摘要:

本研究利用不同程序的化學共沉澱法，合成不同型態的四氧化三鐵奈米微粒，其中實驗重點之一在於使用單一原料: 硫酸亞鐵為前驅鹽, 先使用過氧化氫將之氧化為三價，再以恰當比例混合，並用氫氧化鈉共沉澱合成出四氧化三鐵奈米粒子，當中以TX-100當作保護劑使之均勻分散。實驗重點在於藉由製程上的變化得到不同形態的四氧化鐵粒子，若將前驅鹽溶液和氫氧化鈉溶液分別使用蠕動幫浦同時滴入分散劑TX-100溶液中，所得到四氧化三鐵球形粉末大小均勻。此外吾人亦曾使用兩階段方式添加NaOH，並藉由如IPA, EG, 甘油分子的添加可以得到高轉化率的針狀粒子。成品粉末則使用X光繞射光譜儀(XRD)、超導量子干涉磁量儀(SQUID)、高解像能電子顯微鏡(HRTEM)和掃描式電子顯微鏡(SEM) 、BET來分析粒徑大小、粒徑均勻度、磁性、比表面積與晶體結構等特性，期能探討合成條件與成品特性間的關係，未來則繼續製得電極以作為電池應用，而尋求最佳表現之粉末特性。

銀包覆四氧化三鐵的製備則將硝酸銀及當作還原劑的IPA或是EG加入球形四氧化三鐵懸浮液當中，以不同莫爾比例的硝酸銀進行混合包覆程序，成品粉末也使用相同分析方法, 以鑑定成品粉末的包覆完整性、結晶性質、均勻性及磁性等。

Abstract

In this research, we tried several different precipitation processes to synthesize Fe3O4 nanoparticles with different morphologies. We used only one precursor, i.e. FeSO4, which was oxidized to ferric sulfate by hydrogen peroxide. The two solutions were then mixed in appropriate ratio to obtain Fe3O4 using NaOH as the precipitant. TX-100 was used as a protective agent to keep the particles uniform. When both iron precursor solution and NaOH solution was pumped separately into TX-100 solution, spherical Fe3O4, uniform in size, was obtained. On the other hand, a two-step procedure, with the addition of molecules such as IPA, EG (ethylene glycol) or glycerol, we would get Fe3O4 particles in needle shape and also having complete (100%) conversion. The powders were then characterized by techniques such as XRD, SQUID, HRTEM, SEM, BET to obtain information on many characteristics of powders, such as size and uniformity, particle morphology, magnetic property, specific surface area, crystallinity, etc.. It is our hope to find correlation between these characteristics and processing conditions. These powders will be further processed as electrode materials and tested in a battery to find optimal performance.

For silver coated magnetic particles, we used AgNO3 and either IPA or EG as reducing agent and spherical Fe3O4 nanoparticles as core. The relative ratio between AgNO3 and Fe3O4 was varied with the objective to get uniform coating. The powders thus obtained was also subjected to several characterization techniques to get information on coating uniformity, crystalline nature, and magnetic property.

目錄
第一章、前言 15
第二章、文獻回顧 16
2.1奈米微粒基本原理 16
2.1.1奈米粒子聚集與分散特性: 17
2.1.2加入界面活性劑之影響: 17
2.2磁性的基本原理介紹 18
2.2.1磁性: 18
2.2.2 磁滯曲線 21
2.2.3 磁性與粒徑之關係 23
2.3氧化鐵的介紹 23
2.4製備奈米級四氧化三鐵方法 24
2.4.1奈米微粒的常用製備方法 24
2.5共沉澱法製備四氧化三鐵 29
2.6四氧化三鐵形貌結構 31
2.7 棒狀結構之四氧化三鐵合成 33
2.8 核-殼結構介紹 35
2.9研究目的 37
第三章、實驗 38
3.1實驗藥品 38
3.2實驗儀器 38
3.3製備四氧化三鐵奈米鐵微粒 41
3.3.1球形微粒之合成程序 41
3.3.2針狀微粒的合成程序 43
3.3.3針狀與球形微粒混合溶液的製備(兩階段法) 43
3.3.4 Freeze-Thaw 實驗程序 44
3.3.5銀包覆四氧化三鐵奈米微粒 44
3.3.6電極材料製備程序及電池性能測試步驟 45
第四章、結果與討論 48
4.1四氧化三鐵球形微粒: 48
4.1.1球形微粒各項分析結果 48
4.1.2製備球形微粒中氫氧化鈉用量對pH值之影響 52
4.2四氧化三鐵針狀粒子合成: 53
4.2.1製備針狀結構四氧化三鐵第一階段下產物分析 53
4.2.2製備針狀四氧化三鐵第二階段產物分析 55
4.3四氧化三鐵球形與針狀同時存在 70
4.3.1分析結果討論 70
4.3.2黏度測量 72
4.4 四氧化三鐵球形、針狀和針狀與球形混合之綜合比較 74
4.5銀包覆四氧化三鐵(使用葡萄糖當作還原劑) 75
4.5.1實驗分析結果: 75
4.6表面改質後銀包覆四氧化三鐵(使用IPA或EG當作還原劑及表面改質劑) 81
4.6.1先加入AgNO3後加入IPA 81
4.6.2先加入IPA或EG之後加入AgNO3溶液 84
4.7鎳鐵電池充放電分析 86
4.7.1球形四氧化三鐵/Cu/CNT分析: 86
4.7.2針狀四氧化三鐵/Cu/CNT分析: 90
4.7.3電池充放電分析: 94
第五章、結論 98
第六章、參考文獻 100

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