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研究生：	侯柏脩 Hou, Po-Hsiu
論文名稱：	固態鎂布二次電池充放電機制研究 A Study on Charge-Discharge Mechanism of Solid State Magnesium Cloth Secondary Battery
指導教授：	洪飛義 Hung, Fei-Yi
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2021
畢業學年度：	109
語文別：	中文
論文頁數：	84
中文關鍵詞：	鎂電池、二次電池、固態電解質、充放電
外文關鍵詞：	Magnesium battery, Secondary battery, Solid electrolyte, Charge and discharge
相關次數：	點閱：117 下載：0
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目前商用二次離子電池為鋰離子電池，然而隨著鋰礦的稀少價格逐年攀升，且鋰離子電池在使用上仍存在危險性，例如： (1)高腐蝕性及汙染性的低燃點有機溶劑電解液、 (2)會導致電池短路影響電池使用安全的樹枝狀晶體生成。不僅對環境造成汙染，更有可能對人體造成危害，因此新型態二次離子電池的研發迫在眉睫。本研究以鎂離子固態電池作為主要研究方向，不僅可提升電池的安全穩定性，亦能有效降低電池生產成本。本實驗採用鎂基矽酸鹽類作為固態電解質，鎂基矽酸鹽類為天然無毒性之零污染綠能材料，且固態電解質相較於液態有機溶液電解質擁有較高的熱穩定性，在高溫的環境下仍然可以安全地使用。
本實驗分為兩部分，第一部分為確認鎂基矽酸鹽類能否作為固態電解質之評估，會先針對鎂基矽酸鹽粉末進行結構及電化學分析，結果顯示，以鎂基矽酸鹽類作為固態電解質，其 (001)晶面層間所含之結晶水可形成陽離子通道傳遞離子，於常溫下即擁有良好的離子導電率。再者，研究中將鎂基矽酸鹽類以不同的製程製備純壓錠鎂基矽酸鹽錠 (Ingot-B)與可撓式鎂基矽酸鹽布 (BCD)兩種不同的新型態固態電解質，並將固態電解質導入Mg-Sn電池系統，以鎂箔 (MF)為正極、軋延純錫片作為鎂離子插入型負極組裝成電池進行電池測試。研究結果顯示Ingot-B系統即可驅動發光二極體 (LED)且具備優良之起始電容量，但電容量會隨著充放電次數上升而衰退。然而，BCD系統由於降低矽酸鹽類比例使電容量表現較低，但具備高度循環穩定性，有更長的電池壽命， BCD系統為可撓式電池具備更好貼附性質，有利於固態電池之發展。
本研究第二部分，針對BCD系統之外，分別添加入磷酸鈉 (Na3PO4 BCD)與磷酸鈉尼龍超細纖維 (Na3PO4 NBCD)，並針對這三種BCD進行結構以及電化學分析。第二部分研究中，為降低電池介面阻礙以濺鍍鎂膜 (MS)取代鎂箔 (MF)作為正極，並直接濺鍍於BCD將原本三層結構簡化為二層結構，正極則保留軋延純錫片，組裝成電池進行電池測試。結果顯示，Na3PO4 NBCD系統具備最穩定結構以及最優良電化學性質，且電容量有大幅提升達到改質目的。本實驗最後會將第一部分之高電容量Ingot-B系統與第二部分Na3PO4 NBCD系統進行常溫下電容量對比外，結果顯示Na3PO4 NBCD系統均具備較好之電容量表現與穩定性，表示固態電解質最終改質成功。本研究成功製備出兼具良好表現以及可撓式固態鎂布電池，並解析充放電機制與導入模組化應用，並且設立串並聯模組化電池規格可供儲能工業參考。

Nowadays commercial secondary ion batteries are lithium-ion batteries. However, with the scarcity of lithium mines, the price has increased year by year, and lithium-ion batteries are still dangerous in use, such as (1) Highly corrosive and polluting organic solvents with low ignition points electrolyte, (2) The formation of dendrites that can cause a short circuit of the battery and affect the safety of the battery. It not only pollutes the environment but is more likely to cause harm to the human body, so the research and development of new-type secondary ion batteries are imminent. This research takes magnesium ion solid-state batteries as the main research direction, which can not only improve the safety and stability of the battery but also effectively reduce the production cost of the battery. In this experiment, magnesium-based silicates are used as solid electrolytes. Magnesium-based silicates are naturally non-toxic and zero-pollution green energy materials. Compared with liquid organic solution electrolytes, solid electrolytes have higher thermal stability. It can still be used safely in the high temperature environment.
This experiment is divided into two parts. The first part is to confirm whether magnesium-based silicate can be used as a solid electrolyte. The structure and electrochemical analysis of magnesium-based silicate powder will be carried out first. The result shows that magnesium-based silicate is used as a solid electrolyte, the crystal water contained between the (001) crystal plane layers can form cation channels to transfer ions, and it has good ionic conductivity at room temperature. Furthermore, in the research, the magnesium-based silicate is used to prepare pure pressed ingots, magnesium-based silicate ingots (Ingot-B), and flexible magnesium-based silicate cloth (BCD) in two different new forms using different manufacturing processes. The solid electrolyte is introduced into the Mg-Sn battery system, and the magnesium foil (MF) is used as the positive electrode and the rolled pure tin sheet is used as the magnesium ion insertion type negative electrode to assemble the battery for battery testing. Research results show that the Ingot-B system has excellent initial capacitance, but the capacitance will decline as the number of charges and discharges increases. However, the BCD system has a lower capacity performance due to the reduction in the proportion of silicates, but it has high cycle stability and long battery life. The BCD system is a flexible battery with better adhesion properties, which is beneficial to the development of solid-state batteries.
In the second part of this study, in addition to the BCD system, sodium phosphate (Na3PO4 BCD) and sodium phosphate nylon microfiber (Na3PO4 NBCD) are added separately, and the structure and electrochemical analysis of these three BCDs are carried out. Moreover, in order to reduce the barriers of the battery interface sputtered magnesium film (MS) on the BCD is used as the positive electrode to simplify the original three-layer structure into a two-layer structure, and the positive electrode is kept rolled pure tin sheets, assembled into batteries for battery testing. The results show that the Na3PO4 NBCD system has the most stable structure and the best electrochemical properties. The capacitance has been greatly increased to achieve the purpose of upgrading. This research successfully produces a flexible solid magnesium cloth battery with good performance.

中文摘要	I
Abstract	III
誌謝	XVI
總目錄	XVII
表目錄	XXI
圖目錄	XXII
 第一章 前言	1
 第二章 文獻回顧	3
2-1 二次離子電池原理及發展	3
2-1-1 鋰離子電池	3
2-1-2 鈉離子電池	5
2-1-3 鎂離子電池	6
2-1-4 混合型鎂離子電池	8
2-2 電極製程	9
2-2-1 濺鍍薄膜電極製程	9
2-2-2 軋延加工	10
2-3 電解質之發展	10
2-3-1 液態電解質	10
2-3-2 固態電解質	11
2-3-3 矽酸鹽類	13
2-4 研究目的	14
 第三章 實驗步驟與方法	17
3-1 實驗流程概述	17
3-2 固態電解質元件製備	17
3-3 實驗電極製備方式	18
3-4 材料性質分析	19
3-4-1 X-ray繞射分析	19
3-4-2 掃描式電子顯微鏡與能量分散光譜儀分析	19
3-5 電池組裝	19
3-6 電化學特性分析	20
3-6-1 充放電測試	20
3-6-2 電化學阻抗分析	20
3-6-3 傅立葉轉換紅外線光譜分析	22
3-7 電池應用分析	23
 第四章 結果與討論	28
4-1 鎂基矽酸鹽粉末特性	28
4-1-1 粉末表面形貌特性	28
4-1-2 粉末晶體結構特性	28
4-1-3 粉末壓錠結構特性	29
4-2 固態鎂錫電池性質	29
4-2-1 鎂錫電池交流阻抗率與離子導電率	29
4-2-2 鎂錫電池定電壓充放電特性	30
4-2-3 鎂錫電池固態電解質充放電前後分析	31
4-3 濺鍍鎂布電池性質探討	32
4-3-1 濺鍍鎂膜表面形貌特性	32
4-3-2 各鎂布表面形貌與橫截面特徵	32
4-3-3 鎂布晶體結構特性與FTIR光學性質	33
4-3-4 鎂布電池交流阻抗率與離子導電率	34
4-3-5 MS/ BCD/ Sn充放電特性	34
4-3-6 MS/ Na3PO4 BCD/ Sn充放電特性	35
4-3-7 MS/ Na3PO4 NBCD/ Sn充放電特性	36
4-4 固態電池綜合應用探討	36
4-4-1 壓錠鎂基矽酸鹽與Na3PO4 NBCD比較	36
4-5 鎂布電池機制探討	37
4-5-1 錫電極活化理論與分析	37
4-5-2 固態電解質原子比分析	38
4-5-3 MS/ Na3PO4 NBCD/ Sn極端充放電循環特性	40
4-5-4 濺鍍鎂布電池應用特性	41
4-5-5 電池模組化串聯充放應用評估	42
 第五章 結論	78
 參考文獻	80
                                    

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