臺灣博碩士論文加值系統

由於地殼中鋁含量豐富、成本低廉、理論容量高和固有的安全性，水鋁離子電池（AAIB）作為一種有前景的儲能係統而受到廣泛關注。儘管有這些優點，當代使用鋁或其合金陽極的AAIB仍面臨特定充電/放電過程的挑戰，且其活化機制仍不清楚。本研究探討了表面改質（在離子液體中處理的鋁，稱為T-Al）或合金化方法（例如Al-Cu 或Zn-Al 合金）如何影響各種陰離子水基鋁電解液的性能（例如1M Al(OTF)3、AlCl3 和 Al(NO3)3)。結果表明，表面改質和合金化都不足以支持這些水性電解質中鋁原子的可充電性。在使用這些電解質的對稱電池的整個充電/放電循環中，觀察到鋁及其合金的顯著溶解，並伴隨著顯著的氣體逸出。這些反應導致鋁及其合金在選定的水性電解質中腐蝕。鋁和 T-Al 陽極的腐蝕活性主要是由電解質中存在的氯陰離子或人造固體電解質界面層中的殘留物引發的。對於Al-Cu合金，Al2Cu奈米層狀結構的存在充當催化劑，促進水性電解質中α-Al的連續水解，從而產生H2。在測試的陽極中，鋅鋁合金陽極表現出最嚴重的氣體逸出反應，顯示在這些水性電解質中活性最高。這項研究首次闡明了在水性電解液鋁電池中使用表面改質或合金化方法時鋁陽極的反應機制。

Aqueous aluminum-ion batteries (AAIBs) have gained significant attention as promising energy storage systems due to aluminum's abundance in the Earth's crust, low cost, high theoretical capacity, and inherent safety. Despite these advantages, contemporary AAIBs utilizing aluminum or its alloy anodes face challenges with the specific charge/discharge processes, and their activation mechanisms remain unclear. This study examines how surface modification (aluminum treated in ionic liquids, referred to as T-Al) or alloying approach (such as Al-Cu or Zn-Al alloys) affect performance in various anionic aqueous aluminum-based electrolytes (e.g., 1M Al(OTF)3, AlCl3, and Al(NO3)3). Results indicate that neither surface modification nor alloying sufficiently supports the rechargeability of aluminum atoms from these aqueous electrolytes. Throughout the charge/discharge cycles in symmetric cells using these electrolytes, significant dissolution of aluminum and its alloys was observed, accompanied by notable gas evolution. These reactions caused aluminum and its alloys to corrode in the selected aqueous electrolytes. The corrosive activity of aluminum and T-Al anodes was primarily triggered by chloride anions present in the electrolytes or residual in the artificial solid electrolyte interface layer. In the case of the Al-Cu alloy, the presence of Al2Cu nano-lamellar structures acted as a catalyst, promoting continuous hydrolysis by α-Al in the aqueous electrolytes, thereby producing H2. The Zn-Al alloy anode exhibited the most severe gas evolution reactions among the tested anodes, indicating the highest activity in these aqueous electrolytes. For the first time, this research elucidates the reaction mechanisms at the Al anode when using surface modification or alloying approaches in aqueous electrolyte Al cells.

摘要 i
Abstract ii
目次 iii
圖目次(中文) v
第一章、緒論 1
1.1前言 1
1.2研究背景 1
1.3研究現況 2
1.4研究目的 2
第二章、文獻回顧 3
2.1鋁陽極的人工固體電解質介面 3
2.2鋁陽極的合金化 3
2.2.1 鋅鋁合金 3
2.2.2 鋁銅合金和鋁鈰合金 4
2.3陰極材料 5
2.4電解液 6
2.4.1濃度的影響 6
2.4.2添加劑改質 7
第三章、材料與實驗方法 9
3.1電極製備 9
3.1.1鋁陽極製備 9
3.1.2表面處理的鋁(T-Al) 9
3.1.2.1離子液體 9
3.1.2.2 T-Al陽極製備 10
3.1.3鋁銅合金 11
3.1.4鋅金屬 13
3.2電解液的製備 14
3.3測試裝置 14
3.4電化學測試方法 15
3.4.1循環伏安法(CV)測試 15
3.4.2恆流充放電測試 15
3.4.3交流阻抗(EIS)測試 15
3.4.4 塔菲爾極化法(Tafel)測試 15
3.4.5 伏安特性曲線(I−V 曲線)測試 15
3.5材料表徵方法 16
3.5.1 X射線衍射分析(XRD) 16
3.5.2 X射線光電子能譜(XPS) 16
3.5.3 掃描電子顯微鏡(SEM) 16
3.5.4 光學顯微鏡(OM) 16
3.5.5 傅立葉轉換紅外光譜(FTIR) 16
第四章、結果 17
4.1鋁銅合金的製造與表面特徵 17
4.2 T-Al的製備與表面特徵 19
4.3各種水性電解質對金屬/金屬對稱電池電化學性能的影響 21
4.3.1 在1M 三氟甲磺酸鋁(Al(OTF)3)中進行測試 21
4.3.2 在1M 含水氯化鋁(AlCl3·6H2O)中進行測試 23
4.3.3 在1M 氯化鋁(AlCl3)中進行測試 24
4.3.4 在1M 硝酸鋁(Al(NO3)3)中進行測試 25
4.4 Al82Cu18或Zn電極在1M AlCl3·6H2O和Al(OTF)3水性電解質中反應後的表面特徵 27
4.4.1 表面樣貌、XRD、SEM-EDS 27
4.5 Zn電極在1M AlCl3·6H2O和Al(OTF)3水性電解質中反應過後表面的XPS檢測 29
4.6 用鎢的對稱電池來證明鋁沉積 31
第五章、討論 35
5.1水性電解質中原始鋁陽極和鋁銅合金陽極的鈍化和活化機制 35
5.2處理過的鋁（T-Al）和鋁合金陽極的活性來源 38
5.2.1 T-Al陽極的活化機理 38
5.2.2 Al-Cu合金陽極的活化機理 41
5.2.3 Zn-Al合金陽極的活化機理 43
5.3 用於機械可充電Al-Air電池的Al-Cu合金和AlCl3水電解質 46
第六章、結論 48
參考文獻 49

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