探討不同流場電解液與不同表面積發泡鎳網作鋅空氣電池負極集電網之電化學性質

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姓名

張家綺(Chia-Chi Chang) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

探討不同流場電解液與不同表面積發泡鎳網作鋅空氣電池負極集電網之電化學性質
(Using Nickel foam of different surface area as anode current collector with different flow field for Zn-based batteries)

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摘要(中)

本研究使用發泡鎳網作為鋅二次電池負極集電網，搭配不同轉速之流場電解質，抑制鋅在充電沉積過程中產生樹枝狀晶的問題，並提升單位面積鋅負載量與循環充放電之效率。實驗採用三極式電化學裝置，參考電極為飽和甘汞電極，電解液為含有飽和氧化鋅(ZnO)的6M氫氧化鉀(KOH)溶液，分別在無轉速、300、450與900 rpm轉速下進行電化學測試。
　　Nickel foam在不同電流密度下鍍鋅30分鐘，並使用掃描式電子顯微鏡(SEM)來觀測鋅沉積的樣貌，顯示在高轉速下Nickel foam可以承受更高的電流密度鍍鋅而不產生樹枝狀晶；以循環伏安法測試負極在流場下有較高的氧化峰值，表示搭配流場電解質會有較好的放電表現；以100 mA/cm2電流密度做充放電循環測試，可以發現負極在流場下有較好的循環穩定性，且有較高的庫倫放電效率。
　　不同表面積之Nickel foam可藉由電化學沉積法製備，固定電流180mA/cm2，調整電鍍時間15、30、45分鐘與一小時，搭配不同轉速之流場電解液，經由循環伏安法與充放電循環測試後，可以提升鋅的氧化電流值與庫倫效率，也有較好的循環穩定性，其中鍍鎳30分鐘的實驗組有最高的氧化電流與穩定性，有最好電化學表現。
　　Nickel foam因為其多孔性結構，具有相當高的比表面積，並搭配流場電解質，可有效利用內部的面積，提升Nickel foam的使用率，進而分散單位面積的電流密度，可以使Nickel foam有更多的空間讓鋅沉積，並且承受更大的鍍鋅電流密度，故Nickel foam作為鋅二次電池負極集電網搭配流場電解質可有利於儲能裝置發展前景。

摘要(英)

Using Ni foam as the current collector with different flow field electrolyte for Zn-based secondary batteries could inhibit dendrite formation and enhance electrochemical performance. In this work, electrochemical analysis was conducted in an alkaline electrolyte composed of 6 M KOH with saturated ZnO and under different flow field, 0 rpm, 300rpm, 450 rpm, 900 rpm respectively. Zn was electrodeposited on Ni foam at different current density for 30 minutes, the SEM images showed that with the flow field electrolyte Ni foam could be applied for higher current density without dendrite formation. According to the results of cyclic voltammetry, the anodic peak with high revolutions per minute, especially for 450 rpm, was larger than without flow field electrolyte. It indicated that Ni foam with flow field electrolyte had a better discharge performance. Constant current density, 100 mA/cm2, was applied for the charge/discharge cyclic test. Ni foam with flow field electrolyte exhibited a better discharge efficiency and superior cycle stability. Ni foam of different surface area has been prepared by an electrodeposition technique. We used a constant current density, 180mA/cm2, and set different parameters of time, 15, 30, 45 minutes and 1 hour for the electrodeposition. Under different flow field, Ni foam of different surface area was determined by cyclic voltammetry and charge/discharge cycle test. The anodic current and cycle stability of Ni foam of different surface area was higher than that of the commercial Ni foam. Because of the high porosity and large specific surface area, the inner area of Ni foam could be fully used with the flow field electrolyte. This effect caused the applied current density was being separated, so the real current density per unit area decreased and the space of Ni foam for Zn deposition increased. Owing to these results, Ni foam used as the current collector with the flow field electrolyte is a good choice for energy storage.

關鍵字(中)

★ 鋅空氣電池
★ 發泡鎳網
★ 電化學
★ 負極
★ 集電網

關鍵字(英)

★ Zinc-Air battery
★ Nickel foam
★ Electrochemistry
★ anode
★ current collector

論文目次

摘要 i
Abstract iii
誌謝 v
目錄 vii
圖目錄 xi
表目錄 xvi
一、緒論 1
1-1 前言 1
1-2 研究動機 4
二、文獻回顧 7
2-1 鋅空氣電池的工作原理 7
2-2 鋅空氣電池的發展 10
2-3 鋅空氣電池的負極材料 13
2-4 鋅的電沉積形貌 17
2-5 鋅枝狀晶的抑制 21
2-5-1 電解液添加劑 21
2-5-2 電極改質或添加劑 25
2-5-3 實驗條件控制 28
2-5-4 物理與其他方法 30
2-6 發泡鎳網在儲能產業的應用 33
三、實驗方法及步驟 36
3-1 實驗藥品與器材 36
3-1-1 實驗藥品 36
3-1-2 實驗儀器與器材 37
3-2 實驗步驟 38
3-2-1 發泡鎳網前處理 38
3-2-2 不同表面積之發泡鎳網製備 39
3-2-3 電化學測試裝置 40
3-2-4 電解質液流系統 41
3-3 材料鑑定分析 41
3-3-1 X光繞射儀分析 (X-ray Diffraction, XRD ) 41
3-3-2 場發射掃描式電子顯微鏡 (Field Emission Scanning Electron Microscope, FE-SEM) 41
3-4 電化學分析 42
3-4-1 表面形貌分析 42
3-4-2 枝狀晶生長極限電流 42
3-4-3 循環伏安法 (Cyclic voltammetry, CV) 42
3-4-4 循環穩定性測試 43
四、結果與討論 44
4-1 材料分析鑑定 44
4-1-1 X光繞射分析 44
4-1-2 鋅沉積樣貌 45
4-2 循環伏安法 48
4-2-1 循環伏安圖 48
4-2-2 庫倫效率 51
4-3 鋅枝狀晶生長之極限電流 53
4-4 循環充放電測試 63
4-4-1 放電曲線圖 63
4-4-2 循環效率 66
4-5 不同表面積之發泡鎳網分析鑑定 67
4-5-1 表面形貌鑑定 67
4-5-2 XRD分析鑑定 69
4-6 不同表面積發泡鎳網之循環伏安測試 71
4-7 不同表面積發泡鎳網之循環充放電測試 76
五、結論與未來展望 79
參考文獻 81

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指導教授

李岱洲(Tai-Chou Lee)

審核日期

2017-8-16

推文