以固態法合成LiFePO4/C正極材料與其電性之探討

簡易檢索 / 詳目顯示

回結果列表

研究生：	賴恬郁 Lai, Tien-Yu
論文名稱：	以固態法合成LiFePO4/C正極材料與其電性之探討 Synthesis of the LiFePO4/C Cathode Material by the Solid-State Method and Associated Electrochemical Properties
指導教授：	杜正恭 Duh, Jenq-Gong
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2009
畢業學年度：	97
語文別：	英文
論文頁數：	85
中文關鍵詞：	磷酸鋰鐵、固態法
外文關鍵詞：	LiFePO4/C, solid-state method
相關次數：	點閱：4 下載：0
分享至:	分享至facebook 分享至twitter

查詢本校圖書館目錄查詢臺灣博碩士論文知識加值系統勘誤回報

The LiFePO4 powder was synthesized at 750 oC by the solid-state method. LiFePO4/C composites with glucose as the carbon source were also synthesized from 650 oC to 800 oC. The carbon coating method could improve the conductivity of LiFePO4 cathode materials, and also enhance the retention and capacity of LiFePO4. The Fe2P impurity could improve the conductivity of LiFePO4/C composites. The polarization of LiFePO4/C with appropriate amount of Fe2P is reduced at a higher current rate. However, large amount of Fe2P impurities could prohibit the pathway of lithium ions of LiFePO4/C, resulting in the decrease in the capacity of LiFePO4/C at a higher current rate. Therefore, the amount of Fe2P impurities should be carefully controlled when synthesizing LiFePO4 cathode materials.

The structural transformations, the change in the valence state of iron, and the bonding changes of LiFePO4 taking place during charge and discharge were studied by in-situ X-ray diffraction (XRD) and adsorption (XAS). The Fe2P impurities were revealed for the LiFePO4/C samples. The valence state of iron changed from 2+ to 3+ and the bonding length of Fe-O and Fe-P shrank during the two phase transformation (LiFePO4-FePO4) in LiFePO4 synthesized at 750 oC under charging at 0.14 C. On the contrast, the LiFePO4/C synthesized at 800 oC presented a normal structural transformation process, which was due to the existence of Fe2P impurities. However, the delayed structural transformation of LiFePO4/C synthesized at 750 oC was observed during charge and discharge at a lower rate (0.25 C) rather than at a higher rate (0.5 C). It was argued that the nucleation mechanism of LiFePO4 played an important role in the biphasic transformation of the delayed structure.

此研究係使用固態法在燒結溫度750 oC的條件下合成LiFePO4粉末，在製程溫度650到800 oC中並添加葡萄糖做為碳源的情況下合成多種複合材料LiFePO¬4/C以做比較。鍍碳的方式使LiFePO4的導電度增加，同時也提升LiFePO4的電容量與改善其電性穩定度。Fe2P雜相的存在能有效地增加LiFePO4/C的導電性，適量的Fe2P更能降低LiFePO4/C在高速充放電時的極化現象。但是過量的Fe2P會阻礙LiFePO4/C的1D鋰離子進出通道，致使其電容量在高速充放電下有下降的情形。因此，為了避免上述情形發生，合成LiFePO4/C時必須小心地控制Fe2P雜相生成的量。
本研究中使用高能量同步輻射X光觀察LiFePO4/C充放電過程中發生的結構轉變、價數改變與鍵結變化。合成溫度為750 oC的LiFePO4/C在0.14 C的充電兩相轉變過程中，呈現價數改變與鍵結變化趨勢。相較於在較高充放電速率0.5 C的情形，合成溫度為750 oC的LiFePO4/C在較低的充放電速率0.25 C下，會有重疊的兩相結構轉換區間(相遲疑現象)存在。而合成溫度為800 oC的LiFePO4/C在充放電速率0.25 C下，沒有相遲疑的現象發生。此肇因於LiFePO4兩相轉變時的成核機制在相遲疑現象中扮演了很重要的角色。

List of Tables.....................................    III
Figures Caption....................................    IV
Abstract...........................................    VIII
Chapter 1 Introduction.............................    1
Chapter 2 Literature Review........................    5
    2.1 Lithium Ion Batteries (LIBs) ………..    5
        2.1.1 Overview of Rechargeable Batteries..........................................    5
        2.1.2 Evolution of Lithium Ion Batteries..........................................    6
        2.1.3 Cathode Materials..........................................    7
            2.1.3.1 Layer-Structured LiCoO2 and LiNiO2..................................    7
            2.1.4.2 Spinel LiMn2O4............................................    9
            2.1.4.3 Olivine LiFePO4............................................    11
    2.2 Introduction of the LiFePO4 Structure……………..….......................…….    13
        2.2.1 Structure and phase of the LiFePO4…………………..............................    13
        2.2.2 Lithium Intercalation/Deintercalation Process of
        the LiFePO4………………………..    14
           2.2.2.1 Reaction Model………………………………......................    14
2.2.2.2 In-Situ XRD and XAS studies………………...    15
2.3 Synthesis of LiFePO4 Powder…………………..……    17
    2.4 The Properties of the LiFePO4 Cathode Materials…………..................................    18
       2.4.1 Advantages and Disadvantages of the LiFePO4……........................................    18
2.4.2 Improving the Conductivity of LiFePO4………..    19
            2.4.2.1 Non-Lattice Doping – Carbon Coating………...............................    19
            2.4.2.2 Lattice Doping – High Valence Metal Doping...............................    20
            2.4.2.3 The Presence of Fe2P Impurities in the LiFePO4…..................………    21
Chapter 3 Experimental Procedure….……………………    42
    3.1 LiFePO4 Powder Preparation by the Solid-State Method…......................................42
    3.2 Characterization and Analysis…………    43
       3.2.1 Compositional Evaluation…………………    43
3.2.2 Phase Identification…………………….…………    43
3.2.3 Morphological Observation and Particle Size
        Distribution…………………..………….    43
3.2.4 Near-Surface Structure of Carbon Films……...    44
3.2.5 Electrochemical Characterization.............    44
        3.2.6 In-Situ Synchrotron X-ray Diffraction........................................    45
        3.2.7 In-situ X-ray Absorption Spectroscopy………………...........................    46
Chapter 4 results and discussion……....……….……    49
    4.1 Compositional Evaluation……………….    49
4.2 Phase Identification………...………………………    49
    4.3 Morphology and Microstructure……………………………    50
    4.4 Particle Size…………………………………………………    51
    4.5 Structure of Carbon Films of the LiFePO4/C……………….    51
    4.6 Electrochemical Properties………………………………….    52
    4.7 In-Situ X-ray Adsorption Analysis…………………………    54
4.8 In-Situ X-ray Diffraction Analysis………………………….    57
Chapter 5 Conclusions......................................................................    77
References............................................................................................    79

                                

[1] A. V. Fraioly, W. A. Barber, and A. M. Feldman, R. S. Patent 3, 551 (1970) 205.
[2] J. P. Gabano, French Patent 1, 586 (1969) 804.
[3] J. Moser, U. S. Patent 3, 660 (1972) 163.
[4] A. A.Schneider and J. Noser, U. S. Patent 3, 674 (1972) 562.
[5] M. Wakihara, Materials Science and Engineering R33 (2001) 109.
[6] J. M. Tarascon and D. Guyomard, Electrochemical Acta, 9 (1993) 1221-1231.
[7] P. G. Bruce, Chem. Comm., 19 (1997) 1817.
[8] M. S. Whittingham, Science 192 (1976) 1126–1128.
[9] K. Mizushima, P. C. Jones, P. J. Wiseman, and J. B. Goodenough, Mater. Res. Bull., 15 (1980) 783-789.
[10] J. R. Dahn, U. von Sacken, M. R. Juzkow, and H. Al-Janaby, J. Electrochem. Soc., 138 (1991) 2207-2211.
[11] T. Ohzuku, A. Ueda, M. Nagayama, Y. Iwakoshi, and H. Komori, Electrochemical Acta, 38 [9] (1993) 1159-1167.
[12] M. M. Thackeray, P. J. Johnson, L. A. De Picciotto, P. G. Bruce, and J. B. Goodenough, Mater. Res. Bull., 19 (1984) 179-187.
[13] G. T. K. Fey, K. S. Wang, and S. M. Yang, J. Power Sources, 68 (1997) 159-165.
[14] A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, J. Electrochem. Soc. 144 (4), (1997) .
[15] J.-M. Tarascon and M. Armand, Nature, 414 (2001) 359.
[16] Y. Nishi, J. Power Sources, 100 (2001) 101.
[17] J. Hajek, French Patent, 8 (1949) 10.
[18] J. M. Amarilla, J. L. M. de Vidales, and R. M. Rojas, Solid State Ionics,127 (2000) 73-81
[19] A. A. Schneider, U. S. Patent No. 4,010,043 (1972).
[20] K. A. Klinedinst, U. S. Patent No. 4,176,214 (1979).
[21] T. Ohzuku and R. J. Brodd, J. Power Sources, 174 (2007) 449.
[22] M. M. Thackeray, W. I. F. David, P.G. Bruce and J. B. Goodenough, Mat. Res. Bull. 18 (1983) 461.
[23] T. Nagaura, Prog. Batteries Solar Cells 10 (1991) 209.
[24] K. Ozaea, Solid State Ionics 69 (1994) 212.
[25] 吴宇平,戴晓兵,马军旗,程预江, 锂离子电池- 应用与实践, 化学工业出版社, 北京,2004.
[26] H. Yoshizawa and T. Ohzuku, Abstract #467 IMLB2006, Biarritz, France, June, 2006.
[27] A. Van der Ven, M. K. Aydinol, and G. Ceder, Phys. Rev. B, 58 (1998) 2975-2987.
[28] G. G. Amatucci, J. M. Tarascon, and L. C. Klein,. J. Electrochem. Soc., 143 (1996) 1114.
[29] J. N. Reimers and J. R. Dahn, J. Electrochem. Soc., 139 (1992) 2091.
[30] J. Morales, C. Perez-Vicente, J.L. Tirado, Mater. Res. Bull., 25 (1990) 623.
[31] C. C. Chang, J. Y. Kim, and P. N. Kumta, J. Power Sources, 89 (2000) 56-63.
[32] J. M. Tarascon and D. Guyomard, Electrochimica Acta, 9 (1993) 1221.
[34] T. Ohzuku, M. Kitagowa and T. Hiral, J. Electrochem. Soc., 17 (1990) 769.
[35] R. J. Gummow, A. Dekock and M. M. Thackeray, Solid State Ioics, 69 (1994) 59-67.
[36] R. K. Mishra and G. Thomas, J. Appli. Phys., 48 (1977) 4576-4580.
[37] J. M. Tarascon, E. Wang and F.K. Shokoohi, J. Electrochem. Soc., 138 (1991) 2859-2864.
[38] D. H. Doughy, SAMPLE Journal, 32 (1996) 75-81.
[39] N. Ravet, Y. Chouinard, J. F. Magnan, S. Besner, M. Gauthier, M. Armand, J. Power Sources, 97-98 (2001) 503-507.
[40] J. K. Kim, G. Cheruvally, J. W. Choi, J. U. Kim, J. H. Ahn, G. B. Cho, K. W. Kim and H. J. Ahn, J. Power Sources, 166 (2007) 211
[41] S. Y. Chung, J. T. Bloking and Y.M. Chiang, Nature Mater., Vol. 1 (2002) 123.
[42] W. Ojczyk, J. Marzec, K. Swierczek, W. Zajac, M. Molenda, R. Dziembaj and J. Molenda, J. Power Sources, 173 (2007) 700.
[43] C. Ouyang, S. Shi, Z. Wang, X. Huang, and L. Chen, Phys. Rev. B 69 (2004) 104303.
[44] S. –I. Nishimura, G. Kobayashi, K. Ohoyama, R. Kanno, M. Yashima, A. Yamada, Nature mater. Vol. 7 (2008).
[45] M. S. Islam, D. J. Driscoll, C. A. J. Fisher, and P. R. Slater, Chem. Mater. 17 (2005) 5085-5092.
[46] C. A. J. Fisher and M. S. Islam, J. Mater. Chem. 18 (2008) 1209-1215.
[47] A. Yamada, H. Koizumi, S. –I. Nishimura, N. Sonyama, R. Kanno, M. Yonemura, T. Nakamura, and G. Kobayashi, Nature mater. Vol. 5 (2006).
[48] V. Srinivasan, and J. Newman, Electrochem. Solid State Lett. 9, (2006) A110-A114.
[49] V. Srinivasan and J. Newman, J. Electrochem. Soc., 151(10) (2004) A1517-A1529.
[50] M. Yonemura, A. Yamada, Y. Takei, N. Sonoyama, and R. Kanno, J. Electrochem. Soc., 151 (2004) A1352-A1356.
[51] C. Delmas, M. Maccario, L. Croguennec, F. Le Cras, and F. Weill, Nature mater. Vol. 7 (2008).
[52] G. Chen, X. Song, and T. J. Richardson, Electrochem. Solid State Lett., 9 (6) (2006) A295-A298.
[53] H. -H Chang, C. –C. Chang, H. –C. Wu, M. –H. Yang, H. –S. Sheu, and N. –L. Wu, Electrochem. Commun., 10 (2008) 335–339.
[54] O. Haas, A. Deb, E. J. Cairns, and A. Wokaun, J. Electrochem. Soc., 152 (1), (2005) A191-A196.
[55] S. S. Zhang, J. L. Allen, K. Xu, and T. R. Jow, J. Power Sources, 147 (2005) 234-240.
[56] A. Yamada, S. C. Chung, and K. Hinokuma, J. Electrochem. Soc., 148 (2001) A224-A229.
[57] M. –R. Yang, W. –H. Ke, and S. –H. Wu, J. Power Sources, 146 (2005) 539-543.
[58] M. –R. Yang, W. –H. Ke, and S. –H. Wu, J. Power Sources, 159 (2006) 307-311.
[59] K. S. Park, J. T. Son, H. T. Chung, S. J. Kim, C. H. Lee, and H. G. Kim, Electrochem. Commun. 5 (2003) 839-842.
[60] Z. Xu, L. Xu, Q. Lai, and X. Ji, Mat. Res. Bull. 42 (2007), 883-891.
[61] S. Franger, F. Le Cras, C. Bourbon, and H. Rouault, J. Power Sources, 119-121 (2003) 252-257.
[62] D. Y. W. Yu, K. Donoue, T. Kadohata, T. Murata, S. Matsuta, and S. Fujitani, J. Electrochem. Soc., 155 (2008) A526-A530.
[63] K. S. Park, K. T. Kang, S. B. Lee, G. Y, Kim, Y. J. Park, and H. G. Kim, Mat. Res. Bull. 39 (2004), 1803-1810.
[64] L. N. Wang, Z. G. Zhang, and K. L. Zhang, J. Power Sources, 167 (2007) 200-205.
[65] A. Yamada, M. Tanaka, K. Tanaka, and K. Sekai, J. Power Sources, 82 (1997) 73.
[66] C. H. Mi, X. G. Zhang, X. B. Zhao, and H. L. Li, J. Alloys and Compounds, 424 (2006) 327-333.
[67] F. Croce, A. D’ Epifanio, J. Hassoun, A. Deptula, T. Olczac, B. Scrosati ,Electrochem. Solid-State Lett. 5 (2002) A47.
[68] M. S. Bhuvaneswari, N. N. Bramnik, D. Ensling, H. Ehrenberg, and W. Jaegermann, J. Power Sources, 180 (2008) 553-560.
[69] L. Kavan, I. Exnar, J. Cech, and M. Graetzel, Chem. Mater. 19 (2007) 4716-4721.
[70] S. Lim, C. S. Yoon, and J. Cho, Chem. Mater. 20 (2008) 4560-4564.
[71] H. C. Shin, W. I. Cho, H. Jang, Electrochi. Acta, 52 (2006) 1472-1476.
[72] J. –K. Kim, G. Cheruvally, J. –H. Ahn, and H. –J. Ahn, J. Physics and Chemistry of Solids, 69 (2008) 1257-1260.
[73] C. H. Mi, X. G. Zhang, X. B. Zhao, H. L. Li, J. Alloys and Compounds, 424 (2006) 327-333.
[74] M. Ramsteiner and J. Wagner, Appl. Phys. Lett., 51 (17) (1987) 1355-1357.
[75] R. Kostecki, B. Schnyder, D. Alliata, X. Song, K. Kinoshita, and R. Kotz, Thin Solid Films, 396 (2001) 36-43.
[76] M. Koltypin, D. Aurbach, L. Nazar, and B. Ellis, J. Electrochem. Soc., 10 (2007) A40-A44.
[77] C. M. Burba and R. Frech, J. Electrochem. Soc., 151 (2004) A1032-A1038.
[78] A. A. Salah, A. Mauger, K. Zaghib, J. B. Goodenough, N. Ravet, M. Gauthier, F. Gendron, and C. M. Julien, J. Electrochem. Soc., 153(9) (2006) A1692-A1701.
[79] M. R. Roberts, G. Vitins, and J. R. Owen, J. Power Sources, 179 (2008) 754-762.
[80] N. Ravet, A. Abouimrane, and M. Armand, Nature Mater., Vol. 2 (2003) 702-703.
[81] C. –W. Ong, Y. –K. Lin, and J. –S. Chen, J. Electrochem. Soc., 154(6) (2007) A527-A533.
[82] S. W. Oh, H. J. Bang, S. –T. Myung, Y. C. Bae, S. –M. Lee, and Y. –K. Sun, J. Electrochem. Soc., 155(6) (2008) A414-A420.
[83] Y. Xu, Y. Lu, L. Yan, Z. Yang, and R. Yang, J. Power Sources 160 (2006) 570–576.
[84] H. Liu, J. Xie, and K. Wang, Solid State Ionics, 179 (2008) 1768-1771.
[85] C. W. Kim, J. S. Park and K. S. Lee, J. Power Sources, 163 (2006) 144-150.
[86] M. –S. Song, D. –W. Han, and H. –S. Kwon, Abstract #213, 215th ECS, San Franciso, CA, May, 2009.
[87] M. S. Song, D. -Y. Kim, Y. –M. Kang, Y. -I. Kim, J. –Y. Lee, and H. –S. Kwon, J. Power Sources, 180 (2008) 546-552.
[88] J. D. Wilcox, M. M. Doeff, M. Marcinek and R. Kostecki, J. Electrochem. Soc. 154 (5) (2007) A389-A395.
[89] Y. Liu, C. Pan and J. Wang, J. Electrochem. Soc. 39 (2004) 1091-1094.
[90] D. Ballutaud, F. Jomard, T. Kociniewski, E. Rzepka, H. Girard and S. Saada, Diamond and Relat. Mater. 10 (2001) 405.
[91] A. Deb, Uwe Bergmann, E. J. Cairns, and S. P. Cramer, J. Synchrotron Rad. (2004), 11, 497-504.
[92] T. –H. Cho and H. –T. Chung, J. Power Sources, 133, (2004) 272-276.
[93] A. Deb, Uwe Bergmann, S. P. Cramer, and E. J. Cairns, Electrochi. Acta 50, (2005) 5200-5207.

全文公開日期本全文未授權公開 (校內網路)
全文公開日期本全文未授權公開 (校外網路)

簡易檢索 / 詳目顯示

相關論文