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研究生： Adil Muneeb
Adil Muneeb
論文名稱： 應用在金屬空氣電池和水電解之雙功能觸媒材料設計的關鍵參數研究
Investigation of the key parameters for the design of bifunctional catalytic materials applied in metal-air batteries and water electrolyzers
指導教授： 黃崧任
Song-Jeng Huang
口試委員: 丘群
Chun Chiu
顏維謀
Wei-Mon Yan
李天錫
Tien-Hsi Lee
林景崎
Jing-Chie. Lin
曾有志
Yu-Chih Tzeng
Raman Sankar
Raman Sankar
學位類別： 博士
Doctor
系所名稱： 工程學院 - 機械工程系
Department of Mechanical Engineering
論文出版年： 2021
畢業學年度： 109
語文別： 英文
論文頁數： 102
中文關鍵詞： 金屬空氣電池 、水電解 、氧還原反應 、析氧反應 、析氫反應
外文關鍵詞： Metal-air batteries., Water electrolyzers., Oxygen reduction reaction (ORR)., Hydrogen evolution reaction (HER)., Oxygen evolution reaction (OER).
相關次數： 點閱：438  下載：2 
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  •  上一筆

    • 金屬空氣電池和水電解由於其高能量密度之特性，已被證明是儲能和轉換裝置的重要組成部分。然而，某些挑戰，例如催化材料對析氧反應 OER的緩慢動力學，（在金屬-空氣電池/水電解產生的 O2）。氧還原反應, ORR（金屬空氣電池放電）和析氫反應, HER（水電解中產生H2）目前在工業應用之前仍需解决。這項研究主要專注於探索和合理設計優良的OER、ORR和HER雙功能催化資料，以及在金屬空氣電池和水電解等實用可再生能源儲存和轉換裝置中長期穩定性和增强本徵的活化性。

    在OER和ORR方面，提出了一種雙功能催化材料Pr0.9Ca0.1Co0.8Fe0.2O3-?被設計並研製了具有最佳的Co4+/Co3+氧化態和氧空位比的單一鈣鈦礦型的氧化物，有利於促進對金屬空氣電池充放電。在HER和OER方面，作為一種高效的鹼性介質的水分解介質於新型層狀磷硫化鎳鋰物(NiLiP2S6)晶體被分解催化中被開發並應用於水電解。最終合成了Co和Fe雙金屬磷硫化物，並對其進行了研究，它被確認有助於未來OER催化劑合理的設計和關鍵描述符

    Metal air batteries and water electrolyzers have been proven as the significant face of energy storage and conversion devices due to their high energy densities. However, certain challenges such as sluggish kinetics of catalytic materials towards oxygen evolution reaction OER (charging in metal-air batteries/ O2 production in water electrolyzers), oxygen reduction reaction ORR (Discharging in metal-air batteries), and hydrogen evolution reaction HER (H2 production in water electrolyzers) still need to be addressed before their industrial use. This research work focused mainly on the investigation and rational design of superior bifunctional catalytic materials towards OER, ORR, and HER together with long-term stability and enhanced intrinsic activity employed in practical renewable energy storage and conversion devices such as metal-air batteries and water electrolyzers.
    In terms of OER and ORR, a bifunctional catalytic material Pr0.9Ca0.1Co0.8Fe0.2O3-? is designed and developed as single perovskite oxide with an optimum ratio of Co4+/Co3+ oxidation state and oxygen vacancy that could facilitate charging and discharging towards metal-air batteries. In terms of HER and OER, novel layered nickel lithium phosphosulfide (NiLiP2S6) crystals was devolved as a highly efficient water-splitting catalyst in alkaline media towards water electrolyzer applications. Finally, bimetallic Co and Fe phosphosulphide has been synthesized, and investigations have been made to identify the critical descriptor that can help towards the future rational design of the catalyst towards OER.

    Contents Abstract 5 Acknowledgements 6 LIST OF TABLES 10 LIST OF FIGURES 11 Chapter 1. Introduction and significance of the research impact 14 1.1 Energy outlook and challenges 14 1.1.1 Environmental Pollution 14 1.1.2 Climate change 15 1.1.3 Security of energy supplies 15 1.1.4 Meeting the challenge 15 1.2 Metal Air Batteries 16 1.3 Water Electrolyzers 19 1.4 Electrocatalytic Oxygen Reactions 21 1.4.1 Electrocatalyst development for Oxygen Reduction Reaction (ORR) 21 1.4.2 Electrocatalyst Development for Oxygen Evolution Reaction (OER) 25 1.4.3 Electrocatalyst Development for Hydrogen Evolution Reaction (HER) 26 1.5 Research Objectives and Outline 28 Chapter 2. Experimental methods and characterization techniques 31 2.1 Synthesis Routes 31 2.1.1 Nitrate combustion method 31 2.1.2 Solid state reaction 32 2.1.3 Chemical vapor transport method 32 2.2 Physio-chemical characterizations 33 2.2.1 Transmission electron microscopy (TEM) 33 2.2.2 Scanning electron microscopy 33 2.2.3 X-ray diffraction 34 2.2.4 X-ray photoelectron spectroscopy 34 2.2.5 Raman spectroscopy 34 2.3 Electrochemical characterization 35 2.3.1 Linear sweep voltammetry (LSV) 35 2.3.2 Chronoamperometry (CA) 35 2.3.3 Tafel Plots 35 2.3.4 Impedance measurements 35 Chapter 3. 37 Tailoring Co4+/Co3+ active sites in perovskite towards ORR/OER 37 3.1 Introduction 37 3.2 Experimental Section 38 3.2.1 Material Synthesis 38 3.2.2 Material Characterizations (XRD, TEM, SEM, XPS) 39 3.2.3 Electrochemical Measurements 39 3.3 Results and Discussion: 40 3.3.1 XRD and crystal structure of the perovskite catalysts 40 3.3.2 TEM and SEM 43 3.3.3 XPS 45 3.3.4 ORR/OER electrocatalytic activity and stability of the perovskite oxide catalyst 49 3.4 Summary 56 Chapter 4 57 Novel Layered NiLiP2S6 Crystals towards OER/HER 57 4.1 Introduction 57 4.2 Materials and Methods 58 4.2.1 Preparation of NiLiP2S6 (NLPS) crystal 58 4.2.2 Structural Characterization (XRD, SEM, TEM, XPS) 59 4.2.3 Electrochemical Measurements 60 4.2.4 Overall water splitting test 60 4.3 Results and Discussion 60 4.3.1 XRD and crystal structure 60 4.3.2 TEM and SEM 64 4.3.3 XPS 65 4.3.4 Electrocatalytic performance for OER/HER 66 4.3.5 Application as overall water splitting (water electrolyzer catalyst) 70 4.4 Summary 72 Chapter 5 73 Enhancing the Spin State of Cobalt Cation towards OER 73 5.1 Introduction 73 5.2 Experimental Section 74 5.2.1 Material Synthesis 74 5.2.2 Structural Characterization 74 5.2.3 Electrochemical Measurements 75 5.3 Results and discussion 75 5.3.1 XRD and structure 75 5.3.2 XPS and EPR 77 5.3.3 Electrocatalytic performance for OER 80 5.3.4 DFT 86 5.3.5 Soft X-ray absorption spectroscopy (XAS) 88 5.4 Summary 89 Chapter 6 90 Conclusion and Future Work 90 6.1 Conclusion 90 6.2 Future work 91 References 92 Appendix 101

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