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研究生： 吳禹呈
Wu, Yu-Cheng
論文名稱： 表面改質矽碳奈米複合材料之製備與其於鋰離子電池負極材料之應用
Preparation of Surface-Modified Silicon/Carbon Nanocomposite for Anode Material of Lithium-Ion Battery
指導教授： 郭炳林
Kuo, Ping-Lin
邱繼正
Chiu, Chi-Cheng
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 中文
論文頁數： 86
中文關鍵詞： 鋰離子電池 、矽負極材料 、奈米複合材料 、表面改質
外文關鍵詞： lithium-ion battery, nanocomposite, silicon anode, surface modification
相關次數： 點閱：203  下載：0 
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    • 矽負極材料地殼含量高、價格低廉、低還原電動式(～0.4 V)、高理論電容(4200 mAh g-1)，但在充放電的過程中有劇烈體積變化(～400 %)，造成其在商業化上的阻礙，本實驗在矽表面沉積碳層，藉由碳層緩解矽體積膨脹，並提升矽材料導電性，再進行表面改質使矽碳複合材料表面生成穩定的SEI(Solid electrolyte interphase)層，藉此使矽碳複合材料具有高循環充放電穩定性。
    由拉曼、四點探針、電池效能測試發現mSi@C-x、Li-mSi@C-x由於表面改質破壞的材料之間的G-band，導致材料的導電度下降，進而降低克電容值。而由SEM影響觀察充放電前後的極片表面，發現在mSi@C-x、Li-mSi@C-x表面SEI層沉積較薄，得知本實驗經過表面改質確實可以穩定SEI層沉積；在循環充放電測試中以450 mA g-1進行循環充放電，在450 mA g-1條件下 Li-mSi@C-1首圈可逆電容值為976 mAh g-1，經過200圈充放電後電容維持率仍有69.5%，此電容維持率是遠高於Si@C在200圈充放電後電容維持率0.5%。證明經表面改質並預鋰化處理過後矽碳複合材料雖然會降低導電度使電容值下降，但可以有效穩定表面SEI層沉積並且提高循環壽命穩定性。

    The silicon anode material has high earth abundance, low cost, low operational voltage (~0.4 V), high theoretical capacitance (4200 mAh g-1), but there is a drastic volume change (~400%) in the process of charging and discharging. This problem makes it difficult to commercialize. In this study, the surface-modified silicon/carbon nanocomposite (Li-mSi@C-x) was designed and prepared. The carbon coating could alleviate the volume variation, particle fracture and improve the conductivity of the silicon material. Then, surface modification of silicon/carbon composite (Si@C) could prevent uncontrollable growth of the SEI(Solid electrolyte interphase) during cycling, so that Li-mSi@C-x has better cycle stability.
    The TEM, XRD, and TGA showed that Si@C has successfully prepared. The raman showed that the G-band of mSi@C-x was damaged after modification, so that the performance of mSi@C-x become worse due to the decrease of the conductivity. We used SEM to observe the pole surface after cycles, and found that the SEI layer of mSi@Cx and Li-mSi@Cx was thinner. At current density of 450 mA g-1, the Li-mSi@C-1 anode has an initial specific capacity of 976 mAh g-1, and capacity retention remained 69.5 % after 200 cycles. This capacitance retention rate is much higher than the retention of Si@C. Compared with Si@C, the sample of mSi@C-x and Li-mSi@C-x reduced electric conductivity, but improved cycle stability.

    中文摘要 I Abstract II 誌謝 IX 目錄 X 表目錄 XIII 圖目錄 XIV 第一章 緒論 1 1.1 前言 1 1.2 電池簡介 2 1.3 電池運作原理 4 1.4 研究動機 6 第二章 文獻回顧 7 2.1 負極材料 7 2.2 碳負極材料 10 2.2.1 天然石墨 11 2.2.2 人工石墨 12 2.3 矽負極材料 13 2.3.1 奈米矽材料 15 2.3.2 矽空心結構 16 2.3.3 矽多孔結構 17 2.4 矽碳複合材料 18 2.4.1 核殼矽碳複合材料 18 2.4.2 空心殼結構 19 2.4.3 矽碳奈米線塗佈層 20 2.4.4 嵌入式結構 22 2.5 固態電解質介面(SEI) 23 2.5.1 電解質添加劑 23 2.5.2 金屬氧化物表面塗層 24 第三章 實驗 25 3.1 實驗材料 25 3.2 實驗儀器 26 3.3 實驗樣品製備 27 3.3.1 Si@C之製備 27 3.3.2 mSi@C-x之製備 27 3.3.3 Li-mSi@C-x之製備 28 3.4 鋰電池製備及組裝 29 3.4.1 負極極片製作 29 3.4.2 鈕扣型電池之組裝 30 3.5 表徵分析 31 3.5.1 穿透式電子顯微鏡(Transmission electron microscopy, TEM) 31 3.5.2 掃描式電子顯微鏡(Scanning electron microscope, SEM) 32 3.5.3 X-射線繞射光譜儀(X-ray diffractometer, XRD) 32 3.5.4 顯微拉曼光譜儀(Raman) 34 3.5.5 熱重分析儀(Thermogravimetric analysis, TGA) 34 3.5.6 離子當量交換(Ion exchange capacity, IEC) 34 3.5.7 X光光電子能譜儀(X-ray photoelectron spectroscopy, XPS) 35 3.6 電化學分析 35 3.6.1 電池循環壽命效能(Cycle life test) 35 3.6.2 電池庫倫效率測定(Coulombic efficiency, CE) 36 3.6.3 電池效能測試(C-rate) 36 3.6.4 循環伏安法(Cyclic Voltammetry, CV) 36 3.6.5 塔菲爾方程(Tafel) 37 3.6.6 電化學阻抗頻譜法(electrochemical impedance spectroscopy, EIS) 39 3.6.7 四點探針測試 40 3.6.8 差分電容分析(Differential Capacity, dQ/dV) 41 第四章 結果與討論 42 4.1 Si@C、mSi@C-x、Li-mSi@C-x之材料性質分析 42 4.1.1 材料之穿透式電子顯微鏡影像觀察與粒徑分佈分析 42 4.1.2 X-射線繞射光譜分析 46 4.1.3 拉曼鑑定分析 47 4.1.4 電極極片掃描式電子顯微鏡影像觀察 49 4.1.5 四點探針測試 51 4.1.6 熱重分析 52 4.1.7 離子當量交換分析 54 4.2 電化學性能測試 55 4.2.1 電池效能測試 55 4.2.2 電池循環壽命測試 59 4.2.3 X光光電子能譜儀分析 68 4.2.4 循環伏安法與塔菲爾曲線分析 71 4.2.5 電池庫倫效率分析 75 4.2.6 電化學阻抗分析 76 4.2.7 差分電容圖譜分析 78 第五章 結論 81 第六章 參考資料 83

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