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研究生： 王紹宇
Wang, Shao-Yu
論文名稱： 以SPM技術研究鋰電池之LiCoO2陰極材料電化學性質
The Investigation of Electrochemical Properties in LiCoO2 Cathode of Li Battery via SPM Techniques
指導教授： 劉浩志
Liu, Hao-Chih
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2012
畢業學年度： 100
語文別： 中文
論文頁數： 81
中文關鍵詞： 鋰電池 、掃描探針顯微術 、電化學阻抗分析 、鋰鈷氧
外文關鍵詞： Li battery, Scanning probe microscopy, Electrochemical impedance spectroscopy, LiCoO2
相關次數： 點閱：146  下載：3 
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    • 本研究旨在建立一套結合掃描探針顯微術與電化學阻抗分析的平台，並針對鋰電池內的LiCoO2鋰鈷氧陰極材料作初步的微區阻抗分析。為了瞭解與比較微區阻抗量測和過去一般阻抗量測結果的不同之處，本實驗的鋰電池組裝方式分為”半開放式電池” 及“正常型式電池”兩種，前者即用來搭配微區阻抗量測；且微區阻抗量測亦分為使用三軸探針座上的Tungsten probe或是使用AFM探針進行量測。
    實驗結果發現，使用三軸探針座上的Tungsten probe或AFM探針對半開放式電池作微區阻抗分析時，在Nyquist plot的高頻區都會出現探針與試片之間接觸電阻和接觸電容效應所導致的半圓，而該半圓並不會出現在正常型式電池的量測中。另一方面，使用AFM探針作微區阻抗分析時，低頻區會出現一條反映擴散特性的Warburg阻抗曲線，該曲線並未在使用三軸探針座的量測情況下發現，原因可能是由於AFM探針針尖的電流密度較高，因此對LiCoO2產生更大的離子遷移和極化作用，所以在該微區阻抗分析中較容易觀察到擴散特性。

    The major purpose of this study is to establish a platform, which is to use the combination of scanning probe microscopy and electrochemical impedance spectroscopy techniques to measure the micro-region impedance of the LiCoO2 material in the Li battery.
    In order to discriminate the impedance characteristics between micro-region and normal ones, we have designed and assembled the “semi-exposed cell” and “typical cell” to execute the EIS measurements. The “semi- exposed cell” is used to measure the micro-region impedance; there are two ways to measure the micro-region impedance, one is performed by manipulator, the other is by AFM.
    The experimental results, which are performed by the manipulator or AFM, show an additional semicircle in the high-frequency region in Nyquist plot, and this semicircle is caused by tip-sample contact resistance and contact capacitance.
    There is a Warburg impedance characteristic in low-frequency region measured by AFM, though the Warburg characteristic is not found in the manipulator case. We attribute the Warburg characteristic to the high current density in the AFM tip, which induces larger ion-migration and polarization in the LiCoO2 material, so that we can easily find the diffusion effects in this case.

    摘要 i Abstract ii 誌謝 iii 目錄 v 圖目錄 ix 表目錄 xii 第1章 序論 1 1.1 前言 1 1.2 文獻回顧 2 1.3 研究動機 6 第2章 理論基礎 7 2.1 鋰電池簡介 7 2.1.1 陰極材料 10 2.1.2 陽極材料 14 2.1.3 電解質 15 2.2 電化學阻抗分析法 17 2.2.1 交流法中的複數阻抗 17 2.2.2 等效電路元件 21 2.3 掃描探針顯微術 24 2.3.1 顯微術發展沿革 24 2.3.1.1 光學顯微術(OM) 24 2.3.1.2 電子顯微鏡(EM) 24 2.3.1.3 掃描探針顯微術(SPM) 25 2.3.2 原子力顯微鏡 27 2.3.2.1 基本原理與架構 27 2.3.2.2 接觸式 30 2.3.2.3 非接觸式 31 2.3.2.4 輕敲式 31 2.3.3 掃描阻抗分析顯微術 32 2.3.3.1 基本原理與架構 32 2.3.3.2 金屬探針的使用 33 第3章 實驗方法與流程 37 3.1 實驗藥品 37 3.2 儀器設備 38 3.3 實驗流程 43 3.3.1 實驗架構圖 43 3.3.2 LiCoO2陰極試片之製備 44 3.3.2.1 基板 44 3.3.2.2 前驅液 45 3.3.2.3 旋轉塗佈法步驟 46 3.3.2.4 燒結熱處理 47 3.3.2.5 薄膜表面形貌觀察 47 3.3.3 鋰電池組裝 48 3.3.3.1 正常型式電池 48 3.3.3.2 半開放式電池 49 3.3.4 電化學分析測試 51 3.3.4.1 手套箱設置 51 3.3.4.2 充放電與交流阻抗分析測試 54 第4章 結果與討論 56 4.1 陰極試片表面形貌 56 4.2 交流阻抗圖譜分析 58 4.2.1 正常型式電池 58 4.2.2 半開放式電池 64 4.2.2.1 搭配三軸探針座之量測 64 4.2.2.2 搭配原子力顯微鏡之量測 69 第5章 結論及未來展望 73 5.1 結論 73 5.2 未來展望 74 第6章 參考文獻 76 圖目錄 Fig. 1 1 AFM images and a depth profile of selected 5 x 5 mm area of Li 4 Fig. 1 2 In situ AFM images of n-Sn32Co38C30 electrochemically 4 Fig. 1 3 Lithium intercalation map in LiCoO2. (a) Illustrating the local distribution of lithium diffusivity for a randomly selected cathode area. (b) Electromechanical hysteresis loops extracted from the indicated locations. 5 Fig. 1 4 In situ AFM images of a Sn-foil anode in 1 M LiPF6, EC:DEC (1:2 w/w) recorded at different potentials and the corresponding voltammogram (1st cycle) performed between the OCP (2.7 V) and 0.7 V at 2 mV.[18] 5 Fig. 2 1 Comparison of the different battery technologies in terms of volumetric and gravimetric energy density.[20] 8 Fig. 2 2 The charge/discharge mechanism in “Li batteries” and “Li-ion batteries”. 9 Fig. 2 3 The lattice in LiCoO2. [29] 13 Fig. 2 4 The dissolution/deposition of the Li metal during discharge/charge. 15 Fig. 2 5 The impedance Z plotted as a planar vector using rectangular and polar coordinates.[51] 20 Fig. 2 6 Simulated Nyquist plot of a resistor and a CPE in parallel over the frequency range 1 MHz to 1 mHz ( R = 10 Ω , Q = 0.01 Ω−1sn ). [52] 23 Fig. 2 7 Schematic of a typical AFM.[68] 28 Fig. 2 8 Interatomic force variation versus distance between AFM tip and sample.[5] 29 Fig. 2 9 Schematic of a typical SIM system.[64] 32 Fig. 2 10 Simple equivalent circuit model of the tip/sample contact.[64] 33 Fig. 2 11 The tip of the metal probe for AFM. 34 Fig. 2 12 Force curve testing of the metal probe. 36 Fig. 3 1 MS-700AFM. 38 Fig. 3 2 Ref600. 38 Fig. 3 3 lab master 100. 39 Fig. 3 4 MH-300. 40 Fig. 3 5 DC400. 40 Fig. 3 6 PM490 41 Fig. 3 7 Forced Convection Oven DK-600 41 Fig. 3 8 CH R11B 42 Fig. 3 9 JSM-7001F 42 Fig. 3 10 Experimental flow chart. 43 Fig. 3 11 Schematic representation of Pt-coated Si wafer. 44 Fig. 3 12 The rotator of the spin-coater. 46 Fig. 3 13 Schematic representation of “typical cell” assembling. 49 Fig. 3 14 Schematic representation of “semi-exposed cell” assembling. 50 Fig. 3 15 Schematic representation of the electrochemical testing with manipulator. 50 Fig. 3 16 Schematic representation of the electrochemical testing with AFM. 50 Fig. 3 17 The frame with the OM. 52 Fig. 3 18 Schematic represention of the analyze system. 52 Fig. 3 19 The analysis system with the AFM. 53 Fig. 3 20 The analysis system with the manipulator. 53 Fig. 4 1 The SEM top-view image of the LiCoO2. 56 Fig. 4 2 The SEM cross-sectional image of the LiCoO2. 57 Fig. 4 3 The AFM image of the LiCoO2. 57 Fig. 4 4 EIS data of the “typical cell” measured in three different OCV. 61 Fig. 4 5 The equivalent circuit of the typical cell analysis. 61 Fig. 4 6 Frumkin Impedance Model. [50] 63 Fig. 4 7 Experimental Nyquist plots obtained at the beginning of the deintercalation. [50] 63 Fig. 4 8 (a) EIS data of the “semi-exposed cell” measured in three different OCV by the manipulator; (b) focus on the high-frequency region. 66 Fig. 4 9 The equivalent circuit of the semi-exposed cell analysis with manipulator. 67 Fig. 4 10 Schematic representation of the path of electron in the typical cell. 68 Fig. 4 11 Schematic representation of the path of electron in the semi-exposed cell. 68 Fig. 4 12 (a) EIS data of the “semi-exposed cell” measured in three different OCV by the AFM; (b) focus on the high-frequency region. 71 Fig. 4 13 The equivalent circuit of the semi-exposed cell analysis with AFM. 72 表目錄 Table 2 1常見的鋰電池陰極材料比較表。 11 Table 2 2等效電路元件之相位差值。 19 Table 2 3等效電路元件及其阻抗關係式。 21 Table 2 4金屬探針之懸臂樑相關幾何參數。 35 Table 3 1交流阻抗分析測試之參數設定。 54 Table 4 1正常型式鋰電池在不同開路電壓下所得的各阻抗等效元件模擬參數。 62 Table 4 2半開放式鋰電池搭配三軸探針座量測所得的各阻抗等效元件模擬參數。 67 Table 4 3 半開放式鋰電池搭配AFM量測所得的各阻抗等效元件模擬參數。 72

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