鋅空氣電池之電解質開發

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曾兪銜(YU-HSIEN TSENG) 查詢紙本館藏

畢業系所

材料科學與工程研究所

論文名稱

鋅空氣電池之電解質開發
(Electrolyte development of zinc air battery)

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摘要(中)

研究從鋅空氣電池電解質的觀點切入，在水系電解質中，藉由使用複合添加劑以提高庫倫效率、降低鋅負極的腐蝕速率，並抑制充放電過程中鋅枝晶狀結構的生成，使電池充放電效率增加、循環使用壽命延長。發現四元添加劑為3000 ppm 1-Methylpiperazine、1500 ppm檸檬酸、6000 ppm酒石酸與50 ppm PEI能達到最高庫倫效率90.5%，降低腐蝕電流至196 μA/cm2，而從SEM形貌圖確定枝晶狀結構被抑制生成，呈現菱角狀的結構。
希望鋅空氣電池能輕薄短小，利用聚合物電解質設計有利於鋅空氣電池的物理靈活性，防止電解質洩漏的問題。本研究膠態電解質的製程，使其更容易吸附鹼性電解液，在一般環境下，將零件疊壓成全電池就能進行充放電，不需考慮密閉性問題，在50 mA/cm2電流密度下，放電電壓約為1.1 V。
尋求更高庫倫效率與抑制氫氣的產生，本研究利用高濃度雙三氟甲烷磺酰亞胺鋰(LiTFSI)有極大的幫助，能提高效率至96.3%，多次循環後庫倫效率幾乎不變，可以得知其穩定性很好，SEM形貌圖為蘚苔狀結構，不會形成枝晶狀結構。

摘要(英)

This study cuts into the idea of zinc-air battery electrolyte. In the water-based electrolyte, the battery is charged by using a composite additive to improve the coulombic efficiency, reduce the corrosion rate of the zinc negative electrode, and inhibit the formation of zinc dendritic structure during charge and discharge. The discharge efficiency is increased and the cycle life is prolonged. It was found that the quaternary additive was 3000 ppm 1-Methylpiperazine, 1500 ppm citric acid, 6000 ppm tartaric acid and 50 ppm PEI to achieve a maximum coulombic efficiency of 90.5%, reducing the corrosion current to 196 μA/cm2, It was confirmed from the SEM topography that the dendritic structure was hindered from being generated, and a rhombohedral structure was exhibited.
It is hoped that the zinc-air battery can be light and thin, and the polymer electrolyte design is beneficial to the physical flexibility of the zinc-air battery and the problem of electrolyte leakage. In this study, the process of colloidal electrolyte makes it easier to adsorb alkaline electrolyte. In the general environment, Charge and discharge the parts by stacking them into a full battery, regardless of the tightness problem.At a current density of 50 mA/cm2, the discharge voltage is approximately 1.1 V.
Seeking higher coulombic efficiency and suppressing the generation of hydrogen, this study used the high concentration of lithium hexafluoromethane sulfonate (LiTFSI) to greatly improve the efficiency to 96.3%, and the coulombic efficiency was almost unchanged after repeated cycles. It can be known that its stability is very good, and the SEM topography is a moss-like structure, which does not form a dendritic structure.

關鍵字(中)

★ 枝晶狀結構
★ 庫倫效率
★ 鋅腐蝕
★ 添加劑
★ 膠態電解液
★ 高濃度

關鍵字(英)

★ dendritic structure
★ coulombic efficiency
★ zinc corrosion
★ additives
★ flexible electrolyte
★ high concentration

論文目次

摘要 i
Abstract ii
誌謝 iii
總目錄 iv
圖目錄 vi
表目錄 xii
一、前言 1
二、研究背景與文獻回顧 4
2-1 金屬空氣電池 4
2-2 鋅空氣電池 6
2-3 二次鋅空氣電池電解質 10
2-4 有機酸添加劑 14
2-5 不同胺鹽類及其衍生物 16
2-6 複合添加劑效應之相關文獻 19
2-7 膠態電解液之相關文獻 19
2-8 高濃度LiTFSI之相關文獻 23
三、實驗方法與步驟 28
3-1 不同電解質添加劑對於陽極鋅金屬之庫倫效率行為 31
3-2 不同電解質添加劑對於陽極鋅金屬之枝晶狀結構影響 32
3-3 不同電解質添加劑對於陽極鋅金屬之腐蝕行為 34
3-4 膠態電解液之製作過程 34
四、結果與討論 37
4-1 電解質添加劑對陽極鋅之電化學行為之引響 37
4-1-1 無添加劑時陽極鋅之循環伏安法 37
4-1-2 有機酸類電解質添加劑對鋅陽極綜合比較 44
4-1-3 胺鹽類及其衍生物添加劑對鋅陽極綜合比較 46
4-1-4 複合電解質添加劑對鋅陽極電化學行為之綜合影響 49
4-2 膠態電解液與空氣極進行放電測試 88
4-2-1 不同製作過程之成果 88
4-2-2 進行充放電測試 93
4-3 高濃度電解液對陽極鋅之電化學表現 96
4-3-1 負電位極限對庫倫效率之影響 96
4-3-2 循環伏安法 98
4-3-3 鋅金屬在高濃度LiTFSI之腐蝕行為 102
4-3-4 高濃度LiTFSI電解液在不同基材下測試循環伏安法與庫倫效率 103
4-3-5 高濃度LiTFSI電解液對陽極表面型態之SEM圖 106
五、結論 108
六、參考文獻 110

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指導教授

張仍奎李勝偉(JENG-KUEI CHANG SHENG-WEI LI)

審核日期

2018-10-18

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