矽，做為鋰離子電池中高理論電容量(3579 mA h g-1)負極材料已逐漸被重視而作應用，然而，許多問題仍需要克服如劇烈的體積膨脹~300%、差的循環穩定性，為了解決這些問題奈米結構的矽已逐漸被研究出來，包括矽奈米線、矽奈米顆粒、中空矽球、Yolk-Shell結構等等。然而最主要的問題是使用的導電添加劑與矽本身並無鍵結能力，導致充放電過程中容易失去電子接觸，在此我們提出以導電高分子作為矽基負極黏著劑，藉由高分子本身的高電子電導度(5*10-6 S cm-1)以及具有羧酸官能基的特性，使電池效果能大幅提升。Si/P[T(EH)TPA]在鋰離子電池中，以0.2A g-1電流密度充放電循環兩百圈後，電容量仍有1760 mA h g-1(第二圈的75%)，且在 4A g-1的充放電循環測試經過1000個循環仍能保有880 mAh g-1以上的克電容量。這些測試說明了Si/P[T(EH)-TPA]作為鋰離子電池的黏著劑是極度具有價值的，且能應用在更多新穎的儲能裝置上。
傳統的電極製備方式是直接將材料塗佈於金屬集流體上，然而對於電極與集流體間接觸電阻的研究卻是相對少數。本研究著重於比較不同的集流體作為提升電池穩定性的關鍵，藉由使用碳塗覆之正/負極集流體，由於其具有相對粗糙的表面能提升材料與集流體之間的黏著能力，經由膠帶剝離測試結果，未塗覆碳層的電極其活性材料與集流體明顯剝離，表明塗碳層確實能減少材料剝落的問題，並且藉由EIS測試也顯示塗碳層能有效降低電池內部阻抗。除了半電池的測試外，我們也實際將塗碳層應用於鈕扣型全電池，在1C的充放電速率下，電池的穩定性有很顯著的提升，最後更進一步組裝成軟包式全電池，並且成功的點亮了紫色的LED燈板。

Silicon, as an anode material with high theoretical capacity (3579 mA h g-1) in lithium-ion batteries has been gradually applied. However, many problems still need to be overcome, such as significant volume expansion ~300%, poor cyclic stability. In order to address these issues, the nanostructures have gradually been studied, including silicon nanowires, silicon nanoparticles, hollow silicon spheres, Yolk-Shell structures and so on. However, the main issue is that Si easily to lose the electronic connection during cycling because there is no bonding ability between active materials and conductive additives. Here, we propose to use a conductive polymer as a silicon-based anode adhesive. The high electron conductivity (5*10-6 S cm-1) of the polymer and the carboxylic acid functional group can effectively improve the battery performance. After charging and discharging at a current density of 0.2A g-1 for two hundred cycles, the capacity still has 1760 mA h g-1 (75% of the second circle), and at current density of 4 A g-1 can exceed 1000 cycles and maintain a capacity more than 880 mA h g-1. These tests demonstrate that Si/P[T(EH)-TPA] is extremely valuable as a binder for lithium-ion batteries and can be applied to more innovative energy storage devices.
The traditional way of electrodes for lithium-ion batteries is directly coated materials on metal current collectors. However, only a few studies discuss of internal resistance. This study focuses on comparing different current collectors as the key to improving battery stability. By using carbon-coated positive/negative current collectors prepared by our laboratory, the relatively rough surface enhances the adhesion between the material and the current collector and reducing the detachment of the material during charging and discharging. Through peel test results, the electrode without the carbon layer was significantly peeled off, indicating that the carbon-coating layer can reduce the problem of material flaked. EIS test also shows that the carbon coating layer can effectively reduce the internal impedance of the battery. In addition to the analysis of the half-cell, we also applied the carbon-coated layer to full cell. At the charging and discharging rate of 1C, stability of the battery significantly improved, and finally assembled into a pouch-type full cell and successfully light up the purple LED light board.

中文摘要 I
Abstract II
Contents IV
List of Tables VI
List of Figures VII
Chapter 1 conductive polymer as binder in silicon anode and Its Performance of Lithium-Ion Batteries 1
1.1. Introduction 1
1.1.1. Li-ion batteries for energy storage 1
1.1.2. Si based lithium ion batteries 2
1.1.3. Nanostructured of Si anodes 4
1.1.4. Binders for si based anode 6
1.1.5. Conjugated polymer binders 7
1-2 Experimental 12
1-2-1 Materials 12
1-2-2 Synthesis of monomers 12
1-2-3 Synthesis of polymers 15
1-2-4 Characterization 15
1-2-5 Electrochemical characterization 16
1-3 Results and Discussion 16
1.3.1. Analysis of Polymers 16
1.3.2. Electrochemical performance 20
1-4 Conclusion 29
1-5 References 30
Chapter 2 Studies of carbon-coated current collector on lithium ion batteries 34
2-1 Introduction 34
2-2 Experimental 41
2-2-1 Materials 41
2-2-2 Characterization 41
2-2-3 Electrochemical characterization 41
2-3 Results and Discussion 42
2-4 Conclusion 51
2-5 References 52

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1. Johnson, B. A.; White, R. E., Characterization of commercially available lithium-ion batteries. J. Power Sources 1998, 70 (1), 48-54.
2. Nitta, N.; Yushin, G., High-Capacity Anode Materials for Lithium-Ion Batteries: Choice of Elements and Structures for Active Particles. 2014, 31 (3), 317-336.
3. Hayner, C. M.; Zhao, X.; Kung, H. H., Materials for Rechargeable Lithium-Ion Batteries. 2012, 3 (1), 445-471.
4. Zhang, W.-J., Lithium insertion/extraction mechanism in alloy anodes for lithium-ion batteries. J. Power Sources 2011, 196 (3), 877-885.
5. Tarascon, J. M.; Armand, M., Issues and challenges facing rechargeable lithium batteries. Nature 2001, 414, 359.
6. Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D., Challenges in the development of advanced Li-ion batteries: a review. Energy & Environmental Science 2011, 4 (9), 3243-3262.
7. Wu, H.; Cui, Y., Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today 2012, 7 (5), 414-429.
8. Delong, M.; Zhanyi, C.; Anming, H., Si-Based Anode Materials for Li-ion Batteries: A Mini Review. Nano-Micro Letters 2014, 6 (4).
9. Chan, C. K.; Peng, H.; Liu, G.; McIlwrath, K.; Zhang, X. F.; Huggins, R. A.; Cui, Y., High-performance lithium battery anodes using silicon nanowires. Nature Nanotechnology 2007, 3, 31.
10. Chan, C. K.; Ruffo, R.; Hong, S. S.; Cui, Y., Surface chemistry and morphology of the solid electrolyte interphase on silicon nanowire lithium-ion battery anodes. J. Power Sources 2009, 189 (2), 1132-1140.
11. Ge, M.; Rong, J.; Fang, X.; Zhou, C., Porous Doped Silicon Nanowires for Lithium Ion Battery Anode with Long Cycle Life. Nano Letters 2012, 12 (5), 2318-2323.
12. Cui, L.-F.; Yang, Y.; Hsu, C.-M.; Cui, Y., Carbon−Silicon Core−Shell Nanowires as High Capacity Electrode for Lithium Ion Batteries. Nano Letters 2009, 9 (9), 3370-3374.
13. Cui, L.-F.; Ruffo, R.; Chan, C. K.; Peng, H.; Cui, Y., Crystalline-Amorphous Core−Shell Silicon Nanowires for High Capacity and High Current Battery Electrodes. Nano Letters 2009, 9 (1), 491-495.
14. Hwang, T. H.; Lee, Y. M.; Kong, B.-S.; Seo, J.-S.; Choi, J. W., Electrospun Core–Shell Fibers for Robust Silicon Nanoparticle-Based Lithium Ion Battery Anodes. Nano Letters 2012, 12 (2), 802-807.
15. Li, X.; Meduri, P.; Chen, X.; Qi, W.; Engelhard, M. H.; Xu, W.; Ding, F.; Xiao, J.; Wang, W.; Wang, C.; Zhang, J.-G.; Liu, J., Hollow core–shell structured porous Si–C nanocomposites for Li-ion battery anodes. Journal of Materials Chemistry 2012, 22 (22), 11014-11017.
16. Yao, Y.; McDowell, M. T.; Ryu, I.; Wu, H.; Liu, N.; Hu, L.; Nix, W. D.; Cui, Y., Interconnected Silicon Hollow Nanospheres for Lithium-Ion Battery Anodes with Long Cycle Life. Nano Letters 2011, 11 (7), 2949-2954.
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23. Liu, G.; Xun, S.; Vukmirovic, N.; Song, X.; Olalde‐Velasco, P.; Zheng, H.; Battaglia, V. S.; Wang, L.; Yang, W. J. A. M., Polymers with tailored electronic structure for high capacity lithium battery electrodes. 2011, 23 (40), 4679-4683.
24. Liu, D.; Zhao, Y.; Tan, R.; Tian, L.-L.; Liu, Y.; Chen, H.; Pan, F., Novel conductive binder for high-performance silicon anodes in lithium ion batteries. Nano Energy 2017, 36, 206-212.
25. Klavetter, K. C.; Wood, S. M.; Lin, Y.-M.; Snider, J. L.; Davy, N. C.; Chockla, A. M.; Romanovicz, D. K.; Korgel, B. A.; Lee, J.-W.; Heller, A.; Mullins, C. B., A high-rate germanium-particle slurry cast Li-ion anode with high Coulombic efficiency and long cycle life. J. Power Sources 2013, 238, 123-136.
26. Chockla, A. M.; Bogart, T. D.; Hessel, C. M.; Klavetter, K. C.; Mullins, C. B.; Korgel, B. A., Influences of Gold, Binder and Electrolyte on Silicon Nanowire Performance in Li-Ion Batteries. J. Phys. Chem. C 2012, 116 (34), 18079-18086.
27. Yu, D. Y. W.; Hoster, H. E.; Batabyal, S. K., Bulk antimony sulfide with excellent cycle stability as next-generation anode for lithium-ion batteries. Sci. Rep. 2014, 4, 4562.
28. Nguyen, D.-T.; Kang, J.; Nam, K.-M.; Paik, Y.; Song, S.-W., Understanding interfacial chemistry and stability for performance improvement and fade of high-energy Li-ion battery of LiNi0.5Co0.2Mn0.3O2//silicon-graphite. J. Power Sources 2016, 303, 150-158.
29. Youn, D. H.; Patterson, N. A.; Park, H.; Heller, A.; Mullins, C. B., Facile Synthesis of Ge/N-Doped Carbon Spheres with Varying Nitrogen Content for Lithium Ion Battery Anodes. ACS Applied Materials & Interfaces 2016, 8 (41), 27788-27794.
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