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研究生:吳貴兆
研究生(外文):Wu, Kuei-Chao
論文名稱:磷酸鋰鐵粉末合成研究
論文名稱(外文):A study of LiFePO4 powder synthesis
指導教授:周麗新張延瑜
口試委員:陳學仕周麗新張延瑜
口試日期:2011-7-16
學位類別:碩士
校院名稱:國立清華大學
系所名稱:材料科學工程學系
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2011
畢業學年度:99
語文別:英文
論文頁數:72
中文關鍵詞:磷酸鋰鐵
外文關鍵詞:LiFePO4
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本研究使用半固態法合成LiFePO4粉末。有別於傳統固態法,此方法結合沉澱法與高溫固態燒結,在自組裝沉澱過程中獲得特殊形態粉體,並以600℃到800℃的燒結溫度添加蔗糖作為碳源下合成LiFePO4/C。為得理想碳比例添加,在以前驅物在高溫合成LiFePO4粉末的同時,添加不同的碳比例,使用拉曼光譜儀分析碳膜均勻度和掃描式電子顯微鏡觀察、探討碳在LiFePO4粉末合成中造成的影響。實驗結果得到添加15%蔗糖的樣品,進行3小時750℃熱處理可得到一較佳的包碳粉末。經過感應偶合電漿質譜儀分析粉末成分分析與LiFePO4相同;碳於粉末合成中可當作還原劑避免鐵二價在高溫下氧化,與不添加蔗糖粉體相較,加碳後得到磷酸鋰鐵單一相,而不加碳則得到三價鐵的磷酸鋰鐵與二價鐵的磷酸鋰鐵混合物。經過均勻的覆碳也可抑制高溫合成中晶粒成長現象,增加LiFePO4粉體導電度等優點。添加金屬鎂離子至LiFePO4/C粉末亦可提升導電度,在不影響合成後粉末形貌的情況下,添加金屬鎂的粉末較LiFePO4/C有更高的BET 表面積。以熱重-熱差分析探討結晶溫度與一些相關化學機制,得到接近600℃和700℃兩個散熱峰值,推測分別為磷酸鋰鐵結晶問度與碳石墨化溫度。
LiFePO4 powders were synthesized by the semi-solid-state method. Different from the traditional solid state method, this method combined a precipitation method with a post heat treatment. The self-assembled Fe precursor precipitates had a specialized morphology, which was unique. The mixture obtained by uniformly mixed the Fe precursor with sucrose was heat treated under 600-800℃ for the synthesis of LiFePO4/C. To optimize the carbon coating in the LiFePO4 powders, various amounts of carbon was added to the mixture prior to the high temperature treatment. It was found that sample with 15% sucrose addition sintered at 750℃ for 3 hours had a better carbon coating. Carbon here acted as a reducing agent to prevent divalent iron ions from oxidation, and the carbon coating on the LiFePO4 particles enhance the electronic conductivity. Moreover, carbon could suppress particles from growing at high temperature. LiFePO4/C doped with metal (eg. Mg doping) can also increase the electronic conductivity. In addition, it had higher surface area than LiFePO4/C without doping.
Chapter 1 Introduction…………………………………………………1
Chapter 2 Literature review……………………………………………7
2.1 Lithium Ion Batteries………………………………………………7
2.1.1 Overview of Rechargeable Batteries…………………………..7
2.1.2 History of Lithium Ion Batteries……………………………...11
2.1.3Cathode Materials……………………………………………..13
2.1.3.1 Layer-Structured ………………………………………13
2.1.3.1.1 LiCoO2…………………………………………………...…..13
2.1.3.1.2 LiNiO2…………………………………………..…14
2.1.3.2 Spinel Li2Mn2O4…………………………………….…15
2.1.3.3 Olivine-Structured LiFePO4………………………...…17
2.2 The Properties of the LiFePO4 Cathode Materials……………….20
2.2.1 Structure and Phase of the LiFePO4………………………….20
2.2.2 Lithium ion Intercalation/Deintercalation Process of the LiFePO4…………………………………………………………….23
2.2.2.1 Reaction Model…………………………………………..23
2.2.2.2 Miscibility Gap in LiFePO4………………………….......27
2.3 Improving the Conductivity of LiFePO4………………………....28
2.3.1 Carbon Nano-Coating………………………………………...28
2.3.2 Impurity Doping……………………………………………...31
2.4 Methods of Synthesizing LiFePO4………………….……………32
Chapter 3 Experimental Procedure…………………………………..34
3.1 Preparation of LiFePO4 Powder by Semi-Solid-State Method…..34
3.2 Characterization and Analysis…………………………………….37
3.2.1 Phase analysis………………………………………………...37
3.2.1.1 X-Ray Powder Diffraction……………………………….37
3.2.1.2 Fourier Transform Infrared Spectroscopy ……………….37
3.2.2 Compositional Evaluation……………………………………37
3.2.3 Morphological Observation…………………………………..38
3.2.4Surface Area Analysis (BET Analysis)………………………..38
3.2.5 TGA-DTA…………………………………………………….39
3.2.6 Near-Surface Structure of Carbon Films……………………..39
3.3 Introduction of Equipment………………………………………..40
3.4 List of Reagent Chemicals………………………………………..41
Chapter 4 Result and Discussion……………………………………...42
4.1 Phase Identification of LFP and LFP Composites………………..42
4.1.1 X-Ray Powder Diffraction…………………………………....42
4.1.2 Fourier Transform Infrared Spectroscopy……………………44
4.2 Compositional Evaluation………………………………………...47
4.3 Morphological Observation………………………………………48
4.4 Surface area analysis (BET analysis)……………………………..62
4.5 DTA-TGA………………………………………………………...62
4.6 Near-Surface Structure of Carbon Films………………………….64
Chapter 5 Conclusions………………………………………………...65
Chapter 6 References………………………………………………….66

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