臺灣博碩士論文加值系統

硼系添加劑運用於鋰離子電池研究中正快速地增長. 在此篇研究中, 以鋰鎳錳鈷氧(NMC)作為正極材料, 介相石墨碳微球(MGP)為負極材料, 硼系酯類添加劑(BAME & PBAME)和一種商用的成膜型添加劑1,3-丙烷磺內酯(PS)加入1.0MLiPF6 EC/DEC(1:1 w/w)電解液中進行1C(2000mA),2.5V~4.35V的循環特性比較及研究。BAME,PBAME和PS之間的特性以循環伏安(CV)和交流阻抗測試(EIS)進行驗證。添加劑具有不同的特性促進穩定的固液介面膜(SEI)生成於電極表面上。0.25%的PBAME增加了NMC/MGP電池在-10oC和25oC下的循環壽命。同時，增加了電池在25oC環境下的倍率性能。根據循環伏安測試所示，PBAME促進了電極表面上固液介面膜的鋰鹽如LiF，Li2CO3和Li2O的溶解，並由交流阻抗測試證明此作用降低了固液介面膜的阻抗。但是，PBAME的添加量增加也同時增加了PBAME在正極上裂解的機率。因此，0.25%的PBAME被視為此系統的最佳添加值。

The use of boron-based compounds in lithium ion batteries as an electrolyte additive is a fast-growing area of research. In this study, the effects of boron-based esters including BAME and PBAME on the battery performance of NMC/MGP using 1.0 M LiPF6 in EC/DEC (1:1 w/w) as electrolyte cycled at 1 C (2000 mA) between 2.5 and 4.35V were investigated. 1,3-propane sultone (PS), a commonly used solid electrolyte interface(SEI) film forming additive, was also tested for comparison. The electrochemical properties of the EC/DEC electrolyte with PBAME, BAME, and PS were characterized by discharge/charge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). These additives have unique characteristics that facilitate in forming a stable SEI on the electrode surface. The addition of 0.25% PBAME improved the cycle performance of NMC/MGP at -10oC and 25oC, and enhanced the rate capability at 25oC. According to CV of MGP/Li, the presence of PBAME enhanced the dissolution of lithium salt such as LiF, Li2CO3 and Li2O in SEI, and consequently decreased the resistance of SEI, which was confirmed by EIS. However, the higher PBAME loading increased the probability of the decomposition of PBAME on the cathode. An optimal loading of 0.25% PBAME was observed.

摘要 i
Abstract ii
誌謝 iii
Table of contents iv
List of Figure v
List of Table vii
Chapter 1 - Introduction 1
1.1-Cathode material 2
1.2-Anode material 6
1.3-Functional electrolyte 8
Chapter 2-Paper Review 9
2.1- sulfur-based additive 10
2.2-Boron-based additive 16
Chapter 3- Motivation 20
Chapter 4- Experimental 21
4.1-18650 batteries fabrication 21
4.2-EIS measurement 22
4.3-Cyclic voltammetry 23
Chapter 5-Results and Discussion 24
Chapter 5- Conclusions. 42
References 43

1.O. Kazunori, M. Yokokawa, 10th Int. Seminar of Primary and Secondary Battery. Technology Applications, 1-4 Mar. 1993, Deerfield Beach, FL, USA, Florida Educational Seminars, Boca Raton, FL.
2.FY 2013 Annual Progress Report.
3.K. Mizushima, P.C. Jones, P.J. Wiseman, J.B. Goodenough, Mat. Res. Bull. 15 (1980) 783-789.
4.A. Manthiram, J. B. Goodenough, J. Power Sources 26 (1989) 403–408.
5.A. Manthiram, J. B. Goodenough, J. Solid State Chem. 71 (1980) 349–360.
6.Z. Chena and J. R. Dahn, J. Electrochem. Soc. 149 9 (2002) A1184-A1189.
7.L. X. Yuan, Z. H. Wang, W. X. Zhang, X. L. Hu, J. T. Chen, Y. H. Huang, J. B. Goodenough, J. Energy Environ Sci. 4 (2011) 269–284.
8.Z. H. Lu, D. D. MacNeil, J. R Dahn, J. Electrochem. Solid-State Lett. 4 (2001) A200.
9.T. Ohzuku, Y. Makimura, J. Chem. Lett. (2001) 642.
10.N. Yabuuchi, T. Ohzuku, J. Power Sources 146 (2005) 636–639.
11.A. Bomme, J. R. Dahn, J Electrochem Soc. 156 (5) (2009) A362-A365.
12.B. Stiaszny, J. C. Ziegler, E. E. Krauß, M. Zhang, J. P. Schmidt, E. I. Tiffée, J. Power Sources 258 (2014) 61-75.
13.P. Arora, R. E. White, M. Doyle, J. Electrochem. Soc. 145 (1998) 3647-3667.
14.M. Wohlfahrt-Mehrens, C. Vogler, J. Garche, J. Power Sources 127 (2004) 58-64.
15.J. Vetter, P. Novák, M. R. Wagner, C. Veit, K. C. Möller, J. O. Besenhard, M. Winter, M. W. Mehrens, C. Vogler, A. Hammouche, J. Power Sources 147 (2005) 269-281.
16.L. J. Fu , H. Liu, C. Li, Y. P. Wu, E. Rahmb, R. Holzeb, H. Q. Wua, J. Solid State Sci. 8 (2006) 113–128.
17.Y. K. Sun, C. S. Yoon, I. H. Oh, J. Electrochim. Acta 48 (2003) 503-506.
18.M. Ge, J. Rong, X. Fang, C. Zhou, J. Nano Lett. 12 (2012) 2318-2323.
19.C. K. Chan, H. Peng, G. Liu, K. McIlwrath, X. F. Zhang, R. A. Huggins, Y. Cui, J. Nature Nanotech. 3 (2008) 31 – 35.
20.R. Alcantaraa, F. J. F. Madrigala, P. Lavelaa, J. L. Tiradoa, J. M. Jimenez Mateosb, C. G. de Salazarb, R. Stoyanovac, E. Zhechevac, J. Carbon 38 (2000) 1031–1041.
21.S. Goriparti, E. Miele, F. D. Angelis, E. D. Fabrizio, R. P. Zaccaria, C. Capiglia, J. Power Sources 257 (2014) 421-443.
22.M.S. Whittingham, J. Science 192 (1976) 1126.
23.K. Xu, J. Chem. Rev. 104 (2004) 4303 – 4418.
24.Y. Zhang, Y. Zhang, S. Xia, P. Dong, L. Jin, J. Song, Am. J. Anal. Chem. 04 (2013) 7-12.
25.K. E. Gubbins, J. Mol. Phys. 111 (2013) 3666 –3697.
26.J. B. Goodenough, Y. Kim, J. Chem. Mater. 2010, 22, 587 –603.
27.S. S. Zhang, J. Power Sources 162 (2006) 1379–1394.
28.X. Zuo, M. Xu, W. Li, D. Su, J. Liu, J. Electrochem. and Solid-State Lett., 9 (4) (2006) A196-A199.
29.J. Pires, L. Timperman, A. Castets, J. S. Pena, E. Dumont, S. Levasseur, R. Dedryvere, C. Tessier, M. Anouti, J. RSC Adv. 5 (2015) 42088.
30.X. Sun, H. S. Lee, X. Q. Yang, J. McBreen J. Electrochem. Soc. 149 (3) (2002) A355-A359.
31.Y. K. Choi, K. I. Chung, W. S. Kim, Y. E. Sung, S. M. Park, J. Power Sources 104 (2002) 132-139.
32.X. Sun, H. S. Lee, X. Q. Yang, J. McBreen, J. Electrochem. and Solid-State Lett. 6 (2) (2003) A43-A46.
33.X. Sun, H. S. Lee, X. Q. Yang, J. McBreen, J. Electrochem. Solid-State Lett. 5 (2002) A248.
34.Z. Cai, Y. liu, J. Zhao, L. Li, Y. Zhang, J. Zhang, J. of Power Sources 202 (2012) 341.
35.Y. Liu, L. Tan, L. Li, J. Power Sources 221 (2013) 90.
36.S.Y.Haa, J.G.Hana, Y.M.Songa, M.J.Chuna, S.Hanb, W.C.Shinb, N.S.Choia, J. Electrochi. Acta 104 (2013) 170– 177.
37.林哲暐, 硼系電解液添加劑及水系黏著劑應用於磷酸亞鐵鋰電池 (2016) 碩士論文.
38.Alexander, Charles; Sadiku, Matthew (2006). Fundamentals of Electric Circuits (3, revised ed.). McGraw-Hill. pp. 387–389.
39.M. Doyle, T. F. Fuller, and J. Newman, J. Electrochim. Acta, 39 (1994) 2073.
40.S. J. An, J. Li, C. Daniel, D. Mohanty, S. Nagpure, D. L. Wood, J. Carbon 105 (2016) 52.