在高效能鋰電池負極材料中，矽(silicon)、鍺(germanium)、錫(tin)可以與大量的鋰離子反應，相較於市面上常用的石墨(Graphite)，擁有相當高的電容量。鍺元素(germanium)常被廣泛地討論，不只是因為鍺擁有高電容量(1384mAh/g)，於常溫下，鋰離子的質傳速率，鍺比矽元素高出了約100倍(Two order)，但是目前合成鍺多需於高溫下合成,且無法連續式的製備, 會造成生產成本的增加。在此研究上, 我們提出一種新穎且環保的合成方式。在反微胞(reverse micelle)系統，於常溫的狀態下，可以合成出產率近乎100%，且結晶性十分良好的二氧化鍺(germanium(Ⅳ) oxide)。我們以二氧化鍺奈米粒子製作鋰電池負極材料。相較於常見的非結晶性二氧化鍺薄膜的電池電容量在數十個循環後就會衰退，以結晶性二氧化鍺奈米粒子作為負極可顯示顯著地提升鋰電池的效能。於0.1C充放速率進行100次循環後，可逆電容仍高達約1050mAh/g；於快充快放的情況，8C的速率下，可逆電容有250mAh/g。最後我們也已發展出一套連續式反微胞合成系統製備奈米二氧化鍺，並製作出可適用於多種電子裝置的高電量軟包型電池。

In the high performance Li-ion battery anode material, silicon, germanium and tin have high capacities due to their ability to react with abundant of Li-ion, compared with graphite that used in the market today. Germanium has been widely studied not only because it has high theoretical capacity (1384mAh/g), but also it has the room-temperature diffusion rate two order higher than that of silicon. However, the cost of producing germanium material is really high and cannot be continuously produced. In this study, we propose a novel and environmental-friendly method, which is carried out in a reverse micelle system, for the synthesis of germanium oxide nanoparticles. High yield (almost 100%) and good crystallinity germanium oxide nanoparticles were synthesized. The electrochemical performance of germanium oxide nanoparticles in Li-ion battery is obviously promising, in comparison to amorphous germanium oxide thin film. These anodes which are made of germanium oxide have a reversible capacity approximately 1050mAh/g at a rate of 0.1C. The anode reversible capacity is about 250mAh/g when cycled at 8C. Finally, we attempt to develop a continuous scale-up procedure in producing germanium oxide nanoparticles, and we successfully manufacture high capacity pouch type cell for a variety of electronic devices.

第1章、前言 1
1.1、鋰電池發展： 1
1.2、研究動機： 2
第2章、文獻回顧 4
2.1、鍺基材料的介紹： 4
2.1.1、鍺的簡介： 4
2.1.2、鍺的化學性質： 4
2.1.3、鍺粒子的製備及應用： 6
2.1.4、二氧化鍺的簡介： 7
2.2、使用反微胞法製備二氧化鍺奈米粒子： 9
2.2.1、前言： 9
2.2.2、界面活性劑的基本觀念： 10
2.2.3、微胞的形成： 13
2.2.4、微乳化(microemulsion)系統： 15
2.2.5、使用反微胞方式製備奈米粒子： 16
2.2.6、反微胞法合成二氧化鍺奈米粒子： 17
2.3、鋰電池簡介 22
2.3.1、鋰電池的歷史沿革： 22
2.3.2、鋰電池的工作原理： 23
2.3.3、鋰電池之正極材料： 24
Ⅰ、層狀氧化物： 24
Ⅱ、尖晶石結構： 25
Ⅲ、橄欖石結構： 26
2.3.4、鋰電池之負極材料： 27
Ⅰ、合金材料： 27
Ⅱ、金屬氧化物： 29
2.3.5、鋰電池負極材料使用氧化物： 31
2.3.6、鋰電池負極材料使用二氧化鍺奈米粒子： 35
2.3.7、鋰離子二次電池電解液： 41
2.3.8、鋰離子二次全電池(Li-ion Full Cell)： 45
第3章、實驗材料與器材 50
3.1、實驗藥品： 50
3.1.1、藥品化學結構式： 50
3.2、鑑定儀器： 51
3.2.1、組電池藥品與器材： 51
第4章、實驗合成步驟及電性測試 52
4.1、批次製備奈米二氧化鍺粒子： 52
4.1.1、連續式生產奈米二氧化鍺粒子： 54
4.2、製作鋰電池二氧化鍺負極材料步驟： 55
第5章、實驗結果與討論 59
5.1、批次小量製程(Batch System)： 59
5.2、量產製程(Scale-up System)： 60
5.3、半電池及全電池測試： 62
5.4、結論： 69
Appendix: 69
參考文獻 73

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