||Micro-region Electrochemical Impedance Measurement and Analysis of Lithium Ion Battery with AFM Silicon probe as Anode
||Department of Materials Science and Engineering
lithium ion battery
atomic force microscopy
electrochemical impedance spectroscopy
在鋰離子電池的研究領域中，眾多研究皆為使用電化學阻抗分析法(electrochemical impedance spectroscopy, EIS)來探討電池系統內部的反應與變化。但在傳統的EIS實驗設置中，使用塊材形式的電極對電池進行量測，分析結果往往是整個電池系統的平均值與塊材的性質，不易觀察到電極中微細的變化。有鑑於此，本研究將藉由控制電極的大小以限制電池反應發生的區域，使用AFM探針作為EIS量測中的一極，並以本身即為電極材料的矽探針電極來獲得微區電化學阻抗圖譜，在與對電極反應面積差距極大的狀況下，阻抗圖譜資訊將主要來自於矽針電極的變化。
In the study of lithium ion battery (LIB), major parts of the analysis are carried out with the electrochemical impedance spectroscopy (EIS) to interpret the mechanism of LIB. However, in the traditional EIS set-up, the experiment result is inevitably the average value of the whole measured system, or battery. Therefore, it is difficult to observe the tiny variation of the electrode by utilizing the bulk electrode.
In this study, micro-region EIS analysis system will be constructed by combining the atomic force microscopy (AFM) and EIS. Utilize the AFM silicon probe as the electrode to restrict the reaction area in micro-region. As a result, the Nyquist plot will reflect the variation of working electrode (WE) more straight forward with the counter electrode (CE) having great reaction area than WE.
From the experiment results, the Nyquist plot of micro-region measurement is very distinct to the one of traditional EIS, specifically in the low-frequency region. In common Nyquist plot, low-frequency region often represents the diffusion phenomena, which is usually called Warburg effect, of lithium ion and display it by a tilt line. Then, diffusion coefficient of lithium ion ( DLi+) can be obtained from the related value with this line. More and more, there are different values of DLi+ obtained from the only one Nyqusit plot of micro-region measurement. It means that the micro-region measurement having the ability to distinguish the different structure in the interior of the Si-tip electrode.
一、 序論 1
1-1 前言 1
1-2 研究動機與目的 2
二、 理論基礎簡介 3
2-1 原子力顯微鏡 3
2-2 電化學阻抗量測 4
2-2-1 等效電路元件 5
2-3 鋰離子電池 8
三、 文獻回顧 10
3-1 陽極材料--矽材 10
3-2 原子力顯微鏡表面分析技術與應用 13
3-3 微區電化學阻抗量測 16
四、 實驗方法 19
4-1 實驗用品與藥品 19
4-2 儀器設備 19
4-3 實驗儀器架設 22
4-4 電化學阻抗量測 23
五、 結果與討論 25
5-1 鋰離子電池組裝結構設計 25
5-2 微區電化學阻抗量測與分析 29
5-2-1 微區阻抗圖譜分析與討論--低頻部分 32
5-2-2 微區阻抗圖譜中各介面層間的擴散現象 36
5-2-3 藉由微區阻抗圖譜分析電極材料相變化過程 41
5-2-4 微區阻抗圖譜分析與討論--高頻部分 47
5-2-5 歐傑電子能譜儀縱深分析 47
六、 結論 50
七、 未來展望 52
八、 參考文獻 53
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