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博碩士論文 etd-0523114-154132 詳細資訊
Title page for etd-0523114-154132
論文名稱
Title
無還原添加劑水熱合成磷酸鋰鐵
Hydrothermal Synthesis of Lithium Iron Phosphate without Reducing Additives
系所名稱
Department
畢業學年期
Year, semester
語文別
Language
學位類別
Degree
頁數
Number of pages
84
研究生
Author
指導教授
Advisor
召集委員
Convenor
口試委員
Advisory Committee
口試日期
Date of Exam
2014-06-16
繳交日期
Date of Submission
2014-06-23
關鍵字
Keywords
還原劑、正極材料、鋰離子二次電池、磷酸鋰鐵、水熱法
reducing additive, Cathode material, Hydrothermal process, Lithium-ion secondary battery, Lithium iron phosphate
統計
Statistics
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中文摘要
本研究針對水熱法合成磷酸鋰鐵進行改良,成功研究出無需額外還原性添加劑,並可於大氣環境下合成出純相磷酸鋰鐵的方法。利用X光繞射儀(X-ray diffraction, XRD)確認此磷酸鋰鐵為橄欖石斜方晶系結構,並由拉曼(Raman spectroscopy)、化學分析能譜儀(Electron Spectroscopy for Chemical Analysis, ESCA)判讀樣品中是否存在三價鐵不純物,而材料表面型態變化則以掃描式電子顯微鏡(Scanning electron microscopy, SEM)和穿透式電子顯微鏡(Transmission electron microscopy, TEM)進行觀察,並藉元素分析儀(Elemental analyzer, EA)分析樣品各元素比例是否符合理論。得到磷酸鋰鐵粉體後,在多項電化學測試,例如經過循環伏安法(Cyclic Voltammetry, CV)可看到材料本身具有良好的可逆性,且可由交流阻抗測試(AC-impedance)觀察到材料本身電荷轉移阻抗小,而在定電流0.2C充放電下,材料所表現出的電容量為80mAh/g。
Abstract
LiFePO4 is successfully prepared by hydrothermal synthesis in air without extra reducing additives. The structure and morphology of the resulting LiFePO4 powders were shown by X-ray diffraction (XRD),scanning electron microscope (SEM), and a transmission electron microscope (TEM).The XRD results demonstrate that LiFePO4 powder has an orthorhombic olivine-type structure with a space group of Pnma. Raman spectroscopy and electron spectroscopy for chemical analysis (ESCA) reveal the impurity of Fe3+ in samples. The chemical composition of the LiFePO4 powders was characterized by elemental analysis (EA). Among the conditions, the electrochemical results show the energy capacity is 84 mAh g−1 at 0.2 C-rate.
目次 Table of Contents
論文審定書 i
誌謝 ii
中文摘要 iii
Abstract iv
目錄 v
圖目錄 x
表目錄 xiv
第一章. 緒論 1
1-1. 前言 2
1-2. 研究動機 2
第二章. 文獻回顧 4
2-1. 一次與二次電池發展 5
2-1-1. 一次電池介紹 5
2-1-2. 二次電池介紹 6
2-2. 鋰離子二次電池工作原理 7
2-3. 鋰離子二次電池正極材料 9
2-3-1. LiCoO2, 鈷酸鋰 9
2-3-2. LiNiO2, 鎳酸鋰 10
2-3-3. LiMn2O4, 錳酸鋰 11
2-3-4. LiFePO4, 磷酸鋰鐵 11
2-4. 磷酸鋰鐵合成方法 13
2-4-1. 固態反應法 14
2-4-2. 機械活化法 14
2-4-3. 微波法 15
2-4-4. 水熱法合成磷酸鋰鐵 15
第三章. 實驗方法 17
3-1. 實驗藥品與器材 18
3-2. 實驗步驟 19
3-2-1. 不同鐵源比例調整 19
3-2-2. 零價鐵的反應機制探討 19
3-2-3. 高溫管狀爐鍍碳鍛燒 20
3-2-4. 半電池組裝 21
3-3. 粉體分析鑑定儀器介紹 23
3-3-1. X光繞射儀(XRD) 23
3-3-2. 拉曼光譜儀(RS) 23
3-3-3. 場發射掃描式電子顯微鏡(SEM) 24
3-3-4. 穿透式電子顯微鏡(TEM) 24
3-3-5. 化學分析電子能譜儀(ESCA) 25
3-3-6. 元素分析儀(EA) 25
3-4. 電化學測試儀器介紹 27
3-4-1. 循環伏安法測試(CV) 27
3-4-2. 交流阻抗測試(AC-impedance) 28
3-4-3. 充放電及倍率效能測試(Charge-discharge & c-rate performance) 29
第四章. 結果與討論 30
4-1. 不同鐵源比例調整 31
4-1-1. X光繞射分析 31
4-1-2. 掃描式電子顯微鏡 32
4-1-3. 穿透式電子顯微鏡 34
4-1-4. 拉曼光譜分析 38
4-1-5. 元素分析 40
4-1-6. 化學分析能譜儀 41
4-2. 零價鐵的反應機制探討 43
4-2-1. X光繞射分析 43
4-2-2. 掃描式電子顯微鏡 45
4-2-3. 穿透式電子顯微鏡 48
4-2-4. 拉曼光譜分析 51
4-2-5. 元素分析 52
4-2-6. 化學分析能譜儀 53
4-2-7. 反應機制的推導 54
4-3. 電化學分析 55
4-3-1. 循環伏安法分析 56
4-3-2. 交流阻抗分析 58
4-3-3. 定電流充放電測試 60
4-3-4. 倍率放電測試 61
第五章. 結論 63
第六章. 參考文獻 66
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