改性石墨作為無導電劑鋰離子電池之負極材料/ 矽石墨複合材料作為鋰離子電池的負極

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研究生：	阮妙金 Nguyen, Thi Kim-Dieu
論文名稱：	改性石墨作為無導電劑鋰離子電池之負極材料/ 矽石墨複合材料作為鋰離子電池的負極 Modified graphite as highly-conductive anode materials for conductive carbon free lithium ion batteries/ Silicon-graphite composites as anode material for lithium-ion batteries
指導教授：	段興宇 Tuan, Hsing-Yu
口試委員:	曾院介袁芳偉
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：	2017
畢業學年度：	105
語文別：	英文
論文頁數：	35
中文關鍵詞：	鋰離子電池、改性石墨、矽石墨複合材料
外文關鍵詞：	Lithium-ion batteries, Modified-graphite, Silicon/graphite composites
相關次數：	點閱：2 下載：0
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在过去的20年中，鋰離子電池（LIB）在市場上發揮了重要作用，作為其他可再充電電池系統具有更高重量和體積容量的主要電源供應商。然而，目前的鋰離子電池技術不能滿足從便攜式電子設備到全電動車輛和智能電網的廣泛應用的能源和電力需求。在這方面，亞洲碳素股份有限公司和Tuan教授的實驗室已經合作致力於漸進的LIB。目的是找出基於高容量，高庫侖效率，循環穩定的LIBs組裝改性石墨的最佳條件。這些改性樣品最初是石墨材料，其已經在高壓下處理以轉化其形態。樣品處理過程由公司進行。樣品數量為32個樣品，分別為G201，G202，G203至G232。為了達到這個目的，這些改性石墨樣品最初在相同的工藝（最近在第2章中描述）的半電池中組裝了陽極電極，以便在高容量，良好的庫侖效率和循環穩定性方面找到好的樣品。所有生產的漿料包括83,50重量％的活性物質，8.0重量％的超級P和8.5重量％的PVDF在NMP溶液中攪拌1.5小時。然後，他們的自行車錶演仔細對比，導致獲得四個最佳樣本。在不同的條件下進一步研究這些樣品，例如（i）各種塗層厚度和（ii）不同種類的電解質，以找出最佳樣品，並獲得組裝基於鋰離子電池的改性石墨的配方。此外，通過SEM圖像分析樣品，IV檢驗以獲得對其特徵的更多了解。
為了超越基於負極的改性石墨低能力的弱點，作者不斷開展了“矽/石墨複合材料作為陽極材料”的工作，以克服這個問題。研究表明，矽/石墨複合材料在比容量和初始效率方面有顯著改善。與僅石墨粉末相比，電極具有更高數量的充電/放電循環，具有更穩定的放電容量。

In the last two decades, Li-ion batteries (LIBs) has played a critically important role in the market as a primary power supplier with a higher gravimetric and volumetric capacity than other rechargeable-battery systems. However, current LIB technologies cannot satisfy the energy and power requirements of a wide range of applications, from portable electronic devices to all-electric vehicles and smart grids. In this regard, Asia Carbons and Technology INC company which locates at Taoyuan country, Taiwan (R.O.C) and Prof. Hsing-Yu Tuan Labortary have cooperated to dedicate to the progressive LIBs. Hence, the study was a cooperative work between Prof. Hsing-Yu Tuan Lab and the company. The aim was to find out the optimal conditions for assembling modified-graphite based on LIBs with high capacity, high coulombic efficiency, cycling stable. These modified samples were originally graphite materials, which has been treated under the high pressure to transform their morphologies. The sample treatment process was carried out by the company. The number of samples were 32 samples, namely G201, G202, G203 to G232 in order. In order to achieve the purpose, those modified graphite samples were initially assembled anode electrode in half-cells under the same process (described lately in chapter 2) to find out the good samples in terms of high capacity, good coulombic efficiency and cycling stable. All the produced slurries included 83,50 wt% active materials, 8.0 wt% super P and 8.5 wt% PVDF stirred in NMP solution for 1.5 hours. Then, their cycling performances were carefully compared to each other, based on the predefined goals (KPI), which resulted in obtaining four best samples. These samples were investigated further under different conditions such as (i) various coating thickness and (ii) different kinds of electrolytes to find out the best sample as well as to gain the recipe for assembling modified-graphite based on lithium-ion batteries. Besides that, those samples were analyzed via SEM images, IV test to obtain more understanding about their characteristics.
It is found that the modified sample named G227 stood out as a potential candidate for anode electrode in lithium battery, since it performed stably over 50 cycles with high capacity above 320 mA h/g. Another finding was that electrolyte system which includes ethylene carbonate (EC): dimethyl carbonate (DMC): fluoroethylene carbonate (FEC) 4.5:4.5:1 (v:v) in LPF6 has enhanced the good cycling performance rather than fluoroethylene carbonate (FEC): diethyl carbonate (DEC) 3:7 (v.v) and ethylene carbonate (EC): dimethyl carbonate (DMC) 1:1 (v/v) in LPF6 system. However, this work currently facing an issue that the average capacity is quite low, which needs a lot effort to solve.
In order to surpass the weakness of low capacity of modified graphite based on negative electrodes, the author continuously carried out the work named “silicon/graphite composites as anode materials” to overcome the problem. The study indicated that silicon/graphite composite has a significant improvement on specific capacity and the initial efficiency. The electrodes sustain a higher number of charge/discharge cycles with a more stable discharge capacity compared to the graphite powders only. Two full-cell coins show outstanding stability for the first 50 cycles, leading to a capacity retention of 1st sample and 2nd one are 94.68% and 92.56%, respectively. The average initial efficiency is over 86.00%. This result has exceeded the standard KPI (>85%). Besides that, the cycle performance of Si/graphite composites based-on pouch cell is also investigated. Its areal capacity and specific capacity are 3.92 mA h/cm2 and 604 mA h/g, respectively, which is much better than expected.

文章摘要    i
Abstract    ii
Content    iv
List of Figures    vi
List of Tables    ix
Chapter 1. Modified graphite as highly-conductive anode materials for conductive carbon free lithium batteries    1
1. Introduction    1
1.1. Electrochemical principles of the lithium-ion cell    2
1.1.1. Graphite electrode    2
1.1.2. Lithium ion intercalation into graphite    2
1.1.3. Solid electrolyte interface (SEI)    3
1.1.4. Electrolytess    4
1.2. Modified graphite    5
1.3. Motivation for the study    6
2. Materials and Methodology    7
2.1. Materials    8
2.2. Methodology    8
2.2.1. Testing for cycle capacity of the modified graphite samples    8
2.2.2. Characterization    9
2.2.3. Testing for capacity at various conditions    10
2.3. Fabrication of LIBs    10
3. Results and Discussion    13
3.1. Comparison the capacity of modified samples    13
3.2. Characterization    15
3.3. Capacity performance of three samples at different conditions    17
3.3.1. G220 cycling performance at different conditions    17
3.3.2. G223 cycling performance at different conditions    17
3.3.3. G227 cycling performance at different conditions    18
3.3.4. G231 cycling performance at different conditions    18
3.3.5. Capacity performance over 50 cycles    19
4. Conclusion and Future Work    20
5. References    22
Chapter 2. Silicon-graphite composites as negative electrode for lithium ion batteries    23
1. Introduction    23
2. Materials and Methodology    27
2.1. Materials    27
2.2. Methodology    28
2.3. Fabrication of full-cell coin    29
2.4. Fabrication of pouch cell    30
2.5. Lithium-ion battery electrochemical characterization    31
3. Characterization    31
4. Result and Discussion    32
4.1. SEM and EDS    32
4.2. Lithium-ion battery electrochemical characterization    32
5. Conclusion    34
6. References    35
                                

1. Goriparti, S.; Miele, E.; De Angelis, F.; Di Fabrizio, E.; Zaccaria, R. P.; Capiglia, C., Review on recent progress of nanostructured anode materials for Li-ion batteries. Journal of Power Sources 2014, 257, 421-443.
2. Editors, M. Y. R. J. B. A. K., Lithium-Ion Batteries. Science and Technologies 2009.
3. Yao, Y., Carbon based anode materials for lithium-ion batteries. University of Wollongong Theses Collection 2003.
4. Ellis, B. L.; Lee, K. T.; Nazar, L. F., Positive electrode materials for Li-ion and Li-batteries†. Chemistry of Materials 2010, 22 (3), 691-714.
5. Mattson, I. R., Stability of the Graphite Electrode for Li-ion Batteries. the Norwegian University of Science and Technology (NTNU) 2013.
6. Nitta, N.; Wu, F.; Lee, J. T.; Yushin, G., Li-ion battery materials: present and future. Materials today 2015, 18 (5), 252-264.
7. Agostini, M.; Brutti, S.; Hassoun, J., High voltage Li-ion battery using exfoliated graphite/graphene nanosheets anode. ACS applied materials & interfaces 2016, 8 (17), 10850-10857.
8. Sethuraman, V. A.; Hardwick, L. J.; Srinivasan, V.; Kostecki, R., Surface structural disordering in graphite upon lithium intercalation/deintercalation. Journal of Power Sources 2010, 195 (11), 3655-3660.
9. Profatilova, I. A.; Kim, S.-S.; Choi, N.-S., Enhanced thermal properties of the solid electrolyte interphase formed on graphite in an electrolyte with fluoroethylene carbonate. Electrochimica Acta 2009, 54 (19), 4445-4450.
10. Verma, P.; Maire, P.; Novák, P., A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries. Electrochimica Acta 2010, 55 (22), 6332-6341.
11. Gao, J.; Lowe, M. A.; Kiya, Y.; Abruña, H. c. D., Effects of liquid electrolytes on the charge–discharge performance of rechargeable lithium/sulfur batteries: electrochemical and in-situ X-ray absorption spectroscopic studies. The Journal of Physical Chemistry C 2011, 115 (50), 25132-25137.
12. Fu, L.; Liu, H.; Li, C.; Wu, Y. P.; Rahm, E.; Holze, R.; Wu, H., Surface modifications of electrode materials for lithium ion batteries. Solid State Sciences 2006, 8 (2), 113-128.
13. Zurich, E., Electrochemical and chemical surface modifications of carbons for Li-ion battery. Université de Toulouse III, France 2011.
14. Rosamaria Fong, U. v. S., Studies of Lithium Intercalation into Carbons Using Nonaqueous q Electrochemical Cells. Journal of Electrochemical Society 1990.
15. Xu, K., Electrolytes and Interphasial Chemistry in Li Ion Devices. energies ISSN 1996-1073 2010.
16. Xu, K., Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. Chemical reviews 2004, 104 (10), 4303-4418.
17. Aurbach, D., Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries. Journal of Power Sources 2000, 89 (2), 206-218.
18. Chen, G.; Weng, W.; Wu, D.; Wu, C., PMMA/graphite nanosheets composite and its conducting properties. European Polymer Journal 2003, 39 (12), 2329-2335.
1. Dash, Ranjan; Panalan, Sreekanth. Theoretical limits of energy density in silicon-carbon composite anode based lithium ion batteries. Scientific reports, 2016, 6: 27449.
2. Wu, Hui; Cui, Yi. Designing nanostructured Si anodes for high energy lithium ion batteries. Nano Today, 2012, 7.5: 414-429.
3. Su, Xin, et al. Silicon‐based nanomaterials for lithium‐ion batteries: a review. Advanced Energy Materials, 2014, 4.1.
4. Krause, Andreas, et al. High area capacity lithium-sulfur full-cell battery with prelitiathed silicon nanowire-carbon anodes for long cycling stability. Scientific reports, 2016, 6: 27982.
5. Yim, Chae-Ho; Courtel, Fabrice M. Yaser. A high capacity silicon–graphite composite as anode for lithium-ion batteries using low content amorphous silicon and compatible binders. Journal of Materials Chemistry A, 2013, 1.28: 8234-8243.
6. Markerchie, E., et al. Capacity fading of lithiated graphite electrodes studied by a combination of electroanalytical methods, Raman spectroscopy and SEM. Journal of power sources, 2005, 146.1: 146-150.
7. Wu, Yu-Ping; RAHM, Elke; HOLZE, Rudolf. Carbon anode materials for lithium ion batteries. Journal of Power Sources, 2003, 114.2: 228-236.
8. Yao, Yueping. Carbon based anode materials for lithium-ion batteries. 2003.
9. Ko, Minseong; Chae, Sujong; Cho, Jaephil. Challenges in accommodating volume change of Si anodes for Li‐ion batteries. ChemElectroChem, 2015, 2.11: 1645-1651.
10. Chan, Candace K., et al. High-performance lithium battery anodes using silicon nanowires. Nature nanotechnology, 2008, 3.1: 31-35.
11. Lian, Peichao, et al. Large reversible capacity of high quality graphene sheets as an anode material for lithium-ion batteries. Electrochimica Acta, 2010, 55.12: 3909-3914.
12. Ma, Delong; Cao, Zhanyi; Hu, Anming. Si-based anode materials for Li-ion batteries: a mini review. Nano-Micro Letters, 2014, 6.4: 347-358.
13. Jo, Yong Nam, et al. Si–graphite composites as anode materials for lithium secondary batteries. Journal of Power Sources, 2010, 195.18: 6031-6036.
14. Veluchamy, Angathevar; Doh, Chil-Hoon. Silicon Based Composite Anode for Lithium Ion Battery. In: Nanocomposites and Polymers with Analytical Methods. InTech, 2011.

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