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研究生： 陳天心
Tien-Shin Chen
論文名稱： 濺鍍沉積的鉬鎳鐵三元金屬薄膜以雙層電極形式在鹼性溶液中應用於整體水分解
Sputter-Deposited MoNiFe Trimetallic Thin Films in the Form of Double-Layer Electrodes for Overall Water Splitting in an Alkaline Solution
指導教授： 郭東昊
Dong-Hau Kuo
口試委員: 柯文政
Wen-Cheng Ke
薛人愷
Ren-Kae Shiue
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： 2022
畢業學年度： 110
語文別： 英文
論文頁數： 151
中文關鍵詞： RF sputter 、electrodeposition 、alloy 、Layered double hydroxide 、electrocatalyst 、overall water splitting
外文關鍵詞： RF sputter, electrodeposition, alloy, Layered double hydroxide, electrocatalyst, overall water splitting
相關次數： 點閱：338  下載：0 
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    • Electrochemical water splitting is crucial for producing hydrogen as the green energy carrier in the future. However, the cost is relatively high compare to other hydrogen produce techniques such as steam methane reforming. Nowadays, the noble metal such as platinum is the benchmark catalyst for HER hydrogen evolution reaction (HER) and iridium and ruthenium-based materials for oxygen evolution reaction (OER). This research aims to create a non-noble catalyst for water splitting and replace the noble catalysts.
    In this research, we successfully fabricated double-layer structure anode and cathode on Ni foam for overall water splitting via radio-frequency (RF) sputter and electrodeposition. During the experiment, we first constructed the base layer by sputter trimetallic thin film on Ni foam. Then, second layer was electrodeposited on trimetallic thin film to form anode. For cathode, an inner layer of Ni was firstly sputtered prior to the trimetallic thin film to form the cathode. Parameters such as sputter power and time, the composition ratio of target, and the concentrations of electrolyte for electrodeposition were adjusted. The thin film properties were analyzed by SEM, EDS, XRD, TEM, XPS, Raman measurement, and electrochemical test.
    According to the experimental results, MoNiFe film showed significant performance improvements in both OER and HER, as compared to NiFe film. When MoNiFe was constructed in the form of a double-layer structure, the electrocatalytic electrode performed even better for both cathode and anode. By virtue of the excellent HER and OER performance of the as-prepared cathode and anode, we assembled the cathode and the anode into a two-electrode electrolyzer labeled as MNF-2b/Co3-Fe//Ni60/MNF-2b. This electrolytic cell exhibited a low cell voltage of 1.72 V under 100 mA/cm2. For the material properties analysis, we have verified that the MNF-2b thin film was amorphous or low crystalline alloy. On top of MoNiFe, the electrodeposited second layer of Co3Fe was confirmed to be CoFe-LDH. For the sputtered inner layer under MoNiFe, it was identified as crystalline nickel.

    Electrochemical water splitting is crucial for producing hydrogen as the green energy carrier in the future. However, the cost is relatively high compare to other hydrogen produce techniques such as steam methane reforming. Nowadays, the noble metal such as platinum is the benchmark catalyst for HER hydrogen evolution reaction (HER) and iridium and ruthenium-based materials for oxygen evolution reaction (OER). This research aims to create a non-noble catalyst for water splitting and replace the noble catalysts.
    In this research, we successfully fabricated double-layer structure anode and cathode on Ni foam for overall water splitting via radio-frequency (RF) sputter and electrodeposition. During the experiment, we first constructed the base layer by sputter trimetallic thin film on Ni foam. Then, second layer was electrodeposited on trimetallic thin film to form anode. For cathode, an inner layer of Ni was firstly sputtered prior to the trimetallic thin film to form the cathode. Parameters such as sputter power and time, the composition ratio of target, and the concentrations of electrolyte for electrodeposition were adjusted. The thin film properties were analyzed by SEM, EDS, XRD, TEM, XPS, Raman measurement, and electrochemical test.
    According to the experimental results, MoNiFe film showed significant performance improvements in both OER and HER, as compared to NiFe film. When MoNiFe was constructed in the form of a double-layer structure, the electrocatalytic electrode performed even better for both cathode and anode. By virtue of the excellent HER and OER performance of the as-prepared cathode and anode, we assembled the cathode and the anode into a two-electrode electrolyzer labeled as MNF-2b/Co3-Fe//Ni60/MNF-2b. This electrolytic cell exhibited a low cell voltage of 1.72 V under 100 mA/cm2. For the material properties analysis, we have verified that the MNF-2b thin film was amorphous or low crystalline alloy. On top of MoNiFe, the electrodeposited second layer of Co3Fe was confirmed to be CoFe-LDH. For the sputtered inner layer under MoNiFe, it was identified as crystalline nickel.

    Abstract i Table of contents iii List of figures viii List of tables xv CHAPTER 1 INTRODUCTION 1 1.1 Background of the study 1 1.2 Research Purposes 2 CHAPTER 2 BASIC THEORY AND LITERATURE SURVEY 4 2.1 Basic theory of the research 4 2.1.1 Water splitting 4 2.1.2 HER (Hydrogen Evolution Reaction) 4 2.1.3 OER (Oxygen Evolution Reaction) 5 2.2 Basic theory of Electrochemical characterization of catalyst 7 2.2.1 Overpotential (η) 7 2.2.2 Tafel slope 8 2.2.3 Relative ECSA (Electrochemical surface area) 8 2.2.4 Charge Transfer Resistance (RCT) 8 2.2.5 Stability 8 2.2.6 Faraday efficiency 9 2.3 Fabrications of electrocatalyst 10 2.3.1 Hydrothermal synthesis 10 2.3.2 Electrodeposition 13 2.3.3 RF sputtering in Electrocatalysis 15 2.4 Layered Double Hydroxide (LDH) 17 2.4.1 Anion replacement 18 2.4.2 Nano-structuring in forming hybrid LDHs 19 2.4.3 Vacancy engineering 21 2.5 NiFe-based electrocatalyst 24 2.6 MoNi-based electrocatalyst 28 2.7 NiFeMo trimetallic electrocatalyst 32 CHAPTER 3 EXPERIMENTAL PROCEDURES 36 3.1 Experimental materials and specifications 36 3.2 Experimental instruments 36 3.2.1 Analytical balance 37 3.2.2 Vacuum oven 37 3.2.3 Vacuum Hot press 37 3.2.4 RF sputter machine 37 3.2.5 Ultrasonic processor 37 3.2.6 Experimental procedure 38 3.2.7 Pretreatment of the substrates 39 3.2.8 Target fabrication and RF sputter of metallic thin film 39 3.2.9 Electrodeposition of outer or second layer onto MNF-2b 40 3.3 Characterizations 42 3.3.1 Scanning electron microscopy (SEM) 42 3.3.2 X-ray diffractometry (XRD) 43 3.3.3 X-ray photoelectron spectroscopy (XPS) 45 3.3.4 Micro-Raman spectrometer (Micro-Raman) 46 3.3.5 Transmission electron microscope (TEM) 47 3.3.6 Electrochemical test 48 CHAPTER 4 RESULTS AND DISCUSSION 52 4.1 Screening tests of RF sputtered trimetallic thin films for HER 52 4.1.1 LSV test and Tafel slope for HER of the RF sputtered trimetallic thin films 52 4.2 MoNiFe films deposited at different Mo contents 54 4.2.1 LSV test and Tafel slope for HER of MoNiFe films deposited at different Mo contents 54 4.2.2 EIS analysis for MoNiFe films deposited at different Mo contents 56 4.2.3 LSV analysis for OER of MoNiFe films deposited at different Mo contents 58 4.2.4 EIS analysis for MoNiFe films deposited at different Mo contents 60 4.2.5 CV analysis for MoNiFe films deposited at different Mo contents 62 4.2.6 SEM and EDS analyses for MoNiFe films deposited at different Mo contents 64 4.3 MNF-2 deposited at different sputtering powers (50W, 70W, 90W) 66 4.3.1 LSV test and Tafel plat for analyzing the influence on HER of MNF-2 deposited at different sputtering powers 66 4.3.2 EIS analysis for MNF-2 deposited at different sputtering powers 68 4.3.3 LSV test and Tafel plot for analyzing the influence on OER of MNF-2 deposited at different sputtering powers 70 4.3.4 EIS analyses for MNF-2 deposited at different sputtering powers 72 4.3.5 CV analysis for MNF-2 deposited at different sputtering powers 74 4.3.6 SEM analysis of MNF-2 deposited at different sputtering powers 76 4.3.7 XRD analysis for MNF-2 deposited at sputtering power of 70W 78 4.3.8 TEM and element mapping analyses of MNF-2b thin film 79 4.3.9 XPS analysis of MNF-2b thin film 81 4.4 MNF-2b thin film with a differently electrodeposited top layer to form a two-layer structure 83 4.4.1 LSV test and Tafel plot for analyzing the influence on OER of MNF-2b thin films with an electrodeposited top layer 83 4.4.2 LSV test and Tafel plot for analyzing the influence on OER of MNF-2b thin films with an electrodeposited top layer 85 4.4.3 LSV test and Tafel plot for analyzing the influence on OER of MNF-2b thin films with an electrodeposited top layer at different ratios of Co and Fe 87 4.4.4 EIS test for analyzing the influence on OER resistance of MNF-2b thin films with an electrodeposited top layer at different ratios of Co and Fe 89 4.4.5 CV analysis for influence on OER of MNF-2b thin films with an electrodeposited top layer at different ratios of Co and Fe 91 4.4.6 Comparisons among single-layer MNF-2b, Co3Fe LDH top layer, and double-layer MNF-2b/Co3Fe LDH 93 4.4.7 SEM for analyzing the influence on OER of MNF-2b thin films with an electrodeposited top layer at different ratios of Co and Fe 95 4.4.8 XRD and Raman analyses for the influence on the structure of MNF-2b thin films with an electrodeposited top layer at different ratios of Co and Fe 97 4.4.9 XPS analysis of single-layer Co3Fe LDH and double-layer MNF-2b/Co3Fe LDH 98 4.5 Influence on HER for MNF-2b with different sputter metals as an inner layer 102 4.5.1 LSV test and Tafel plot for analyzing the influence on HER for MNF-2b with different sputter metals as an inner layer 102 4.5.2 LSV test and Tafel plot for analyzing the influence on HER for MNF-2b with an inner Ni layer deposited at different periods 104 4.5.3 EIS test for analyzing the influence on HER resistance of MNF-2b with an inner Ni layer deposited at different periods 106 4.5.4 CV analysis for the influence on HER of MNF-2b with an inner Ni layer deposited at different periods 108 4.5.5 Comparisons among single-layer MNF-2b and Ni60, and double-layer MNF-2b/Co3Fe 110 4.5.6 SEM analysis for MNF-2b with an inner Ni layer deposited at different periods 112 4.5.7 XRD analysis for MNF-2b with an inner Ni layer deposited for 60 min 114 4.5.8 TEM and EDS mapping analyses of Ni60/MNF-2b 115 4.6 Full cell characterization 117 4.6.1 Overall water splitting 117 4.6.2 Stability test 119 4.6.3 Faraday efficiency 121 4.6.4 Overall water splitting with AEM for MNF-2b/Co3Fe LDH//Ni60/MNF-2b 124 4.6.5 Faraday efficiency of MNF-2b/Co3Fe LDH//Ni60/MNF-2b cell tested with an anion membrane 125 CHAPTER 5 CONCLUSIONS 126 REFERENCES 128

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