由於化學共沈法是將反應物以原子級狀態混合，能有效減少反應複雜性並兼具有高均勻性、高反應性、高品質及精確的化學計量比。本實驗係以化學共沉法製備不同比例的鋰鋁錳（鎳、鈷）氧化物粉末，並探討此化合物的合成方式以及特性分析。
以化學共沉法製得鋰鋁鈷、鋰鋁錳、鋰鋁鎳三者之前導化合物，經冷凍乾燥，分別於600℃、900℃、1000℃下煆燒6小時，以製備鋰鋁鈷、鋰鋁錳、鋰鋁鎳氧化物，之後由XRD分析其產物，知其主要產物分別為LiAlxCo1-xO2 , LiAlxMn1-xO2 , LiAlxNi1-xO2。經粒徑分析，知所製產物大小分別為0.72 □m , 0.91 □m ,1.25 □m顯示化學共沈法製備產物可得到較小的粒徑。
利用LCR測量儀測量各燒結體之電容值經公式換算成介電常數知各燒結體的介電常數除了LiAl1/3Co2/3O2之外，其餘均不甚高，LiAlxMn1-xO2在20以下，LiAlxNi1-xO2在10以下、LiAl2/3Co1/3O2除了在較低頻、低溫燒結下，其餘皆在40以下，屬低界電材料。但隨著摻雜鋁的增多、試片燒結溫度或量測頻率的升高，其介電常數會隨之下降。
利用磁性測量儀量測試樣之磁化係數倒數與溫度關係變化之情形，知鋰鋁錳氧化物磁性屬反鐵磁性，而鋰鋁鎳、鋰鋁鈷氧化物的磁性皆屬順磁性。

Chemical coprecipitation has high homogeneity , high reactivity , high quality and exact stoichiometry. This study is to that powders of various ratios of lithium-aluminum-manganese /nickel/cobalt oxides are prepared by chemical coprecipitation . The preparation and characterization of the products are investigated.
The precursors where prepared by coprecipitation of lithium- aluminum-cobalt oxides lithium-aluminum-manganese oxides , lithium-aluminum-nickel oxides and were dried by freeze dryer. The products were obtained by calcining the precursors at 600 ℃ , 900 ℃ , 1000 ℃ , respectively. The main compositions are LiAlxMn1-xO2 , LiAlxNi1-xO2 and LiAlxCo1-xO2 , respectively , as examined for these products by XRD. The particle sizes are 0.72 μm , 0.91μm , and 1.25μm, respectively. Nano-sized particles were obtained through coprecipitation.
LCR meter was used to measure the electrical capacitance of the samples. Dielectric constants were calculated from the electrical capacity via the formula. The dielectric constants of those materials are low except LiAl1/3Co2/3O2. The dielectric constants of LiAlxMn1-xO2 are less than 20 and those of LiAlxNi1-xO2 are less than 10. The dielectric constants of LiAl1/3Co2/3O2 are less than 40 except those calcined at low temperature and measured at low frequencies. The dielectric constant decreases with increasing the sintering temperature , the measuring frequencies and the amounts of doping aluminum.
From the relationship of magnetic susceptibility and temperature by SQUID, the magnetic property of lithium-aluminum-manganese , lithium-aluminum-nickel and lithium-aluminum-cobalt oxides are shown antiferromagnetic , paramagnetic and paramagnetic properties , respectively.

中文摘要………………………………………………………………….I
英文摘要…………………………………………...…………………...III
誌謝……………………………………………………………………...V
目錄……………………………………………………………………..VI
表目錄……………………………………………………….……….....XI
圖目錄………………………………………………………………...XIV
第一章 緒論 …..………………………………………………………1
1-1 前言...…………..……………………..………………………..1
1-2 鋰二次電池...………..………………..………………………..1
1-2-1 電池基本原理………….……………………………..1
1-2-2 鋰離子二次電池……………………………………...2
1-3 文獻回顧………………………………………………………….6
1-3-1 鋰鈷氧化物(LiCoO2)…………………………………6
1-3-2 鋰鎳氧化物(LiNiO2)…………………………………6
1-3-3 鋰錳氧化物(LiMnO2)……………………………...7
1-4 研究動機與方向………………………………………………9
第二章 理論基礎……………………………………………………..10
2-1 化學溶液共沉法……….………………………....…………..10
2-2 燒結…………………………………………....……………...12
2-3 磁性原理…………………………………....…….…………..14
第三章 實驗…………………………………………………………..19
3-1 實驗藥品………..…………………..……..…….……………19
3-2 實驗儀器…………………………..……....…….…………....21
3-3 LiAlxM1-xO2之置備及性質測試..…………………………….24
3-3-1 反應原理…………………..…………...……………24
3-3-2 反應流程………………..…………….……………..24
3-3-3 溶液配置……………………..……………………...26
3-3-4 乾燥及研磨…………………..……………………...27
3-3-5 共沉粉體性質分析………………..………………...27
3-3-6-1 煆燒及煆燒後粉末性質分析……………………..27
3-3-6-2 組合電池組(cell)及衝放電分析…………………..28
3-3-7 壓錠及燒結………………………………………….29
3-3-8 燒結體的性質測定………………………………….29
第四章 結果與討論：鋰鋁錳氧化物.……………………………….31
4-1 共沉粉體的性質探討………..…..…………………………...31
4-1-1 TGA/DTA分析………………………………………31
4-1-2 FTIR分析……………………………………………31
4-1-3 XRD分析……………………………………………32
4-1-4 SEM分析…………………………………………….32
4-1-5 EDS分析…………………………………………….33
4-1-5 共沈粉體粒徑分析………………………………….33
4-2 煆燒及煆燒後粉末的性質分析……………..………………39
4-2-1 FTIR光譜分析………………………………………39
4-2-2 X光繞射分析………..……………………………...39
4-2-3 晶格常數…………………..………………………...44
4-2-4 掃瞄式電子顯微鏡及EDS分析………………….…45
4-2-5 煆燒物粉末粒徑分析……………………………….45 4-3 燒結體的性質分析…………………………………………...50
4-3-1 線收縮率及體密度………………………………….50
4-3-2 交流電阻及介電性質分析阻抗分析……………….50
4-3-3 磁性測定…………………………………………….52
4-4 充放電分析…………………………………………………..59
第五章 結果與討論：鋰鋁鎳氧化物….……………………………..62
5-1 共沉粉體的性質探討…………..……..…..………………….62
5-1-1 TGA/DTA分析………………………………………62
5-1-2 FTIR分析……………………………………………62
5-1-3 XRD分析……………………………………………62
5-1-4 SEM分析…………………………………………….63
5-1-5 EDS分析…………………………………………….63
5-1-6 共沈粉體粒徑分析………………………………….63
5-2 煆燒及煆燒後粉末的性質分析……………..……………….70
5-2-1 FTIR光譜分析………………………………………70
5-2-2 X光繞射分析………..……………………………....70
5-2-3 晶格常數…………………..………………………...75
5-2-4 掃瞄式電子顯微鏡及EDS分析………………….…75
5-2-5 煆燒物粉末粒徑分析……………………………….75 5-3 燒結體的性質分析…………………………………………...80
5-3-1 線收縮率及體密度………………………………….80
5-3-2 交流電阻及介電性質分析………………………….80
5-3-3 磁性測定…………………………………………….81
5-4 充放電分析…………………………………………………...87
第六章 結果與討論：鋰鋁鈷氧化物….……………………………..90
6-1 共沉粉體的性質探討…………..……..…..………………….90
6-1-1 TGA/DTA分析………………………………………90
6-1-2 FTIR分析……………………………………………90
6-1-3 XRD分析……………………………………………90
6-1-4 SEM分析…………………………………………….91
6-1-5 EDS分析…………………………………………….91
6-1-6 共沈粉體粒徑分析………………………………….91
6-2 煆燒及煆燒後粉末的性質分析……………..………………98
6-2-1 FTIR光譜分析………………………………………98
6-2-2 X光繞射分析………..……………………………...98
6-2-3 晶格常數…………………..……………………….103
6-2-4 掃瞄式電子顯微鏡及EDS分析…………………..103
6-2-5 煆燒物粉末粒徑分析……………………………...103 6-3 燒結體的性質分析………………………………………….108
6-3-1 線收縮率及體密度………………………………...108
6-3-2 交流電阻及介電性質分析………………………...108
6-3-3 磁性測定..………………………………………….109
6-4 充放電分析………………………………………………….115
第七章 結論與建議…………………………………………………120
參考文獻……………………………………………………...……….122
自述……………………………………………………………………129

1.Mabuchi, A.；Tokumitsu, K. ；Kasuh, T. “Charge-Discharge Characteristics of the Mesocarbon Microbeads Heat-Treated at Different Temperatures” Journal of The Electrochemical Society , Vol.142 , No.4 , 1041~1046 , 1995.
2.Liu, P.；Wu, H. “Construction and Destruction of Passivating Layer on LixC6 in Organic Electrolytes: an Impedance Study” Journal of Power Sources , Vol.56 , 81~85 , 1995.
3.Winans, R. E.；Carrado, K. A. “Novel Forms of Carbon as Potential Anodes for Lithium Batteries “Journal of Power Sources , Vol.54 , 11~15 , 1995.
4.Blomgren, G. E.；Eveready Battery Co. , “Positive Electrode Materials for Nonaqueous Secondary Batteries” Role of Ceramics in Advanced Electrochemical Systems , 103~112 , The American Ceramic Society , 1996.
5.Mizashima, K.；Jones, P. J. ；Wiseman, P. J. and Goodenough, J. B. “”Solid State Ionics, Vol.15, 783 ,1980.
6.Julien, C.；Ziolkiewicz, S.；Lemal, M.；Massot, M. “Synthesis , Structure and Electrochemistry of LiMn2-yAlyO4 Prepared by a Wet-Chemistry Method” J. Mater. Chem. , Vol.11 , 1837~1842 , 2001.
7.Hwang, B. J.；Santhanam, R.；Liu, D. G.；Tsai, Y. W. “Effect of Al-Substitution on the Stability of LiMn2O4 Spinel , Synthesized by Citric Acid Sol-Gel Method” Journal of Power Sources , Vol.102 , 326~331 , 2001.
8.Strobel, P.；Anne, M.；Chabre, Y.；Palacin, M. R.；Seauin, L.； Vaughan, G.；Amatucci, G.；Tarascon, J. M. “Characteristics of the 4 V Plateau in LiMn2(O4−xFx) Studied by in Situ Synchrotron X-ray Diffraction” J. Power Sources , Vol.81~82 , 458~462,1999.
9.Sun, Y.-K.；Jeon, Y.-S.；Leeb, H.-J. “Overcoming Jahn-Teller Distortion for Spinel Mn Phase” Electrochem. Solid-State Lett. Vol.3 , 7~9 , 2000.
10.Dean, J. A. “Solubility Products” Lange’s Handbook of Chemistry” Chap.5 , McGraw-Hill Book Company , New York , 1970.
11.“精密陶瓷材料概論” , 譯者：黃忠良
12.Chikazumi, S.；Charap, S. H. “Physics of Magnetism” John Wiley and Sons , 37~109 , 1985.
13.Cullity, B. D.；“Introduction to Magnetic Materials” Addison-Wesley , Chap.3 , 85~203 , 1972.
14.Rouanet, A. “Phase Diagrams for Ceramists” No.5232 , 1981
15.Robinson, J. W. ”Handbook of Spectroscopy” Crc. Press , 96~99 , 1974.
16.Lange, F. F. “Sinterability of Agglomerated Powders” J. Am. Ceram. Soc. , Vol.67 , 83~89 , 1984.
17.Sacks, M. D.；Pask, H. A. “Sintering of Mullite-Containing Materials : Ⅱ , Effect of Agglomeration” J. Am. Ceram Soc. Vol.65 , 70~77 , 1982.
18.Shannon, R. D.； Prewitt, C. T.；Acta Crystallogr. B25 , 925 , 1969.
19.Shannon, R. D.；Prewitt, C. T.；Acta Crystallogr. B25 , 1046 , 1970.
20.Richardson, T. J.；Wen, S. J.；Striebel, K. A.；Ross, P. N.；Jr.；Cairns, E. J. “FTIR Spectroscopy of Metal Oxide Insertion Materials：Analysis of LixMn2O4 Spinel Electrodes” Materials Research Bulletin , Vol.32 , no.5 , 609~618 , 1997.
21.Ammundsen, B.；Desilvestro, J.；Groutso, T.；Hassell, D.；Metson , J. B.；Regan, E.；Steiner, R.；Pickering, P. J. “Formation and Structural Properties of Layered LiMnO2 Cathode Materials” Journal of The Electrochemical Society , Vo1.147 , 4078~4082 , 2000.
22.Myung, S.-T.；Komaba, S.；Kumagai, N. “Enhanced Structural Stability and Cyclability of Al-Doped LiMn2O4 Spinel Synthesized by the Emulsion Drying Method” Journal of the Electrochemical Society , Vol.148 , 482~A489 , 2001.
23.Tucker, M. C.；Reimer, J. A.；Cairns, E. J. “A Li Nuclear Magnetic Resonance Study of Metal-Substituted Lithium Manganese Oxide Spinels” Journal of the Electrochemical Society , Vol.148 , A951~A959 , 2001.
24.Shao-Horn, Y.；Middaugh, R. L. “Redox Reaction of Cobalt , Aluminum and Titanium Substituted Lithium Manganese Spinel Compounds in Lithium Cells” Solid State Ionics , Vol.139 , 13~25 , 2001.
25.Jamg, Y.；Huang, B.；Wang, H.；Maskaly, G. R.；Ceder, G.； Sadoway, D. R.；Chiang, Y.-M.；Liu, H.；Tamura, H. “Synthesis and Characterization of LiAlyCo1-yO2 and LiAlyNi1-yO2” Journal of Power Sources , Vol.81~82 , 589~593 , 1999.
26.Gummow, R. J.；Kock, A.；Thackeray, M. M. “Improved Capacity Retention in Rechargeable 4V Lithium Manganese Oxide Cell” Solid State Ionics , Vol.69 , 59~67 , 1994.
27.Amine, K.；Tukamoto, H.；Yasuda, H.；Fujita, Y. “Preparation and Electrochemical Investigation of LiMn2-xMexO4(Me:Ni,Fe,and x = 0.5,1) Cathode Materials for Secondary Lithium Batteries” Journal of Power Sources , Vol.68 , Iss.2 , 604~608 , 1997.
28.Sigala, C.；Verbaere, A.；Mansot, J. L.；Guyomard, D.；Piffard, Y.； Tournoux, Y. “The Cr-Substituted Spinel Mn Oxides LiCryMn2-yO4(0≦y≦1) : Rietveld Analysis of the Structure Modifications Induced by the Electrochemical Lithium Deintercalation” Journal of Solid State Chemistry , Vol.132 , 372~381 , 1997.
29.Hernan, L.；Morales, J.；Sanchez, L.；Santos, J. “Use of Li-M-Mn-O (M=Co,Cr,Ti) Spinels Prepared by a sol-gel Method as Cathodes in High-Voltage Lithium Batteries” Sloid State Ionics , Vol.118 , 79~185 , 1999.
30.Feng, Q.；Kanoh, H.；Miyai, Y.；Ooi, K. “Li+ Extraction/Insertion Reactions with LiZn0.5Mn1.5O4 Spinel in the Aqueous-Phase” Chemistry of Materials , Vol.7 , 379~384 , 1995.
31.Ein-Eli, Y.；Howard, W. F.；Lu, S. H.；Mukerjee, S.；McBreen, J.；Vaughey, J. T.；Thackeray, M. M. “LiMn2-xCuxO4 Spinels (0.1 < x < 0.5): A New Class of 5 V Cathode Materials for Li Batteries. I. Electrochemical , Structural , and Spectroscopic Studies” Journal of the Electrochemical Society Studies,Vol.145,1238~1244 , 1998.
32.Amatucci, A.；Pasquier, A. D.；Blyr, A.；Zheng, T.；Tarascon, J. M. “The elevated temperature performance of the LiMn2O4/C system: failure and solutions” Electrochimica Acta , Vol.45 , 255~271 , 1999.
33.Strobel, P.；Anne, M.；Chabre, Y.；Palacin, M. R.；Seauin, L.；Vaughan, G.；Amatucci, G.；Tarascon, J. M. “Characteristics of the 4 V plateau in LiMn2(O4−xFx) studied by in situ synchrotron X-ray diffraction” Journal of Power Sources , Vol.81~82 , 458~462,1999.
34.Sun, Y.-K.；Jeon, Y.-S.；Leeb, H.-J. “Overcoming Jahn-Teller Distortion for Spinel Mn Phase” Electrochem. Solid-State Lett. Vol.3 , 7~9 , 2000.
35.Park, S.-H.；Park, K.-S.；Sun, Y.-K.；Nahm, K.-S. “Synthesis and Characterization of a New Spinel , Li1.02Al0.25Mn1.75O3.97S0.03 , Operating at Potentials Between 4.3 and 2.4 V” Journal of The Electrochemical Society , Vol.147 , 2116~2121 , 2000.
36.Sun, Y.-K.；Oh, B.；Lee, H. J. “Synthesis and Electrochemical Characterization of Oxysulfide Spinel LiAl0.15Mn1.85O3.97S0.03 Cathode Materials for Rechargeable Batteries” Electrochimica Acta , Vol.46 , 541~546 , 2000.
37.Nakai, I.；Takahashi, K.；Shiraishi, Y.；Nakagome, T.；Izumi, F.； Ishii, Y.；Nishikawa, F.；Konishi, T. “X-Ray Absorption Fine Structure and Neutron Diffraction Analyses of De-Intercalation Behavior in the LiCoO2 and LiNiO2 Systems” Journal of Power Sources , Vol.68 , 536~539 , 1997.
38.Tao, S.；Wu, Q.；Zhan, Z.；Meng, G. “Preparation of LiMO2 (M=Co,Ni) Cathode Materials for Intermediate Temperature Fuel Cells by Sol-Gel Precess” Solid State Ionics, Vol.124, 53~59, 1999.
39.Ferracin, C. L.；Amaral, F. A.；Bocchi, N. “Characterization and Electrochemical Performance of the Spinel LiMn2O4 Prepared from ε-MnO2” Solid State Ionics , Vol.130 , 215~220 , 2000.
40.Kumta, P, N.；Gallet, D.；Waghray, A.；Blomgren, G. E.；Setter, M. P. “Synthesis of LiCoO2 Powers for Lithium-Ion Batteries from Precursors Derived by Rotary Evaporation” Journal of Power Sources , Vol.72 , 91~98 , 1998.
41.Arai, H.；Okada, S.；Sakurai, Y.；Yamaki, J.-I. “Reversibility of LiNiO2 Cathode” Solid State Ionics , Vol.95 , 75~282 , 1997.
42.Johnson, W. D.；Jr. “Nonconventional Powder Preparation Techniques”Ceram. Bull. , 221~224 , 1981.
43.Robison, J. W. “Handbook of Spectroscopy”Crc. Press , 96~99,1974.
44.Lange, F. F. “Sinterability of Agglomerated Powers” J. Am. Ceram. Soc. , Vol.65 , 70~77 , 1982.
45.Anthony, R . W. “Basic Solid State Chemistry” John Wiley & Sons , 344~345 , 1984.
46.John, D. A. “Lange’s Handbook of Chemistry” chap.4 , 4.23~4.38 , 14th edn. , McGraw-Hill , New York , 1992.
47.劉柏柔“固態電解質對鋰離子電池性能之研究”義守大學材料科學與工程研究所，1999.