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研究生： 涂慧娟
Hui-Jyuan Tu
論文名稱： 碳源粒徑對磷酸亞鐵鋰/碳鋰離子電池複合陰極材料之影響
Optimization of carbon coating on LiFePO4 with different sizes of polystyrene spheres as carbon sources
指導教授： 費定國
George Ting-Kuo Fey
口試委員:
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程與材料工程學系
Department of Chemical & Materials Engineering
畢業學年度： 96
語文別： 中文
論文頁數： 83
中文關鍵詞： 陰極材料 、磷酸亞鐵鋰/碳 、碳結構 、聚苯乙烯微球 、表面型態 、鋰離子電池
外文關鍵詞： Li-ion batteries, Cathode material, LiFePO4/C, Carbon structure, PS sphere, Morphology
相關次數： 點閱：12  下載：0 
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    • 由於磷酸亞鐵鋰(LiFePO4)之污染低、成本低、熱穩定性高，以及循環壽命長，且可耐大電流放電等優點，使其成為前景看好之陰極材料之一。然而導電度低、量產不易、振實密度低與鋰離子擴散速率慢，則為此材料固有之缺點。近年來，許多學者紛紛使用各種碳源進行表面改質，以改善LiFePO4導電度不佳之缺點，並增進其電化學性能。本論文利用不同粒徑之聚苯乙烯(Polystyrene, PS)微球為碳源，對LiFePO4進行表面改質，以探討碳源粒徑對LiFePO4/C複合陰極材料之影響。
    由SEM下觀察LiFePO4/C粉體，可發現以最小粒徑0.22 μm PS球為碳源之複合陰極材料，遏止粒子間團聚之效果最佳，LiFePO4/C粒子分布介於100－600 nm之間。此材料於充放電截止電壓分別為4.0與2.8 V，0.2 C下，第一次放電電容量為145 mAh g-1，為所有材料中最高者。然而其循環壽命僅為289次，為所有材料中最短者。相反的，以粒徑最大之2.75 μm PS球為碳源，所合成之LiFePO4/C複合材料，則具有較高導電度(4.44 S cm-1)及表面積(20.58 m2 g-1)。此材料於相同充放電條件下之初始放電電容量僅有132 mAh g-1，但循環壽命卻長達755次。吾人亦利用XRD、SEM、TEM/EDS/SAED、拉曼光譜與慢速循環伏安法等鑑定，以釐清碳源粒徑對LiFePO4/C複合材料之物化性與電池性能影響。

    LiFePO4 is a promising alternative cathode material because of its low material cost, environmental friendliness, superior thermal safety, and long operational life. However, the main problem with LiFePO4 is its hard to scale up, low electronic conductivity, low tap density, and slow lithium ion mobility. In recent years, many researchers have used carbon coating to overcome the low electronic conductivity. They have tried various techniques and organic materials to optimize the effect of carbon coating on the cell performance of LiFePO4/C. In this thesis, different sizes of polystyrene (PS) spheres were employed as carbon sources to synthesize the carbon-coated LiFePO4 and to study how sphere size impacts the electrochemical properties of LiFePO4/C composites.
    From SEM images, PS sphere with smallest size of 0.22 μm were more effective at preventing the aggregation of LiFePO4 particles. LiFePO4/C with 0.22 μm PS sphere as a carbon source delivered the highest first cycle discharge capacity of 145 mAh g-1 at a 0.2 C. However, it just maintained 289 cycles 80 % capacity retention. On the other hand, the composite prepared using the largest size (2.75 μm) PS sphere, with greater electronic conductivity (4.44×10-4 S cm-1) and surface area (20.58 m2 g-1), showed the lowest initial discharge capacity of 132 mAh g-1, but longest cycle life of 755 cycles. In order to understand how carbon coating influences the electrochemical properties of LiFePO4/C composite cathode materials, we analyzed them using several kinds of instruments, such as XRD, SEM, TEM/EDS/SAED, TOC, BET, Raman spectroscopy, four-point probe conductivity measurements, cyclic voltammetry, and so on.

    中文摘要 I 英文摘要 II 致 謝 III 目 錄 IV 圖 目 錄 VII 第一章 緒 論 1 1.1 前言 1 1.2鋰離子電池陰極材料發展與簡介 3 1.3研究目的及架構 7 第二章 文獻回顧 8 2.1 LiFePO4陰極材料介紹 8 2.2 LiFePO4陰極材料之改質 10 2.2.1摻雜不同金屬改質 11 2.3.2粒徑大小對LiFePO4之影響 13 2.2.3. LiFePO4之表面改質 14 2.2.3.1應用碳塗佈層改質 14 2.3.2.2以其他物質進行改質 30 第三章 實驗方法 35 3.1實驗儀器設備 35 3.2實驗藥品 36 3.3實驗步驟 37 3.3.1製備不同粒徑PS球 37 3.3.2製備LiFePO4/C複合陰極材料 38 3.4材料鑑定分析 39 3.4.1動態光散射 (Dynamic Light Scattering, DLS)量測 39 3.4.2 X光繞射（X-ray Diffractometer, XRD）分析 40 3.4.3掃描式電子顯微鏡 （Scanning Electron Microscope, SEM）觀測 40 3.4.5高解析穿透式電子顯微鏡（High Resolution Transmission Electron Microscope, HR-TEM）分析 41 3.4.5拉曼光譜（Raman Spectroscopy）鑑定 41 3.4.6微分掃描熱卡儀（Differential Scanning Calorimeter, DSC）檢測 41 3.4.7總有機碳（Total Organic Carbon, TOC）量測 42 3.4.8導電度（Four-Point probe）測試 42 3.4.9表面積（Brunauer Emmett Teller, BET）量測 43 3.5材料電化學特性分析 44 3.5.1電池性能測試 44 3.5.2慢速循環伏安分析 44 第四章 結果與討論 46 4.1不同粒徑PS球之合成 46 4.1.1起始劑種類變因 46 4.1.2合成溫度變因 47 4.2 LiFePO4/C鑑定分析 52 4.2.1 X光繞射結構分析 52 4.2.2掃描式電子顯微鏡觀測 55 4.2.3穿透式電子顯微鏡分析 57 4.2.4拉曼光譜鑑定 64 4.2.5碳含量、導電度與表面積測定 68 4.2.6電池性能評估 69 4.2.7長循環測試 70 4.2.8特徵曲線測試 72 4.2.9慢速循環伏安測試 74 4.2.10微分掃描熱卡儀分析 75 第五章 結論 78 第六章 參考文獻 80

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