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研究生： 李健豪
Lee, Jian-Hao
論文名稱： 環保型鈉離子電池材料特性與充放電機制研究
A Study on Material Characteristics and Charge-discharge Mechanism of Eco-friendly Sodium-ion Battery
指導教授： 洪飛義
Hung, Fei-Yi
呂傳盛
Lui, Truan-Sheng
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： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 94
中文關鍵詞： 鈉電池 、電解液 、固態電解質 、天然礦鹽 、充放電
外文關鍵詞： Sodium battery, Electrolyte solution, Solid electrolyte, Natural ore, Charge and discharge
相關次數： 點閱：67  下載：0 
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    • 目前常見的商用電池與儲能裝置常為鋰離子電池，但鋰離子電池常用的有機電解液，具有易燃與高揮發性等缺點，遇水會產生劇毒氣體，若使用不慎，將導致爆炸與環境汙染。本研究採用的鈉離子電池系統，不使用有機電解液，選擇水溶液電解質與固態電解質進行實驗，以提高電池的使用安全性並兼顧環境保護。
    本實驗使用水溶液電解質組成濕式鈉離子電池，其中鈉鹽選擇磷酸鈉，兩種正極材料選用鈉錳氧與鈉錳鐵氧化合物，負極則使用碳黑。實驗結果顯示，使用磷酸鈉水溶液作為電解液時，上述兩種正極皆能有效進行循環充放電測試。此外，添加適量硝酸鐵共同燒結的鈉錳鐵氧化合物，能使電極結構在充放電時更穩定，同時減少錳離子在磷酸鈉電解液中溶出，使平均放電克容量與維持率提升。
    在固態電解質部分，本研究使用分布廣泛且價格低廉的天然鈉礦鹽作為固態電解質材料，與鈉錳氧正極跟碳黑負極組成乾式鈉離子電池進行研究。天然鈉礦鹽因層間陽離子在(001)晶面層間吸附水的幫助，能有效地與電極進行傳遞與嵌脫，故天然鈉礦鹽全電池在室溫下就有極佳的離子導電率。考量天然鈉礦鹽中，層間鈉離子含量較少，故放電克容量偏低。因此，本研究亦針對天然鈉礦鹽進行兩步驟成分改質，使表面鈉離子濃度提高。實驗結果顯示，兩步驟改質可使負極與電解質交界處產生固態電解質界面膜，能幫助鈉離子進行嵌脫反應，使電池放電克容量表現顯著上升。
    採用磷酸鈉電解液之濕式鈉離子電池與改質天然鈉礦鹽電解質之乾式鈉離子電池，皆展現良好的放電表現與穩定性，且同時具有價格低廉、安全與環境友善等優點，可供儲能產業應用於海濱與水源保護區等場域。

    Lithium-ion batteries are common commercial batteries and energy storage devices, but organic electrolytes commonly used in lithium-ion batteries have shortcomings such as flammability and high volatility, which are harmful to the environment. The sodium-ion batteries used in this study does not use an organic electrolyte, but an aqueous electrolyte and a solid electrolyte to improve the safety and environmental protection.
    The aqueous sodium-ion battery is composed of Na3PO4 (aq) as the electrolyte, Na-Mn-O and Na-Mn-Fe-O as the cathodes, and carbon black as the anode. The experimental results show that both of the batteries are effective to the cyclic charge-discharge test. In addition, adding an appropriate amount of Fe(NO3)3·9H2O for sintering can make the structure more stable during charge and discharge, and at the same time reduce the dissolution of Mn ions in the electrolyte, so that the average discharge capacity and retention rate are improved.
    The solid-state sodium-ion battery is composed of natural sodium ore as the solid electrolyte, Na-Mn-O as the cathode and carbon black as the anode. Natural sodium ore has excellent ionic conductivity at room temperature due to the adsorption water between the (001) interlayers. Considering the low interlayer sodium ion content of the natural sodium ore, this study also modified the natural sodium ore to increase the surface sodium ion concentration. The experimental results show that the two-step modification can create a solid electrolyte interface (SEI) between the anode and the electrolyte, thereby significantly increasing the discharge capacity of the battery.
    This study uses an aqueous electrolyte and a solid electrolyte to assemble the low-cost, eco-friendly and high-safety batteries with excellent discharge capacity and stability.

    中文摘要 I 英文延伸摘要 III 誌謝 XVIII 目錄 XX 表目錄 XXV 圖目錄 XXVI 第一章 前言 1 1-1 研究背景 1 1-2 研究動機與目的 1 第二章 理論基礎與文獻回顧 3 2-1 鈉離子二次電池及其工作原理 3 2-2 鈉離子二次電池正極材料 4 2-2-1 聚陰離子類化合物 4 2-2-2 普魯士藍類化合物 5 2-2-3 過渡金屬氧化物 6 2-3 過渡金屬氧化物製備方法 7 2-3-1 水熱法 7 2-3-2 溶劑熱法 8 2-3-3 溶膠-凝膠法 8 2-3-4 固相反應法 8 2-4 鈉離子二次電池負極材料 9 2-4-1 合金材料 9 2-4-2 金屬氧化物 10 2-4-3 碳材料 11 2-5 鈉離子二次電池常見之電解質 12 2-5-1 非水電解液 12 2-5-2 水系電解液 13 2-5-3 固態電解質 14 2-6 電池活化方法 17 2-7 研究目的 18 第三章 實驗步驟與方法 22 3-1 實驗流程概述 22 3-2 實驗粉末製備 22 3-2-1 鈉錳氧粉末材料製備 22 3-2-2 鈉錳鐵氧粉末材料製備 23 3-3 正極材料鈉錳氧、鈉錳鐵氧電極與負極材料碳黑電極製備 23 3-4 水溶液電解質製備 24 3-5 固態電解質製備 24 3-6 固態電解質之富鈉處理製備 24 3-7 電池組裝 25 3-8 材料性質分析 25 3-8-1 X射線繞射分析 25 3-8-2 掃描式電子顯微鏡與能量散佈光譜分析 26 3-8-3 傅立葉轉換紅外線光譜分析 26 3-8-4 拉曼光譜分析 26 3-9 電化學特性分析 27 3-9-1 循環充放電測試 27 3-9-2 電化學阻抗分析 27 3-9-3 感應耦合電漿質譜儀分析 28 第四章 結果與討論 33 4-1 水系鈉離子二次電池鈉錳氧與鈉錳鐵氧正極材料基礎性質探討 33 4-1-1 粉末表面巨觀與微觀結構分析 33 4-1-2 粉末結晶性與元素比例分析 34 4-1-3 粉末鍵結特性分析 35 4-1-4 粉末電極交流阻抗分析 36 4-2 鈉錳氧與鈉錳鐵氧粉末電極充放電循環特性探討 37 4-2-1 充放電循環效能探討 37 4-2-2 充放電循環後電解液ICP分析 39 4-3 固態鈉離子二次電池天然鈉礦鹽固態電解質基礎材料性質探討 39 4-3-1 粉末與高分子膜表面巨觀與微觀結構分析 39 4-3-2 粉末與高分子膜結晶性與元素比例分析 40 4-3-3 粉末與高分子膜鍵結特性分析 41 4-3-4 交流阻抗分析 41 4-4 天然鈉礦鹽固態電解質之充放電循環特性探討 42 4-4-1 充放電性能探討 42 4-4-2 粉末在不同溫度下結晶性分析 43 4-4-3 循環充放電後高分子膜鍵結特性 44 4-5 改質天然鈉礦鹽固態電解質基礎材料性質探討 44 4-5-1 改質天然鈉礦鹽高分子膜巨觀與微觀結構分析 45 4-5-2 改質天然鈉礦鹽粉末結晶性分析 46 4-5-3 改質天然鈉礦鹽高分子膜元素比例分析 47 4-6 改質天然鈉礦鹽固態電解質之充放電循環特性探討 47 4-6-1 充放電性能探討 47 4-6-2 交流阻抗分析 48 4-7 Na0.7MnO2.05/ HNBV/ CB全電池充放電傳遞機制 50 第五章 結論 88 參考文獻 89

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