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研究生： 潘彥廷
Pan, Yen-Ting
論文名稱： 石墨烯海綿結構包覆於矽奈米顆粒作為高循環壽命與高電容量鋰離子電池負極材料之應用
Silicon Nanoparticles in Graphene Sponge for Long-Cycling-Life and High-Capacity Lithium Ion Battery
指導教授： 曾永華
Tzeng, Yon-Hua
學位類別： 碩士
Master
系所名稱： 電機資訊學院 - 微電子工程研究所
Institute of Microelectronics
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 78
中文關鍵詞： 鋰離子電池 、矽 、負極材料 、石墨烯 、鑽石
外文關鍵詞： Graphene, Diamond, Silicon, Anode, Battery
相關次數： 點閱：183  下載：0 
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    • 能源不管是現在、過去或是未來都是一大議題，除了燃燒石油作為能量來源之外，另尋其他有效能源極變為重要、迫切，同時也需要發展更有效率的儲能技術來應對能量存放及攜帶移動的問題，其中鋰管事離子電池的使用為現今最有效儲存能源的方式之一，被視為發展儲能電源的前瞻技術。對於先進之鋰離子電池，在性質方面有高電容量、高功率、低成本、與高循環壽命等嚴苛要求，以及更重要的安全性考量，將鋰離子電池成功應用以符合未來趨勢的前提為提升鋰離子電池的效能，其中鋰離子電池正負極材料的製作技術與選擇更是直接影響鋰離子電池的性能、成本與安全性。
    矽負極材料因其擁有大於石墨約十倍的電容量，已被視為前瞻性之鋰離子電池負極材料，但其最大的限制在於充放電時矽的體積變化率過大，而影響電池的性能。因此本研究將使用微波式電漿增強化學氣相沈積系統(Microwave Plasma Enhanced Chemical Vapor Deposition, MPECVD)在矽材上成長石墨烯奈米牆(Graphene Nano Walls, GNWs)並藉由掃描式電子顯微鏡、拉曼光譜儀及X-Ray繞射儀分析。結果顯示多層石墨烯的形貌直立於矽粉上如同牆一般，因此稱之為石墨烯奈米牆。矽顆粒上成長石墨烯奈米牆可保護矽過度與電解液反應，且能當作體積變化的緩衝層，並讓矽顆粒破裂後仍能保持良好的導電性。經石墨烯奈米牆包覆之矽所製成的負極，在2000 mAh/g的定電容量循環充放電下，能有穩定的100次循環壽命，而未經處理的矽負極僅有數十次的循環壽命。此外透過電化學分析結果，可顯示石墨烯奈米牆包覆可以幫助矽負極的循環壽命增加，以改善負極材料之使用效能，突破能源產業技術瓶頸。

    A microwave plasma enhanced chemical vapor deposition (MPECVD) method is used to synthesis the Graphene nanowalls (GNWs) coated on silicon nanoparticles. The structure is analyzed by scanning electron microscope (SEM), Raman Spectroscope and X-Ray Diffractometer (XRD). The results show that the GNWs coated silicon exist some multilayer graphene stand on it just as walls, so that why we call it graphene nanowalls. This structure can provide a good electrochemical property. From the cycle performance, it shows that the battery can maintain at 2000 mAh/g for 100 cycles, with a capacity fading of less than ~0.05 %. GNWs act as a protection and conductive channels so that enhance the performance of silicon anode.

    摘要 I Abstract II 誌謝 XI 目錄 XII 圖表目錄 XVII 第一章 緒論 1 第二章 基礎理論與文獻回顧 3 2.1 鋰離子電池工作原理 3 2.2 鋰離子電池之負極材料介紹 4 2.3 矽之負極材料 5 2.4 矽之奈米結構 7 2.4.1 矽奈米粒子 8 2.4.2 矽奈米線及奈米管 9 2.4.3 矽奈米薄膜 12 2.4.4 多孔矽材料 13 2.5 矽碳複合材料 15 2.5.1 矽-非晶碳 15 2.5.2 矽-一維碳材料 16 2.5.2.1 奈米碳管之介紹 16 2.5.2.2 奈米碳管應用於矽負極材料 17 2.5.3 矽-二維碳材料 18 2.5.3.1 石墨烯之介紹 18 2.5.3.2 石墨烯應用於矽負極材料 19 2.5.4 矽-三維碳材料 20 2.5.4.1 鑽石之介紹 20 2.5.4.2 鑽石應用於負極材料 21 2.6 高分子聚合物 24 2.6.1 高分子黏結劑 25 2.6.2 導電黏結劑 27 第三章 實驗方法與步驟 28 3.1 實驗流程簡介 28 3.2 矽包覆石墨烯奈米牆之製備 29 3.3 矽包覆石墨烯奈米牆之分析 32 3.3.1 掃描式電子顯微鏡(Scanning Electron Microscope) 32 3.3.2 拉曼光譜分析儀(Raman Spectroscope System) 33 3.3.3 X-Ray繞射分析儀(X-Ray Diffractometer, XRD) 35 3.4 鋰離子二次半電池之組裝 36 3.4.1 負極極片製作 36 3.4.2 半電池組裝 37 3.5 電化學性質測量及量測後之分析 39 3.5.1 充放電測試機 39 3.5.2 電化學測試機 40 3.5.2.1 循環伏安分析(Cyclic Voltammetry, CV) 41 3.5.2.2 電化學阻抗分析(Electrochemical Impedance Spectroscopy, EIS) 41 3.5.3 電化學量測後之極片分析 44 第四章 實驗結果與討論 45 4.1 矽石墨烯奈米牆 45 4.1.1 光譜分析儀之電漿分析 46 4.1.2 掃描式電子顯微鏡之分析 47 4.1.3 拉曼光譜儀之分析 50 4.1.4 X-ray繞射儀之分析 51 4.2 半電池之電化學性質分析 52 4.2.1 製程之循環性能比較 52 4.2.2 粒徑大小之循環性能比較 54 4.2.3 奈米級之矽負極分析 60 4.2.3.1 循環充放電分析 60 4.2.3.2 定電容之循環充放電分析 62 4.2.3.3 循環伏安分析 65 4.2.3.4 電化學阻抗分析 66 4.2.3.5 電化學量測後之分析 68 第五章 結論與未來展望 69 第六章 參考文獻 71

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