy storages compared with bulk CuP2. Being utilized for back-gate field effect transistor (FET) measurement, CuP2 nanowires possess a p-type behavior intrinsically with an on/off ratio larger than 104 and its single nanowire electrical transport property exhibits a hole mobility of 147 cm2 V−1 s−1, representing the example of a CuP2 transistor. In addition, CuP2 nanowires can serve as an appealing anode material for a lithium-ion battery electrode. The discharge capacity remained at 945 mA h g−1 after 100 cycles, showing a good capacity retention of 88% based on the first discharge capacity. Even at a high rate of 6 C, the electrode still exhibited an outstanding result with a capacity of ∼600 mA h g−1. Ex-situ transmission electron microscopy and CV tests demonstrate that the stability of capacity retention and remarkable rate capability of the CuP2 nanowires electrode are attributed to the role of the metal phosphide conversion-type lithium storage mechanism. Finally, CuP2 nanowire anodes and LiFePO4 cathodes were assembled into pouch-type lithium batteries offering a capacity over 60 mA h. The full cell shows high capacity and stable capacity retention and can be used as an energy supply to operate electronic devices such as mobile phones and mini 4WD cars. However, due to increasing demand for lithium-ion batteries, lithium metal on earth cannot meet the need so that the price of lithium increases year by year. Future work must be looking for high abundance of alternative materials as ion conduction of battery. Sodium ion battery is currently one of the most feasible option. We applied previously calcined copper phosphide nanowires to sodium ion batteries, and electrochemical results shows that capacity possesses 975 mA h g-1 after 100 charge/discharge cycle, with retention 95%.

中文摘要 1
Abstract 2
Table of Contents 4
List of Tables 6
List of Figures 7
Chapter 1. Thesis Introduction 12
1.1 Semiconductor Nanowires 12
1.1.1 Semiconductor Nanowires Synthesis 12
1.1.2 Reference 14
1.2 Introduction on transition-metal phosphides 16
1.2.1 Transition-metal phosphides 16
1.2.2 Copper phosphide 17
1.2.3 Reference 19
1.3 Introduction on Lithium-ion Batteries 23
1.3.1 Lithium-ion Batteries 23
1.3.2 Anode nanomaterials of Lithium Ion Batteries 25
1.3.3 Phosphide as anode material of Lithium ion Batteries 29
1.3.4 Reference 31
1.4 Introduction on Sodium-ion Batteries 36
1.4.1 Sodium-ion Batteries 36
1.4.2 Anode materials of Sodium Ion Batteries 37
1.4.3 Reference 41
Chapter 2. Experimental Section 43
2.1 Materials 43
2.2 CuP2 Nanowires Synthesis and Characterization 43
2.3 Lithium-ion Batteries Assembly and Electrochemical Characterization 46
2.3.1 Coin Cell Assembly and Characterization 46
2.3.2 Pouch-type Full Cell Assembly 47
2.3.3 Sodium-ion Batteries Assembly 47
Chapter 3. Result and Discussion 49
3.1 CuP2 Nanowires Characterization 49
3.2 CuP2 Nanowires Lithium-ion Batteries 57
3.2.1 Electrochemical Performance 57
3.2.2 Mechanism 67
3.2.3 Full cell test and Application 72
3.3 CuP2 Nanowires Sodium Ion Batteries 77
3.4 Field Effect Transistor 82
Chapter 4. Conclusion 85

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