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研究生： 蔡宗諭
Tsung-Yu Tsai
論文名稱： 無黏合劑鉻摻雜鋰鎳錳氧/碳纖維高電壓複合正極與奈米碳管/碳纖維複合負極應用於鋰離子電池之研究
Study of Binder-Free Cr-doped LiNi0.5Mn1.5O4/Carbon Fiber High Voltage Composite Cathode and Carbon Nanotube/Carbon Fiber Composite Anode for Lithium-Ion Battery Application
指導教授： 劉奕宏
Yi-Hung Liu
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
論文出版年： 2020
畢業學年度： 108
語文別： 中文
論文頁數： 140
中文關鍵詞： 碳纖維 、高電壓 、無黏合劑電極 、奈米碳管 、鋰離子電池
外文關鍵詞： Carbon fiber, High voltage, Binder-free electrode, Carbon nanotube, Lithium ion battery
相關次數： 點閱：18  下載：0 
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    • 隨著電動汽車的與日俱增，具有高能量密度和功率密度的鋰離子電池愈來愈被重視。近期有文獻證實，透過摻雜定量的過渡金屬元素，能使LiNi0.5Mn1.5O4材料的費米能階提高，進而滿足高電壓的需求。此外為了滿足現代人對3C產品輕薄短小的要求，減少像是黏合劑和導電劑以減少電池的重量，且同時保持電池的容量與活性材料和電極間的黏著性都是常被探討的議題。本實驗結合 LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4 活性物質與碳纖維，透過電沉積法與水熱法，並結合鍛燒與抽氣過濾合成無黏合劑LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4 高電壓複合式正極材料。另一方面，透過電泳沉積與鍛燒開發出無黏合劑 CNT/CF 複合型負極材料。
    正極材料的部分，從 XRD 的分析可得知，增加鍛燒時間可有效增強峰值強度，但同時也會因為氧缺失而造成 LixNi1-xO 雜質項的產生，而定量的鉻摻雜 (x≥0.2) 可以有效改善結晶性，進而完全去除雜質項。而從充放電測試中得知摻雜鉻的正極材料 (x=0.1- 0.4) 因 Cr-O 鍵的強結合能，降低在鍛燒時氧氣的損失，以致於在 4.0 V 處 (Mn3+) 展現出較窄的平台，進而抑制電容量快速衰退。其中當 x=0.2 時，LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4 正極材料具有最理想的放電容量 (135 mAh/g)，即使在 5 C 的電流速率下，仍表現出118 mAh/g 的放電容量及 87.4 % 的容量保持率，而在第200個循環後也仍保持 134.7 mAh/g 的放電容量及 97.6 % 的容量保持率，表明定量摻雜鉻確實可優化在高電壓充放電區間的循環性能。
    負極材料的部份，根據 EDS 圖上均勻的分佈層可得知，奈米碳管確實均勻的披覆在碳纖維上。且從循環充放電與循環壽命測試可得知，跟原始的碳纖維相比，藉由 CNT 的修飾改善負極材料在高電流速率下容易快速衰退的問題，即便在 0.5 C 的速率下仍保持 283 mAh/g 的放電容量，並在100個循環後保持 344 mAh/g 的放電容量及 86 % 的容量保持率，表明CNT的修飾可以優化負極材料的放電電容，且改善在高電流速率下的電化學穩定性。

    With increasing demands of large-scale electronic applications such as electric vehicles (EVs), lithium ion batteries (LIBs) with high energy density and power density are desired. Recent researches has confirmed that doping quantitative transition metal will increase the Fermi level of the spinel LiNi0.5Mn1.5O4 material, which can improve the cycle performance in high voltage. In addition, to meet the aforementioned requirement, an electrode design that can accommodate more active material loading while reduce additives such as binders and conductive agents without losing any capacity is therefore expected. In the current study, we aim to combine nickel-manganese-chromium based cathode materials and CFs, developing a binder-free LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4 high voltage composite cathode by using electrochemical deposition together with hydrothermal reaction and suction filtration. On the other hand, we develop a binder-free carbon nanotube (CNT)/CF composite anode by using an electrophoretic deposition method.
    For the LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4 cathode material. From XRD experiment results, it is found that increasing the calcination time can improve crystal purity, but it also lose oxygen and turn into disproportionate spinel LiNi0.5Mn1.5O4 and LixNi1−xO, so we dope Cr to stabilize the spinel structure of LiNi0.5Mn1.5O4 with increasing crystallinity. The composite cathode demonstrates favorable electrochemical performance against high-voltage operation due to the stronger bonding energy of Cr–O. Among them, the LiCr0.2Ni0.4Mn1.4O4 cathode material exhibits the best cyclic and rate performance. It can deliver the discharge capacity of 135 mAh/g at 0.2 C rate. Even at 5 C rate, it still delivers over 87.4 % capacity retention compared to that of 0.2 C. Through long cycle test, the LiCr0.2Ni0.4Mn1.4O4 cathode material delivers the discharge capacitie of 135.7 mAh/g with 97.6 % capacity retention after 200 cycles.
    In addition, the morphology of the CNT/CF composite has been examined using energy-dispersive x-ray spectroscopy, and the results indicate that a CNT layer uniformLy deposites on the CFs. The CNT/CF anode shows better performance than the CF anode in terms of specific capacity, cycling stability, and rate capability. Even at 0.5 C rate, it still delivers discharge capacitie of 283 mAh/g. Through long cycle test, the CNT/CF anode material indicates the discharge capacitiey of 344 mAh/g with 86 % capacity retention after 100 cycles.

    摘要 i Abstract ii 誌謝 iii 目錄 iv 圖目錄 viii 表目錄 xiv 第一章、緒論 1 1-1 鋰電池產業應用及未來趨勢 1 1-1-1鋰離子電池用於電動車的發展趨勢 3 1-1-2鋰離子電池用於智慧型手機的發展趨勢 4 1-2 鋰離子電池組成及工作原理 4 1-3 鋰離子電池組成材料 6 1-3-1 鋰離子電池正極材料 6 1-3-2 鋰離子電池負極材料 11 1-3-3 黏著劑 12 1-3-4 隔離膜 14 1-3-5 電解質 15 1-3-6 集電體 15 1-4 研究動機 16 第二章、文獻回顧 17 2-1 LiMn2O4 17 2-2 LiNi0.5Mn1.5O4 (LNMO) 正極材料 17 2-3 過渡金屬摻雜 26 2-4 碳材集電體 33 2-5 無黏合劑電極 39 第三章、實驗方法 43 3-1 實驗架構 43 3-2 複合型電極和鈕扣型電池製備 45 3-2-1 實驗藥品與儀器 45 3-2-2 碳纖維前處理 46 3-2-3 複合型活性材料製備 47 3-2-4 LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4複合正極製備 48 3-2-5 CNT/CF複合型負極製備 49 3-2-6 鈕扣型電池CR2032製備 49 3-3 電極材料分析與電化學性質測試 50 3-3-1 X光繞射分析 (X-ray Diffraction, XRD) 51 3-3-2 穿透式電子顯微鏡 (Transmission Electron Microscopy, TEM) 52 3-3-3 場放射掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 53 3-3-4 傅 立 葉 轉 換 紅 外 線 光 譜 分析 (Fourier Transform Infrared Spectroscopy, FTIR) 54 3-3-5 熱重量分析 (Thermogravimetric Analyzer, TGA) 54 3-3-6 X射線光電子能譜分析 (X-ray Photoelectron Spectroscopy, XPS) 55 3-3-7 充放電測試 55 3-3-8 循環伏安法分析 (Cyclic Volrammetry, CV) 56 3-3-9 交流阻抗分析 (Electrochemical Impedance Spectra, EIS) 56 第四章、結果與討論 57 4-1 碳纖維表面前處理 57 4-1-1 表面型態分析 57 4-2 正極材料-Li-Ni-Mn-O複合型電極 60 4-2-1 X光繞射分析-鎳錳化合物 60 4-2-2 X光繞射分析-電沉積時間 61 4-2-3 表面型態分析-電沉積時間 62 4-2-4 X光繞射分析-鍛燒時間 63 4-3 Li-Ni-Mn-Cr-O複合型電極 65 4-3-1 表面型態分析-電沉積液 65 4-3-2 X光繞射分析-電沉積電流 70 4-3-3 X光繞射分析-鉻摻雜比例 71 4-3-4 X光繞射分析-鍛燒時間 72 4-3-5 表面型態分析-鉻摻雜比例 75 4-3-6 表面官能基分析-鉻摻雜比例 78 4-3-7充放電測試 82 4-3-8快速充放電測試 86 4-3-9 循環伏安法測試 89 4-3-10 循環壽命測試 90 4-3-11 電化學阻抗測試 92 4-4 負極材料-Carbon Nanotube (CNT) / CF複合型電極 96 4-4-1 表面型態分析-電泳沉積效率 96 4-4-2 表面型態分析-官能基&熱穩定性 99 4-4-3 充放電測試 101 4-4-4 快速充放電測試 102 4-4-5 循環伏安法測試 104 4-4-6 循環壽命測試 105 4-4-7 電化學阻抗測試 106 第五章、結論與未來展望 108 5-1 結論 108 5-1-1 LiNi0.5(1-x)Mn1.5(1-x/3)CrxO4/CF高電壓複合正極 108 5-1-2 CNT/CF複合負極 110 5-2 未來展望 111 第六章、參考文獻 112 附錄 119

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