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研究生: 徐啟寧
Chi-Ning Hsu
論文名稱: 以電沉積技術開發用於整體水分解的層狀雙氫氧化物電極
Layered Double Hydroxide Electrode Developed by Electrodeposition Technique for Overall water splitting
指導教授: 郭東昊
Dong-Hau Kuo
口試委員: 薛人愷
Ren-Kae Shiue
柯文政
Wen-Cheng Ke
學位類別: 碩士
Master
系所名稱: 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年: 2020
畢業學年度: 108
語文別: 中文
論文頁數: 118
中文關鍵詞: 電沉積層狀雙氫氧化物薄膜電催化性能整體水分解
外文關鍵詞: electrodeposition, Layered Double Hydroxide, thin film, electrical property, overall water splitting
相關次數: 點閱:370下載:14
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本研究使用電沉積技術成功製備出具高電催化特性的雙功能NiFe-LDH/Ni(OH)2雙層薄膜,並在實驗中,探討不同的層狀雙氫氧化物的電催化性能,以及不同的電沉積參數對薄膜的電化學特性與表面特徵之影響。透過SEM、XRD、Raman及XPS來分析薄膜的表面特徵,並使用雙頻道恆電位/電流/交流阻抗儀來量測其電催化性能。
本實驗改變電沉積電壓與時間製備單層之NF3b薄膜與雙層之NF3b/N2與NF3b/N3薄膜。由SEM結果得知NF3b薄膜呈現出直立片狀結構; NF3b/N2呈現出表面具有微小顆粒的直立片狀結構;NF3b/N3呈現出表面平整光滑的直立片狀結構。拉曼量測結果得知NF3b薄膜為NiFe-LDH結構;NF3b/N2與NF3b/N3薄膜為Ni(OH)2結構。
電化學量測結果顯示,NF3b/N2具有最佳的OER電催化性能,
LSV量測可以得到,在200 mA/cm2的電流下,過電勢為257 mV,Tafel斜率值為126 mV/dec。NF3b/N3則具有最佳的HER性能,在-10 mA/cm2的電流下,過電勢為-151 mV,Tafel斜率值為86 mV/dec。本實驗將NF3b/N2薄膜與NF3b/N3薄膜作為電極,使用1 M KOH作為電解質,組裝成簡易的鹼性電解槽,並測試用於整體水分解的電催化性能,在LSV量測中得到,在10 mA/cm2的電流下,所需電壓為1.63 V,在CstC的測試中也顯現出良好的穩定性。


In this research, 1st-layer Ni-Fe-LDH/2nd-layer Ni(OH)2 composite thin films were fabricated and utilized for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) to simultaneously conduct electrocatalytic water splitting process. The composite thin films were deposited on Ni foam by electrodeposition technique. To find out the optimum performances of the catalysts, the first layer was fabricated with different voltages of -0.7 – -1.15 V and fixed deposition time of 2.5 min. The second layer was done with a fixed potential at -1 V and different deposition times of 1 – 3 min. The electrochemical properties and characteristics of the as-deposited composite thin films were analyzed with XRD, SEM, Raman, XPS measurements, and electrocatalytically tested with HER and OER as well as overall water splitting.
It was found that the morphology of 1st-layer Ni-Fe LDH with deposition potential at -1 V and time at 2.5 min showed as the lamellar sheets standing perpendicularly to Ni foam substrate. The first layer LDH was then electrodeposited with Ni to form a thin second layer of Ni(OH)2 which was confirmed with Raman spectroscopy analysis. The performance of the composite thin films were tested with Ni(OH)2 deposited with different deposition times. The electrochemical measurements indicated the NF3b/N2 thin film electrode exhibited the best properties for OER. With the current density of 200 mA/cm2, the overpotential and Tafel slope for oxygen evolution reaction were 257 mV and 126 mV/dec, respectively. On the other hand, the NF3b/N3 thin film electrode exhibited the best properties for HER. The best HER performance exhibited with the overpotential of -151 mV and Tafel slope of 86 mV/dec at current density of -10 mA/cm2. To show the overall water splitting process, NF3b/N2 and NF3b/N3 thin film electrodes were repectively utilized as anode and cathode with 1 M KOH as electrolyte. For the overall water splitting reaction, the electrolytic cell had the overpotantial of 1.63 V at 10 mA/cm2, while it has 348 mA/cm2 at 2.0 V. At the constant currednt test for cell stability, the cell gradually reached stable overpotential of 1.84 V at 20 mA/cm2. This work contributed to a simple electrodeposition method to fabricate double-layer composite thin film for a promising and stable electrocatalytic water splitting reaction in alkaline solution.

摘要 I Abstract II 致謝 IV 圖目錄 VIII 表目錄 XIII 第一章、緒論 1 1.1前言 1 1.2 研究動機與目的 2 第二章、文獻回顧與原理 5 2.1 水分解的電化學原理 5 2.1.1 HER反應機制 6 2.1.2 OER反應機制 7 2.2層狀雙氫氧化物 (Layered Double Hydroxide , LDH) 9 2.3 雙功能電催化劑 18 第三章、實驗方法與步驟 29 3.1實驗材料與規格 29 3.2實驗設備 30 3.2.1分析電子天平 30 3.2.2真空烘箱 30 3.2.3超音波震盪機 30 3.3實驗步驟 31 3.3.1基板前處理 32 3.3.2電沉積溶液配置 32 3.3.3電沉積薄膜 32 3.3.4薄膜性質量測 34 3.4分析儀器介紹與量測參數 35 3.4.1 高解析度場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscopy, FESEM) 35 3.4.2 三電極電化學反應量測系統 36 3.4.3 高功率X光繞射技術(High Power X-Ray Diffractometry, XRD) 39 3.4.4顯微拉曼光譜儀 (Micro-Raman spectrometer) 40 3.4.5 X光光電子能譜儀(X-ray Photoelectron Spectroscopy, XPS) 41 第四章、結果與討論 42 4.1材料篩選之量測與探討 42 4.2改變電沉積電壓對NiFe-LDH薄膜之電性分析及探討 44 4.2.1改變電沉積電壓之NiFe-LDH薄膜用於析氧反應之LSV量測 44 4.2.2改變電沉積電壓之NiFe-LDH薄膜於析氧反應之EIS阻抗特性分析 47 4.2.3改變電沉積電壓之NiFe-LDH薄膜CV量測 49 4.3改變電沉積時間對NiFe-LDH薄膜之電性分析及探討 52 4.3.1改變電沉積時間之NF3y薄膜用於析氧反應之LSV量測 52 4.3.2改變電沉積時間之NF3y薄膜EIS於析氧反應之阻抗特性分析 56 4.3.3改變電沉積時間之NF3y薄膜CV量測 58 4.3.4 對NF3b薄膜之CstC量測 61 4.4 第二層薄膜材料篩選之量測與探討 62 4.5第二層薄膜電沉積時間對NiFe-LDH薄膜之電性影響 64 4.5.1改變電沉積時間之NF3b/Nz薄膜於析氧反應之LSV量測 64 4.5.2改變電沉積時間之NF3b/Nz薄膜於析氫反應之LSV量測 68 4.5.3改變電沉積時間之NF3b/Nz薄膜於析氧反應之EIS阻抗特性量測 71 4.5.4改變電沉積時間之NF3b/Nz薄膜於析氫反應之EIS阻抗特性量測 73 4.5.5改變電沉積時間之NF3b/Nz薄膜其CV量測 75 4.6 NF3b/N2與NF3b/N3薄膜電極用於整體水分解(OWS, Overall water splitting)的電化學量測 78 4.6.1將NF3b/N2與NF3b/N3薄膜用於整體水分解的LSV量測 78 4.6.2將NF3b/N2與NF3b/N3薄膜用於整體水分解的CstC量測 80 4.7改變實驗條件之NFx、NF3y與NF3b/Nz薄膜表面特徵分析與探討 81 4.7.1改變電沉積電壓之NFx薄膜其SEM分析 81 4.7.2改變電沉積時間之NF3y薄膜其SEM分析 83 4.7.3改變第二層薄膜電沉積時間之NF3b/Nz薄膜其SEM分析 85 4.7.4 單層NF3b以及雙層NF3b/N2與NF3b/N3薄膜之XRD分析 87 4.7.5 單層NF3b以及雙層NF3b/N2與NF3b/N3薄膜之拉曼分析 89 4.7.4 單層NF3b與雙層NF3b /Ni薄膜之XPS分析 90 第五章、結論 93 參考文獻 97

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