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研究生:陳運昇
研究生(外文):Yun-Sheng Chen
論文名稱:應用溶膠-凝膠法製備鋰電池奈米鋰鈷氧化物(LiCoO2)粉末及其特性之研究
論文名稱(外文):Preparation and characterization of nanometric-sized LiCoO2 powders for lithium-ion battery by sol-gel process
指導教授:黃芳榮楊文都
指導教授(外文):Fang-Jung HuangWein-Duo Yang
學位類別:碩士
校院名稱:國立高雄應用科技大學
系所名稱:化學工程系碩士班
學門:工程學門
學類:化學工程學類
論文出版年:2007
畢業學年度:95
語文別:中文
論文頁數:118
中文關鍵詞:纖維素溶膠-凝膠鋰離子二次電池
外文關鍵詞:Hydroxypropyl celluloseLithium-ion batterieslithium cobalt oxides.
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本研究以檸檬酸/纖維素為配位劑,硝酸鈷、硝酸鋰等為原料,應用溶膠-凝膠技術(sol-gel),由檸檬酸-纖維素和金屬離子配位,形成錯合物,再生成聚酯形態的樹酯(Polyester-type resin)中間物,製得奈米LiCo1-xO2鋰離子二次電池正極材料。配合FTIR、DTA/TGA 、XRD、Raman和SEM等分析,探討溶膠之重要配製參數檸檬酸/金屬離子莫耳比,以了解凝膠於轉變成LiCoO2的化學反應機構,研究製程對LiCoO2粉末之顯微結構等性質的影響。結果顯示檸檬酸/金屬離子莫耳比為1、添加Hydroxypropyl cellulose濃度在5×10-4mol/L與水/檸檬酸莫爾比為20的條件下,可於600 oC下製得層狀之LiCoO2奈米粉末,其顆粒大小約為60-80 nm。
接著以上述合成條件探討出較佳製備條件之研究,改變其熱處理時間、鋰化學計量數等變因後發現,當熱處理溫度600℃、熱處理時間4小時及鋰化學計量數為1時,於空氣下熱處理其所合成出來的LiCoO2具有最佳的層狀結構且粒徑最小。
Nanometric-sized lithium cobalt oxides powders, used as a cathode meterials for lithium-ion batteries, by sol-gel technique using a sol synthesized from the raw materials of lithium nitrate and cobalt nitrate. In which, citric acid was used as a chelating agent, and Hydroxypropyl cellulose was as a dispersant, to produce the resin of chelate from citric acid and metal ions. The precursors were characterized by FTIR, DTA/TGA, XRD, Raman and SEM, and those mechanisms for the evolution of LiCoO2 powders in this process was proposed and discussed in the context of the microstructure. In this study, it reveals that the preparatory conditions such as the molar ratio of citric acid/total metal ions at 1, Hydroxypropyl cellulose concentration at 5×10-4M, molar ratio of H2O /citric acid at 20, and reaction temperature at 600℃ a layer-structural LiCoO2 phase, the particle size of about 60-80nm was synthesed and the ideal preparatory condition will be obtained.
第一章緒論...........................................................1
1-1前言.............................................................1
1-2研究動機與目的.....................................................5
第二章理論基礎........................................................6
2-1鋰離子二次電池.....................................................6
2-1-1鋰離子二次電池...................................................6
2-1-2鋰離子二次電池工作原理...........................................12
2-1-3鋰離子二次電池正極材料...........................................14
2-2鋰鈷氧化物(LiCoO2)合成之文獻回顧…..................................19
2-2-1固態反應法(Solid state reaction)................................19
2-2-2化學共沉法(Chemical copreciptation) ............................21
2-2-3微波合成法(Microwave synthesis).................................23
2-3溶膠-凝膠法.......................................................24
2-3-1溶膠-凝膠法.....................................................24
2-3-2溶膠-凝膠法之製程步驟............................................27
2-3-3Pechini Process...............................................32
第三章實驗方法與步驟..................................................35
3-1鋰鈷氧化物溶膠體溶液製備藥品與分析儀器...............................35
3-1-1製備藥品.......................................................35
3-1-2分析儀器.......................................................36
3-2陶瓷粉末的合成....................................................38
3-2-1LiCoO2粉末的合成鋰鈷氧化物......................................38
3-2-2製程變數配置...................................................39
3-2-3LiCoO2奈米粉末製備.............................................40
3-3鋰離子電池組裝...................................................41
3-3-1 正極極片之製備.................................................42
3-3-2 鋰離子電池之製備..............................................43
第四章結果與討論.....................................................44
4-1檸檬酸/金屬離子莫爾比對LiCoO2粉末的影響.............................44
4-1-1傅立葉轉換紅外光譜儀分析.........................................44
4-1-2熱重量/示差熱分析...............................................51
4-1-3 X-光繞射儀之晶相分析...........................................55
4-1-4拉曼散射光譜分析................................................64
4-1-5粉末微結構分析..................................................68
4-1-6循環伏安法之電化學分析...........................................71
4-1-7充放電之電化學分析..............................................73
4-2溶液中水含量對LiCoO2粉末的影響.....................................76
4-2-1傅立葉轉換紅外光譜儀分析.........................................76
4-2-2熱重量/示差熱分析...............................................78
4-2-3X-光繞射儀之晶相分析............................................80
4-2-4拉曼散射光譜分析................................................84
4-2-5粉末微結構分析..................................................86
4-3Hydroxypropyl cellulose濃度對LiCoO2粉末的影響.....................87
4-3-1傅立葉轉換紅外光譜儀分析.........................................87
4-3-2熱重量/示差熱分析...............................................89
4-3-3X光繞射儀之晶相分析.............................................91
4-3-4粉末微結構分析..................................................95
4-4熱處理時間變化....................................................96
4-4-1傅立葉轉換紅外光譜儀分析.........................................96
4-4-2 X-光繞射儀之晶相分析...........................................98
4-4-3拉曼散射光譜分析...............................................102
4-4-4粉末微結構分析.................................................104
4-5鋰化學計量數之變化................................................105
4-5-1 X-光繞射儀之晶相分析...........................................105
4-5-2拉曼散射光譜分析...............................................109
第五章結論..........................................................111
參考文獻...........................................................112
1.林振華,充電式鋰離子電池,台北:全華科技圖書出版社,2001.
2.陳安莉、洪永益,2001年奈米技術與分子電子學的重大發現,科學發展月刊,國科
會,2002.
3.伊邦躍,奈米時代,台北:五南圖書出版社,2002.
4.馬遠榮,奈米科技,台北:商周出版社,2002.
5.黃德歡,改變世界的奈米科技,台北:時報文化出版社2002.
6.孫清華,可充電電池技術大全,台北:全華科技圖書出版社,2001.
7.R. Koksbang, J. Barker, H. Shi and M. Y. Saidi, “Cathode materials for lithium rocking chair batteries”, Solid State Ionics, 84, 1-21, 1995.
8.洪為民,“工業材料”, 117期,p. 54, 1996.
9.楊家諭,“二次鋰離子電池性能介紹”,工業材料, 126期,p. 115, 1997.
10.Y. K. Sun, I. H. OH and S. A. Hong, “Synthesis of Ultrafine LiCoO2 Powder by the Sol-Gel Method”, Journal of Materials Science, 31, 3617-3621, 1996.
11.I. H. OH, S. A. Hong and Y. K. Sun, “Low-temperature Preparation of Ultrafine LiCoO2 Powder by the Sol-Gel”, Journal of Materials Science, 32, 3177-3182, 1997.
12.M. P. Pechini, “Method of Preparing Lead and Alkaline Earth Titanates and Niobates and Coating Method Using the Same to Form a Capacitor”, U. S. Pat., 330(3), 697, 1967.
13.W. D. Yang, Y. H. Chang and S. H. Huang, “Influence of Molar Ratio of Citric Acid to Metal Ions on Preparation of La0.67Sr0.33MnO3 Materials via Polymerizable Complex Process”, J. of the European Ceramic Society, 25, 3611-3618, 2005.
14.M. Popa and M. Kakihana, “Synthesis of Lanthanum Cobalite (LaCoO3) by the Polymerizable Complex Route”, Solid State Ionics, 151, 251-257, 2002.
15.Z. Shao, G. Li, G. Xiong and W. Yang, “Modified Cellulose Adsorption Method for the Synthesis of Conducting Perovskite Powders for Membrane Application”, Powder Technology, 122, 26-33, 2002.
16.Z. P. Shao, G. X. Xiong, Y. J. Ren, Y. Cong, W. S. Yang, Journal of Materials Science, 35, 5639, 2000.
17.翁再賢,“LiCoO2陰極材料重要製程評估與改質研究”,國立中央大學化學工程研究所碩士論文,2002.
18.T. Nagaura and K. Tozawa, Progess in Batteries and Solar Cells, 9, 209, 1990.
19.李日琪,“鋰離子電池陽極碳材料開發”,國立中央大學化學工程研究所碩士論文,2000.
20.許雪萍、施德旭、洪為民, “鋰離子二次電池正極材料介紹”,工業材料,110, 48, 1996.
21.M. Yoshio, Y. Todorov, K. Yamato, H. Noguchi, J. I. Itoh, M. Okada and T. Mouri, “Preparation of LiyNi1-xMnxO2 as a Cathode for Lithium-ion Battery”, Journal of Power Sources, 74, 46-53, 1998.
22.洪逸明,“鋰離子二次電池陰極材料LiMn2O4±δ之合成及其電化學性質”,國立成功大學材料科學及工程研究所博士論文,2001。
23.廖國宏,“磷酸鐵鋰陰極材料研究”,國立暨南國際大學應用化學研究所碩士論文,2004。
24.R. J. Gummow, and M. M. Thackeray, “Lithium Cobalt Nickel Oxide Cathode Materials Prepared at 400℃ for Rechargeable Lithium Batteries”, Solid State Ionics, 53, 681-687, 1992.
25.T. Ohzuku, H.Konori, K. Sawai and T. Hirai, “Natural Graphite as An Anode for Rechargeable Nonaqueous Cells”, Chem. Express , 5, 773 , 1990.
26.林世彬、洪敏雄、方冠榮,“鋰離子二次電池陰極材料LiNiO2之合成及其性質”,國立成功大學材料科學及工程學系博士論文,2002。
27.Y. Shao-Horn, S. A. Hackney, C. S. Johnson, A. J. Kahaian, and M. M. Thackeray, “Structural Features of Low-Temperature LiCoO2 and Acid-Delithiated Products”, Journal of Solid State Chemistry, 140, 116-127, 1998.
28.Kim, M. K., Park, K. S., Son, J. T., Chung, J. H. T. and Kim, “The Electrochemical Properties of Thin-Film LiCoO2 Cathode Prepared by Sol-Gel Process”, Solid State Ionics, 152, 267-272, 2002.
29.C. H. Lu and P. Y. Yeh, “Ultrafine Lithium Cobalt Oxide Powder Derived from a Water-in-Oil Emulsion Process”, J. Mater. Chem., 10, 599, 2000.
30.詹益松,”可攜帶的能源-鋰二次電池”,工業材料,220, 155-162, 1996.
31.L. D. Dyer, B. S. Borie and G. P. Smith, “Alkali Metal-Nickel Oxides of the Type MNiO2”, J. Am. Chem. Soc., 78, 1499, 1954.
32.G.. T. K. Fey, R. F. Shiu, V. Subramanian, C. L. Chen, “The Effect of Varying the Acid to Metal Ion Ratio R on the Structural, Thermal, and Electrochemical Properties of Sol-Gel Derived Lithium Nickel Cobalt Oxides”, Solid State Ionics, 148, 291-298, 2002.
33.G.. T. K. Fey, C. L. Chen, V. Subramanian, C. L. Chen, “Sol-Gel Synthesis of LiNi0.8Co0.2O2 via an Oxalate Route and its Electrochemical Performance as an Intercalation Material for Lithium Batteries”, Materials Chemistry and Physics, 79, 21, 2003.
34.R. K. B. Gover, M. Yonemura, A. Hirano, R. Kanno, Y. Kawamoto, C. Murphy, B. J. Mitchell, J. W. Richardson, “The Control of Nonstoichiometry in Lithium Nickel cobalt Oxides”, Journal of Power Sources, 81, 535-541, 1999.
35.R. Gover, R. Kanno, B. Mitchell, A.Hirano, Y. Kawamoto, “The Effect of Sintering Time on the Structure and Electrochemical Properties of LiNi0.8Co0.2O2”, Journal of Power Sources, 90, 82-88, 2000.

36.R. K. B. Gover, R. Kanno, B. J. Mitchell, A. Hirano, Y. Kawamoto, “The Role of Nickel Content on the Structure and Electrochemical Properties of Lix(NiyCo1-y)O2”, Journal of Power Sources, 97-98, 316-320, 2001.
37.M. M. Thackeray, “Manganese Oxides for Lithium Batteries”, Progress in Solid State Chemistry, 25, 1, 1997.
38.M. Kakihana, “Invited Review “Sol-Gel” Preparation of High Temperature Superconducting Oxides”, Journal of Sol-Gel Science and Technology, 6, 7-55, 1996.
39.C. S. Hsieh and T. S. Liou, , Quality Engineering, 13(3), 449, 2001.
40.C. Delmas and I. Saadoune, “Electrochemical and Physical Properties of the LixNi1−yCoyO2 Phases”, Solid State Ionics, 53, 370-375, 1992.
41.H. Yan, X. Huang, Z. Lu, H. Huang, R. Xue and L. Chen, “Microwave synthesis of LiCoO2 cathode materials”, Journal of Power Sources, 63, 530-532, 1997.
42.蔣孝澈, “溶凝膠製作與應用專輯”, 化工, 46, p.12~p.15,1999。
43.周幸妃, “以有機前導物法製備鋅鐵氧化物粉末之探討”,國立成功大學資源工程研究所碩士論文,2003。
44.蔡政達, “利用FT-IR 和13C-NMR 光譜探討檸檬酸製程合成鈦酸鋇陶瓷粉末之研究”, 國立成功大學材料科學及工程研究所博士論文, 1999。
45.汪建民, 陶瓷技術手冊(上), 經濟部, 台北, 1994。
46.陳慧英,黃定加和朱琴億, “溶膠凝膠法在薄膜製備上之應用”,化工技術期刊,無機薄膜之製備與應用專輯, 第80期, p.152~p.167, 1999。
47.J. Livage and C. Sanchez, “Sol-Gel Chemistry”, J. Non-Cryst. Solids, 145, 11-19, 1992.
48.M. Kakihana, “Sol-Gel Preparation of High Temperature Superconducting Oxides”, J. Sol-Gel Sci. Tech., 6, 7, 1996.

49.L. W. Tai and P. A. Lessing, “Modified Resin-Intermediate Processing of Perovskite Powders: Part I Optimization of Polymeric Precursors”, J.Mater. Res., 502, 2, 1992.
50.L. W. Tai and P. A. Lessing, “Modified Resin-Intermediate Processing of Perovskite Powders: Part ⅡProcessing for Fine, Nonagglomerated Sr-doped Lanthanum Chromite Powders”, J. Mater. Res. 7, 511, 1992.
51.M. Gugliemi and G. Carturan, “Precursor for Sol-Gel Preparations”, J. Non-Crystalline Solids., 100, 16-30, 1998.
52.D. Hennings and W. Mayr, “Thermal Decomposition of (Ba,Ti) Citrates into Barium Titanate”, J. Solid State Chem., 26, 329-338, 1978.
53.M. Kakihana, T. Nagumo, M. Okamoto, and H. Kakihana, “Coordination Structures for Uranyl Carboxylate Complexes in Aqueous Solution Studied by IR and 13C NMR Spectra”, J. Phys. Chem., 91, 6128, 1987.
54.S. Tao , Q. Wu, Z. Zhan, G. Meng, “Preparation of LiMO2 (M=Co, Ni) cathode materials for intermediate temperature fuel cells by sol-gel processes”, Solid State Ionics, 124, 53-59, 1999.
55.W. Huang and R. Frech,“Vibrational Spectroscopic and Electrochemical Studies of the Low and High Temperature Phases of LiCo1-xMxO2(M = Ni or Ti) ”, Solid State Ionics, 86-88, 395-400, 1996.
56.M. Kakihana, M. M. Milanova and M. Arima, T. Okubo, M. Yashima and M. Yoshimura, “Polymerized Complex Route to Synthesis of Pure Y2Ti2O7 at 750℃ using Yttrium-Titanium Mixed-Metal Citric Acid Complex”, Journal of tha American Ceramic Society, 79, 1673, 1996.
57.Y. K. Sun and I. H. OH, “Synthesis of LiNiO2 Powders by a Sol-Gel Method”, J. Mater. Sci. Lett., 16, 30-32, 1997.
58.J. D. Tsay and T. T. Fang, “Effects of Molar Ratio of Citric Acid to Cations and pH Value on the Formation and Thermal-Decomposition Behavior of Barium Titanium Citrate”, Journal of tha American Ceramic. Society., 82, 1409, 1999.
59.L. W. Tai and P. A. Lessing, “Modified Resin-Intermediate Processing of Perovskite Powders. Part I: Optimization of Polymeric Precursors”, J. Mater. Res. 7, 502, 1992.
60.R. J. Gummow, M. M. Thackery, W. I. F. David and S. Won , “LixCoO2 (0<x≦1): a New Cathode Material for Batteries of High Energy Density.” Mat. Res. Bull., 15, 783, 1980.
61.M. Yoshio, H. Tanaka, K. Tominaga, and H. Noguchi, “Synthesis of LiCoO2 from Cobalt-Organic Acid Complexes and Its Electrode Behaviour in A Lithium Secondary Battery”, Journal of Power Sources, 40, 347-353, 1992.
62.G. Ting-Kuo Fey, R.F. Shiu, T. Prem Kumar and C.L. Chen, “Preparation and Characterization of Lithium Nickel Cobalt Oxide Powders via a Wet Chemistry Processing”, Materials Science and Engineering, B100, 234-243, 2003.
63.E. Antolini, “LiCoO2: Formation, Structure, Lithium and Oxygen Nonstoichiometry, Electrochemical Behaviour and Transport Properties”, Solid State Ionics, 170, 159-171, 2004.
64.J. R. Dahn, U. Vonsacken, and C. A. Michal, “Structure and Electrochemistry of Li1-yNiO2 and a New LiNiO2 Phase with the Ni(OH)2 Structure”, Solid State Ionics, 44, 87-97, 1990.
65.N. Ding, J. Zhu, Y. X. Yao and C. H. Chen, “The Effect of γ-Radiation on LiCoO2”, Chemical Physics Letters, 426, 324-328, 2006.
66.C. Julien, “Local Cationic Environment in Lithium Nickel-Cobalt Oxides Used as Cathode Materials for Lithium Battery”, Solid State Ionics, 136-137, 887-896, 2000.
67.C. Julien, “Study of the Local Order in LiNi1-yCoyO2 Oxides Synthesized by Soft Chemistry”, Ionic, 5, 351-357, 1999.

68.S. G. Kang, S. Y. Kang, K. S. Ryu and S. H. Chang, “Electrochemical and Structural Properties of HT-LiCoO2 and LT-LiCoO2 Prepared by the Citrate Sol-Gel Method”, Solid State Ionics, 120 , 155-161, 1999.
69.K. Kushida and K. Kuriyama, “Sol-Gel Growth of LiCoO2 Film on Si Substrates by a Spin-Coating Method”, Journal of Crystal Growth, 237-239, 612-615, 2002.
70.S. W. Song, K. S. Han, H. Fujita and M. Yoshimura, “In Situ Visible Raman Spectroscopic Study of Phase Change in LiCoO2 Film by Laser Irradiation”, Chemical Physics Letters, 344, 299-304, 2001.
71.T. Ohzuku, S. Takeda, and M. Iwanaga, “Solid –State Redox Potentials for Li[Me1/2Mn3/2]O4 (Me:3d-Transition Metal) Having Spinel-Framework Structures: a Series of 5 Volt Materials for Advanced Lithium-ion Batteries”, J. Power Sources, 81, 90-94, 1999.
72.M. Broussely, F. Perton, and J. Labat, “Li/LiNiO2 and Li/LiCoO2 Rechargeable System: Comparative Study and Performance of Practical Cells”, J. Power Sources, 43, 209-216, 1993.
73.W. S. Yoon and K. B. Kim, “Synthesis of LiCoO2 Using Acrylic Acid and Its Electrochemical Properties for Li Secondary Batteries”, Journal of Power Sources, 81-82, 517-523, 1999.
74.Y. S. Horn, S. A. Hackney, A. J. Kahaian, and M. M. Thackerayw, “Structural Stability of LiCoO2 at 400℃”, Journal of Solid State Chemistry, 168, 60-68, 2002.
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1. 趙淑珠、蔡素妙(2002)。家庭的意義:大學生的家庭概念調查研究。中華輔導學報,第11期,167-189頁。
2. 羅國英(2000)。母親教養期望與親職壓力及青少年親子關係知覺的關聯-兼談學業成就於其中的角色。東吳社會工作學報,6,35-72。
3. 李柏英(2002)。<評價歷程的理論與測量:探討價值觀與情境關聯的新取向>。《應用心理研究》14,79-116。
4. 蘇芳瑩、許美瑞(1993)。台灣報紙的家庭概念(1988-1999):以家庭功能、家人關係為例。中華家政學刊,第33期,85-102頁。
5. 趙淑珠(1999)。家庭系統中之性別議題。應用心理研究。2期,125-139。
6. 曾端真(1993)。家庭功能。諮商與輔導。第91期,16-21頁。
7. 楊國樞(1981)。中國人的性格與行為:形成及蛻變。中華心理學刊。23卷1期,7-28。
8. 游美惠(2004)。性別權力與知識建構:《親職教育》教科書的論述分析。女學學誌:婦女與性別研究,17,1-45。
9. 沈慶鴻(2001)。由代間傳遞的觀點探索婚姻暴力對目睹兒童的影響。中華心理衛生學刊,14(2),65-86。
10. 吳明燁(1998)。青少年初期父親與母親管教行為之比較。東吳社會學報,7,39-79。
11. 吳聰賢(1974)。從子女價值談人口增加問題。綜合月刊,63,
12. 30.詹益松,”可攜帶的能源-鋰二次電池”,工業材料,220, 155-162, 1996.
13. 20.許雪萍、施德旭、洪為民, “鋰離子二次電池正極材料介紹”,工業材料,110, 48, 1996.
14. 9.楊家諭,“二次鋰離子電池性能介紹”,工業材料, 126期,p. 115, 1997.
15. 蘇建文、龔美娟(1994)。母親的依附經驗教養方式與學前兒童依附關係之相關研究。教育心理學報,27期,1-33。
 
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