以電化學沉積法製備奈米氧化釩及錫在多孔鎳電極上與其儲電特性

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許清樺(Ching-Hua Hsu) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

以電化學沉積法製備奈米氧化釩及錫在多孔鎳電極上與其儲電特性
(Electrochemical deposition of nanostructured vanadium oxide and tin on porous nickel substrates and investigation of their energy storage performance)

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★ 熱解法製備硬碳材料應用於鈉離子電池負極	★ 活性碳粉之表面官能基及粒徑尺寸對超高電容特性的影響
★ 離子液體電解質於鈉離子電池之應用	★ 研發以二氧化錫為負極材料的鈉離子電池：電解液、輔助性碳材料與黏著劑的優化

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摘要(中)

在本實驗中以一貫的電化學方式製備電極，實驗首先在銅鎳共鍍液中，使用合金去合金法製作多孔鎳奈米基材，此材料具高比表面，且結構均勻度高，極適合應用於儲電元件之電流收集器上。
　　本研究將釩氧化物沉積於上，並探討其擬電容特性。在3 M硝酸鉀電解液中，使用多孔鎳為基材的電極相較於平板基材，其奈米結構可以大幅提升其電容值，改善高速下之維持率，降低內電阻，對於整體效能皆有顯著提升。
　　而日常生活中之儲能元件，以鋰電池使用最廣泛，高能量密度之負極材料，在鋰離子遷入過程產生巨大之體積膨脹，使用多孔鎳搭配錫電極，其奈米結構將有效的降低絕對膨脹值，而基材均勻性也能避免應力過於集中，而比較平板與多孔基材，多孔基材確實也表現出較高電容值，而在15 A g-1的快充速度下電容值還有459mAh g-1之表現。
　　而使用基材間接達奈米化雖為一可行方式，但若使用離子液體為電鍍液，則可一步驟直接沉積出奈米結構，而在離子液體系統中，無電解水之副反應，沉積效率也可大幅提升，而在工業中製程，使用離子液體也可避免等候時間過長，導致氧化物及其他副產物生成，而在適當條件下，以0.3 A g-1之條件充放也展現出可與水溶液系統比較之效能，其首圈放電電容為863 mAh g-1 ,而可逆電容達641 mAh g-1。

摘要(英)

In this study, the electrodes were prepared by electrochemical manner. In the beginning, porous nickel substrate was prepared by alloy/dealloy method in an aqueous solution containing Cu(II) and Ni(II). This material has high specific surface and uniform structure, very suitable for electrical storage devices as current collector.
The first study, vanadium oxide deposited on porous Ni and explored its capacitance characteristics in 3 M KNO3 electrolyte. A porous nickel substrate compared to flat substrates, which can proof nanostructures greatly increase their capacitance value and improve the maintenance at high rate, low internal resistance leading to the overall performance significantly enhanced.
The 2nd study is lithium batteries fabrication, the most widely used energy storage components. Using porous nickel with tin electrode, the absolute expansion will effectively reduce and the uniformity structure of the substrate can avoid concentration of stress. Between two kind substrates, the porous substrate exhibited higher capacitance value at high current density (15 A g-1), the capacity reached 459 mAh g-1.
Although applying nano substrate is a possible way, the ionic liquid is used as the plating solution can directly deposited nanostructures give the better method. In details for the ionic liquid system, without the side reaction of electrolysis of water, the deposition efficiency can be greatly improved for further industry processes, the utilization of ionic liquid will avoid oxides and other byproducts generated in long waiting time. At the first cycle, the lithiated capacity is 863 mAh g-1 and the reversible capacity is 641 mAh g-1 (0.3 A g-1), which is comparable to those prepared in aqueous solution.

關鍵字(中)

★ 超高電容器
★ 多孔鎳
★ 鋰離子電池
★ 負極

關鍵字(英)

★ Supercapacitors
★ Porous nickel
★ Lithium ion battery
★ Negative electrode

論文目次

摘要 I
Abstract II
致謝 III
目錄 IV
表目錄 VI
圖目錄 VII
一、緒論 1
二、研究背景暨文獻回顧 3
2-1　儲電元件概述 3
2-2　超高電容器 5
2-3　鋰離子電池 8
2-4　釩氧化物製備方式 14
2-5　錫基負極材料 21
2-6　奈米孔洞材料 23
2-6-1　去合金化的原理 24
2-6-2　電鍍銅鎳合金及其去合金化的原理 25
2-7　離子液體簡介 28
2-8　離子液體於鍍錫之應用 30
三、實驗方法與步驟 33
3-1　電極製備 33
3-1-1　多孔鎳基材 33
3-1-2　平板鎳及多孔鎳基材沉積釩氧化物電極 34
3-1-3　平板鎳及多孔鎳基材沉積錫電極 34
3-1-4　離子液體沉積之錫電極 35
3-2　材料特性分析 37
3-3　釩氧化物之電化學特性分析 37
3-3-1　循環伏安法 37
3-3-2　計時電位法 37
3-4　鈕扣電池製備 37
3-5　錫之電化學特性分析 39
3-5-1　循環伏安法 39
3-5-2　計時電位法 39
四、結果與討論 40
4-1 平板暨多孔之摻鉀釩氧化物電極 40
4-1-1　電極表面形貌 40
4-1-2　電極結晶結構 41
4-1-3　電極組成元素及價數分析 41
4-1-4　電化學特性 42
4-2 平板暨多孔錫電極 54
4-2-1　電極表面形貌 54
4-2-2　電極結晶結構與組成元素 55
4-2-3　電極沉積效率 55
4-2-4　電化學特性 56
4-3 離子液體中沉積之錫電極 67
4-3-1　電極表面形貌 67
4-3-2　電極結晶結構 68
4-3-3　電極沉積效率 68
4-3-4　電化學特性 69
五、結論 85
參考文獻 87

參考文獻

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指導教授

張仍奎(Jeng-Kuei Chang)

審核日期

2013-8-27

推文