臺灣博碩士論文加值系統

本研究分為兩系統探討電解液添加劑對鋅金屬沉積/溶解與電池效能之影響。第一個系統探討單鹽類系統，硫酸鋅電解液在非對稱電池測試中得出最適合濃度為2 M，在1 mA cm-2下約有58圈之循環壽命，當電解液中添加2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol (簡稱BIS-TRIS)後，於1 mA cm-2下約有有759圈之循環壽命；在改變充放電速率的測試條件下，2 M硫酸鋅電解液於1 mA cm-2下約有100圈循環壽命，當電解液中添加BIS後，於1 mA cm-2下約有有393圈之循環壽命；在醋酸鋅電解液於非對稱電池之測試中，電解液之最佳濃度為1 M，在1 mA cm-2下約有234圈之循環壽命，於電解液中添加BIS後，於1 mA cm-2下約有697圈之循環壽命，在改變充放電速率下，1.0 M醋酸鋅電解液於1 mA cm-2下約有162圈之循環壽命，於電解液中添加BIS-TRIS後，於1 mA cm-2下約有805圈之循環壽命。因此，在單鹽類系統中，若於電解液中添加BIS-TRIS後將可提升電池之循環壽命。
第二個系統為混合鹽類系統，以第一個系統之最佳濃度為基礎，加入硫酸鋰/醋酸鋰，並使用鋰離子電池正極材料進行半電池測試。從實驗中可知當電解液為2 M硫酸鋅-1 M硫酸鋰-0.1 M硫酸錳時，經過200圈之充放電測試後，電池之容量保持率約為57.8%，於電解液中添加BIS-TRIS後，其電池之容量保持率可達88%；當電解液為高濃度硫酸系統4 m硫酸鋅-2 m硫酸鋰時，經過200圈之充放電測試後，電池之容量保持率約為52%，於電解液中添加BIS-TRIS後，其電池之容量保持率可達84%；當電解液為醋酸鋅混合系統1 M醋酸鋅-1 M醋酸鋰時，經過150圈之充放電測試後，電池之容量保持率約為42%，於電解液中添加BIS後，其電池之容量保持率可達99%。因此，於混合鹽類系統中，若於電解液中添加BIS-TRIS後也可提升電池之循環壽命。
最後藉由SEM觀測電池正極與負極之表面型態，可清楚發現當電解液中添加BIS後其電極表面沉積物均呈現較為平整之片狀結構，而未添加BIS之電極表面則呈現較為不規則之塊狀結構。同時亦透過XRD檢測其表面副產物之生成，結果顯示當電解液中添加BIS後其副產物之特徵峰強度皆低於未添加BIS之電解液，因此可知當電解液中添加BIS能使鋅離子更均勻的沉積與剝離，並能抑制副產物之生成進而提升電池之循環壽命。

This study is divided into two systems to investigate the effect of electrolyte additives on zinc metal plating/stripping and battery performance. The first system discusses the single-salt system, and the most suitable concentration of zinc sulfate electrolyte in the symmetric battery test is 2 M, it has 58 cycle life at 1 mA cm-2, while adding 2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol has 759 cycle life; there has 100 cycle life of 2 M zinc sulfate at different rate, and after adding BIS, there has a cycle life of 393 ; in the symmetric battery test of zinc acetate electrolyte, optimum concentration is 1 M, it has about 234 cycle life at 1 mA cm-2, after adding BIS, there is a cycle life of 697 cycles. There has 162 cycle life of 1.0 M zinc acetate at different rate, and has a cycle life of 805 after adding BIS-TRIS.
The second system is a hybrid system, based on the optimal concentration of the first system, add lithium sulfate/lithium acetate, and use lithium-ion battery cathode material for full battery test. From the experiment, it can be concluded that the capacity retention is 57.8% after 200 cycles in 2 M zinc sulfate-1 M lithium sulfate-0.1 M manganese sulfate, and 88% capacity retention after adding BIS-TRIS . In a high concentration system, 4 m zinc sulfate-2 m lithium sulfate has a capacity retention of 52% after 200 cycles, and 84% capacity retention after adding BIS-TRIS. While in the zinc acetate hybrid system, 1 M zinc acetate-1 M lithium acetate has 42% capacity retention after 150 cycles, and 99% capacity retention after adding BIS.
Finally in the electrode surface analysis, The surface of the positive、 negative electrode can be observed by SEM, after the addition of BIS, the surface deposits are relatively flat and flaky, if not added, it is irregular block. Formation of surface by-products detected by XRD, it was found that the intensity ratios of the characteristic peaks of the by-products after the addition of BIS were lower than those without the addition of BIS. It can be observed that BIS can enable more uniform plating/stripping of zinc ions, and can suppress the generation of by-products to improve the cycle life of the full cell.

碩士論文 1
摘要 i
Abstract iii
誌謝 v
目錄 vi
表目錄 ix
圖目錄 x
第一章 緒論 1
1.1 前言 1
1.2 二次電池發展 1
第二章 文獻回顧與原理 3
2.1 水性鋅離子二次電池簡介及原理 3
2.2 水性電解液類型 4
2.3 酸性水性電解液 4
2.4 離子混合型電解液 7
2.5 鋅枝晶 10
2.6 電解液添加劑 11
2.7 研究動機 13
第三章 實驗部份 15
3.1 實驗材料 15
3.2 實驗儀器 16
3.3 實驗流程圖 17
3.4 實驗步驟 17
3.4.1 電解液配製 17
3.4.2 非對稱電池組裝 18
3.4.3 半電池組裝 19
3.5 電解液分析 21
3.5.1 拉曼光譜儀(Raman Spectrum) 21
3.6 極片分析 21
3.6.1 X-光繞射分析(X-ray diffraction analysis, XRD) 21
3.6.2 掃描電子顯微鏡(Scanning electron microscope, SEM) 21
3.7 電化學量測 22
3.7.1 循環充放電測試(Cyclic charging-discharging test) 22
3.7.2 交流阻抗分析(Electrochemical impedance spectroscopy, EIS). 22
第四章 結果與討論 23
4.1 單鹽類系統 23
4.1.1 硫酸鋅系統 23
4.1.1.1 硫酸鋅濃度之影響 23
4.1.1.2 BIS添加劑之影響 25
4.1.1.3 電解液性質分析 27
4.1.1.4 電極表面分析 29
4.1.1.5 半電池 32
4.1.2 醋酸鋅系統 34
4.1.2.1 醋酸鋅濃度之影響 34
4.1.2.2 BIS添加劑之影響 35
4.1.2.3 電解液性質分析 37
4.1.2.4 電極表面分析 39
4.1.2.5 半電池 41
4.1.3 單鹽類系統綜合討論 43
4.2 混合鹽類系統 44
4.2.1 硫酸鋅混合系統 44
4.2.1.1 硫酸鋅-硫酸鋰混合系統 44
4.2.1.2 硫酸鋅-硫酸鋰-硫酸錳混合系統 46
4.2.1.3 高濃度混合系統 47
4.2.1.4 電解液性質分析 49
4.2.1.5 電極表面分析 50
4.2.1.6 半電池 54
4.2.2 醋酸鋅混合系統 58
4.2.2.1 醋酸鋅-醋酸鋰混合系統 58
4.2.2.2 電解液分析 60
4.2.2.3 電極表面分析 61
4.2.2.4 半電池 62
4.2.3 混合鹽類綜合討論 64
第五章 結論 65
第六章 未來工作 67
參考文獻 68

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