電解質添加劑對鋅二次電池陽極電化學性質的影響

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姓名

林玉羚(Yu-ling Lin) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

電解質添加劑對鋅二次電池陽極電化學性質的影響
(Effects of various electrolyte additives on electrochemical deposition/dissolution of the anode in zinc secondary batteries)

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摘要(中)

本研究從鋅空氣電池電解質的觀點切入，目的為解決鋅陽極在充放電過程中形成枝晶狀結構、在鹼性水溶液中易腐蝕及提升循環效率等問題。在含有25 g/L氧化鋅之6 M氫氧化鉀溶液中，加入3000 ppm不同添加劑，結果發現添加酒石酸者，可使循環效率從75.3 %提升至83.8 %為最多。
表面型態方面，添加檸檬酸者經過循環充放電後，鋅晶粒無明顯枝晶狀結構出現。添加CTAB、PEG 600與PEG 1000較有助於細化電極表面生成的鋅晶粒，抑制形成枝晶狀結構；XRD分析結果也同時發現，其鋅晶粒之(002)結晶面繞射強度較無添加劑者低。
在腐蝕抑制方面，從極化曲線可知，有機酸類如EDTA、不同分子量之PEG、離子液體陰離子鹽類如LiPF6、NaBF4、NaDCA、介面活性劑如CTAB添加劑都有減緩鋅腐蝕的作用，而PEG 1000添加劑使鋅金屬的腐蝕電位從-1.517 V上升至-1.489 V，腐蝕電流從498.05 μA/cm2下降至159.87 μA/cm2，抑制鋅溶解效果最佳。

摘要(英)

From the point of zinc-air battery electrolyte, we aim at solving the zinc anode dendritic structure which is formed during charge/discharge process, easing corrosion and enhance current efficiency in an alkaline aqueous solution. In this study, 6 M potassium hydroxide solution containing 25 g/L zinc oxide was added 3000 ppm of different additives found that by adding tartaric acid, can promote current efficiency from 75.3% to 83.8%.
In morphology, after charge-discharge cycles, the solution adding citric acid has no significant dendritic structure. Adding CTAB, PEG 600 and PEG 1000 refine zinc grains and inhibit the formation of dendritic structure; XRD analysis also found that the diffraction intensity of basal plane (002) in Zn is lower compared no additives solution.
In corrosion inhibition, polarization curves shows that organic acids such as EDTA, PEG of different molecular weight, ionic liquids anionic salts such as LiPF6, NaBF4, NaDCA, surfactants such as CTAB has a slowing effect of zinc corrosion additives, and PEG 1000 Additives make corrosion potential of zinc metal increased from -1.517 V to -1.489 V, the corrosion current decreased from 498.05 μA / cm2 to 159.87 μA / cm2 which has best property of anti-corrosion in Zn metal.

關鍵字(中)

★ 枝晶狀結構
★ 循環效率
★ 添加劑
★ 鋅腐蝕
★ 鹼性溶液

關鍵字(英)

★ Dendrite formation
★ Current efficiency
★ Additives
★ Zn corrosion
★ Alkaline solution

論文目次

摘要 ............................................................................................................................................. I
ABSTRACT .............................................................................................................................. II
誌謝 .......................................................................................................................................... III
總目錄 ...................................................................................................................................... IV
表目錄 .................................................................................................................................... VII
圖目錄 ................................................................................................................................... VIII
一、前言 .................................................................................................................................. 1
二、研究背景與文獻回顧 ...................................................................................................... 4
2- 1 金屬空氣電池 .................................................................................................................... 4
2-1- 1 鋰空氣電池 ................................................................................................................ 4
2-1- 2 鋅空氣電池 ................................................................................................................ 6
2- 2 二次鋅空氣電池電解質 .................................................................................................. 10
2-2- 1 有機酸類添加劑 ...................................................................................................... 12
2-2- 2 聚乙二醇添加劑 ...................................................................................................... 13
2-2- 3 表面活性劑添加劑 .................................................................................................. 14
2- 3 離子液體概論 .................................................................................................................. 19
2- 4 離子液體在鋅二次電池電解質上的應用 ...................................................................... 22
2-4- 1 離子液體做為電解質應用 ...................................................................................... 22
2-4- 2 離子液體做為腐蝕抑制劑 ...................................................................................... 23
2-4- 3 離子液體做為表面勻平劑 ...................................................................................... 23
三、實驗方法與步驟 ............................................................................................................ 28
3- 1 實驗材料 ........................................................................................................................... 28
3-1- 1 基礎電解質 ............................................................................................................... 28
3-1- 2 電解質添加劑 ........................................................................................................... 28
3-1- 3 電極材料 .................................................................................................................. 29
3- 2 不同電解質添加劑對於陽極鋅金屬之庫倫效率行為 .................................................. 29
3-2- 1 電化學測試 .............................................................................................................. 29
3-2- 2 循環伏安法 (Cyclic Voltammetry, CV) .................................................................. 30
3- 3 不同電解質添加劑對於陽極鋅金屬之枝晶狀結構影響 .............................................. 30
3-3- 1 三極式電化學法 ...................................................................................................... 30
3-3- 2 計時電位法 (chronopotentimetry, CP) .................................................................... 30
3-3- 3 掃描式電子顯微鏡(Scanning Electron Microscope, SEM) .................................... 31
3-3- 4 粉末X 光繞射儀(X-ray Powder Diffractometer, XRD) ......................................... 31
3- 4 不同電解質添加劑對於陽極鋅金屬之腐蝕行為 .......................................................... 32
3-4- 1 三極式電化學法 ...................................................................................................... 32
3-4- 2 開路電位(Open Circuit Potential, OCP) .................................................................. 32
3-4- 3 動態電位極化曲線(Potentiodynamic Polarization) ................................................ 32
四、結果與討論 .................................................................................................................... 35
4- 1 無添加劑時陽極鋅之電化學行為表現 .......................................................................... 35
4-1- 1 循環伏安法 .............................................................................................................. 35
4-1- 2 循環伏安法掃描速率與負電位極限對庫倫效率之影響 ...................................... 38
4-1- 3 鋅金屬之表面形態 .................................................................................................. 39
4-1- 4 鋅金屬之腐蝕行為 .................................................................................................. 40
4- 2 有機酸類電解質添加劑對鋅陽極電化學行為之影響 .................................................. 49
4-2- 1 循環伏安法 ............................................................................................................... 49
4-2- 2 有機酸類電解質添加劑對鋅陽極循環效率之影響 .............................................. 50
4-2- 3 有機酸類電解質添加劑對鋅陽極表面形態之影響 .............................................. 52
4-2- 4 有機酸類電解質添加劑對鋅陽極腐蝕行為之影響 .............................................. 54
4- 3 不同分子量之聚乙二醇電解質添加劑對鋅陽極電化學行為之影響 .......................... 62
4-3- 1 循環伏安法 .............................................................................................................. 62
4-3- 2 不同分子量之聚乙二醇電解質添加劑對鋅陽極循環效率之影響 ...................... 63
4-3- 3 不同分子量之聚乙二醇電解質添加劑對鋅陽極表面形態之影響 ...................... 64
4-3- 4 不同分子量之聚乙二醇電解質添加劑對鋅陽極腐蝕行為之影響 ...................... 66
4- 4 不同離子液體陰離子電解質添加劑對鋅陽極電化學行為之影響 .............................. 73
4-4- 1 循環伏安法 ............................................................................................................... 73
4-4- 2 不同離子液體陰離子電解質添加劑對鋅陽極循環效率之影響 .......................... 75
4-4- 3 不同離子液體陰離子電解質添加劑對鋅陽極表面形態之影響 .......................... 76
4-4- 4 不同離子液體陰離子電解質添加劑對鋅陽極腐蝕行為之影響 .......................... 78
4- 5 不同表面活性劑電解質添加劑對鋅陽極電化學行為之影響 ....................................... 85
4-5- 1 循環伏安法 .............................................................................................................. 85
4-5- 2 不同表面活性劑電解質添加劑對鋅陽極循環效率之影響 .................................. 86
4-5- 3 不同表面活性劑電解質添加劑對鋅陽極表面形態之影響 .................................. 87
4-5- 4 不同表面活性劑電解質添加劑對鋅陽極腐蝕行為之影響 .................................. 89
五、結論 ................................................................................................................................ 96
六、參考文獻 .......................................................................................................................... 97

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指導教授

張仍奎(Jeng-kuei Chang)

審核日期

2015-8-25

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