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研究生:張惠菁
研究生(外文):Hui-Ching Chang
論文名稱:元素成分調控於鉍銻銅氧之熱電特性探討
論文名稱(外文):Influence of Element Manipulation on the Thermoelectric Properties of BiCuTeO
指導教授:楊英杰楊英杰引用關係林麗瓊林麗瓊引用關係陳貴賢陳貴賢引用關係
指導教授(外文):Ying-Jay YangLi-Chyong ChenKuei-Hsien Chen
口試委員:廖建能陳俊維
口試委員(外文):Chien-Neng LiaoChun-Wei Chen
口試日期:2019-03-25
學位類別:博士
校院名稱:國立臺灣大學
系所名稱:電子工程學研究所
學門:工程學門
學類:電資工程學類
論文種類:學術論文
論文出版年:2019
畢業學年度:107
語文別:英文
論文頁數:100
中文關鍵詞:熱電鉍碲銅氧熱傳熱電優值冷壓碇熱壓碇
DOI:10.6342/NTU201901177
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隨著地球資源的過度消耗與可預見的能源短缺問題,發展新的能源是迫在眉梢的任務。熱電元件是具有發展潛力的綠色能源,因其能直接將熱能與電能相互轉換。但是,過低的能量轉換效率是目前阻礙熱電元件發展及普及化的原因之一。當前熱電研究的重點包括提升其熱電優值(ZT),與探討熱電材料的物理、化學機制。鉍碲銅氧(BiCuTeO)近年來的研究顯示該材料是具有潛力的熱電材料,適合被使用在中溫區(500~900 ºC)的應用中。在本論文中,利用調控鉍、碲、銅、氧四個元素的比例,並分別利用冷壓碇(Cold press)與熱壓碇(Hot press)技術,達到增進鉍碲銅氧塊材的熱電表現的目的。
材料的分析包含晶體結構,成份分析,以及熱電特性。由霍爾量測的結果顯示出鉍碲銅氧材料為P型半導體。X光晶體繞射顯示出該材料為多晶材料,而且,隨著元素的量調控,X光繞射圖譜中的雜項強度也跟著改變,表示雜項在樣品裡的比例有改變的趨勢。另外,不但主相裡的元素比例與所占樣品百分比跟著改變,樣品的顆粒大小也跟著變化。這些改變都會影響樣品的熱電表現。這些都會在這本論文裡有詳細的探討。
Thermoelectric (TE) devices that are used to convert waste heat directly into electricity address some of the problems of the prevailing energy crisis and global climate-change issues. Of the various TE materials that are available, metal oxides exhibit high thermal and chemical stability in air, so they are suited to many TE applications. However, in the mid-temperature region (from 500~900 ºC), most feature a TE figure of merit (ZT) that is less than the required value of 2. BiCuTeO is a good thermoelectric material, because it features an intrinsically low thermal conductivity and higher carrier concentration than BiCuSeO. This study manipulates the elemental composition in BiCuTeO to improve the thermoelectric performance of BiCuTeO. XRD and EPMA are used to determine the characteristics of samples and the thermoelectric properties are determined using ZEM and LFA. It is concluded that the manipulation of the elemental composition affects the fractional ratio and the properties of the secondary phases of a sample, which alters the thermoelectric performance of the sample. This study gives a detailed characterization and a discussion of the effect of manipulating the nominal elemental composition of BiCuTeO. The findings of this study are relevant to the search for novel high-performance TE materials.
Table of Contents
口試委員會審定書
誌謝…………………………………………………………………………………………………………………………………………………I
中文摘要………………………………………………………………………………………………………………………………………II
Abstract...…………………………………………………………………………………………………………………………III
Table of Contents……………………………………………………………………………………………………………IV
List of Figures………………………………………………………………………………………………………………VII
List of Tables………………………………………………………………………………………………………………XIII
Chapter 1 Background and Motivation………………………………………………………………1
Chapter 2 Overview of BiCuTeO………………………………………………………………………………7
2.1 Introduction of BiCuTeO……………………………………………………………………………………7
2.2 Strategies to Increase the Thermoelectric Performance……9
2.2.1 Increasing the Seebeck Coefficient……………………9
2.2.2 Maintaining the Carrier Mobility…………………………9
2.2.3 Decreasing the Lattice Thermal Conductivity………………………10
Chapter 3 Experimental and Analysis Techniques………………………………15
3.1 Synthesis………………………………………………………………………………………………………………………15
3.2 Pelletizing Samples……………………………………………………………………………………………15
3.2.1 Cold Pressing Technique……………………………………………………………………15
3.2.2 Hot Pressing Technique…………………………………………………………………………16
3.3 X-ray Powder Diffraction (XRD)………………………………………………………………17
3.4 ZEM-3…………………………………………………………………………………………………………………………………18
3.5 Laser Flash Analysis (LFA)…………………………………………………………………………19
3.6 Archimedes Method…………………………………………………………………………………………………20
3.7 Field Emission Electron Probe Microanalyzer (FE-EPMA)…21
3.8 Hall Measurement……………………………………………………………………………………………………21
Chapter 4 Study of the Effect of a Change in the Elemental Composition of BiCuTeO………………………………………………………………………………………………23
4.1 Preparation of BiCuxTeO, BixCuTeO, BiCuTexO, BiCuTeOx and (BiCu)xTeO (x=0.94-1.06)………………………………………………………………………………23
4.1.1 Flow Chart for the Synthesis………………………………………………………………23
4.1.2 Calculation of the Stoichiometric Ratio for the 5 batches: BiCuxTeO, BixCuTeO, BiCuTexO, BiCuTeOx and (BiCu)xTeO………………………………………………………………………………………………………………………………………………24
4.2 Characterization of theStructure……………………………………25
4.2.1 BiCuxTeO (x=0.94-1.06) ………………………………………………26
4.2.2 BixCuTeO (x=0.94-1.06) ………………………………………………30
4.2.3 BiCuTexO (x=0.94-1.06) ………………………………………………34
4.2.4 BiCuTeOx (x=0.94-1.06) ………………………………………………38
4.2.5 (BiCu)xTeO (x=0.94-1.06) …………………………………………42
4.3 Thermoelectric Properties………………………………………………………46
4.3.1 Electrical Conductivity (σ)……………………………………46
4.3.2 The Seebeck Coefficient (S) …………………………………50
4.3.3 Power Factor (PF) ……………………………………………………………52
4.3.4 Electronic Thermal Conductivity (κe)……………54
4.3.5 Lattice Thermal Conductivity (κL)……………………56
4.3.6 Thermal Conductivity (κ)……………………………………………58
4.3.7 Figure of Merit (ZT)………………………………………………………60
4.4 Summary……………………………………………………………………………………………………………………………62
Chapter 5 Study of the Bi and O Manipulations on BiCuTeO……63
5.1 Preparation of (BiO)xCuTe (x=0.94-1.06)………………………………………63
5.1.1 Flow Chart of the Synthesis Process……………………………………63
5.1.2 Calculation of the Stoichiometric Ratio of (BiO)xCuTe (x=0.94-1.06)………………………………………………………………………………………………………64
5.2 Results and Discussion………………………………………………………………………………………………………………………………65
5.3 Summary………………………………………………………………………………………………………………………………………75
Chapter 6 Increasing the Thermoelectric Performance of BiCuTeO by Addition of Excess Bi……………………………………………………………………76
6.1 Preparation of BixCuTeO (x=1.00-1.08)……………………………………………76
6.1.1 Flow Chart of the Synthesis Process……………………………………76
6.1.2 Calculation of the Stoichiometric Ratio of BixCuTeO (x=1.00-1.08)………………………………………………………………………………………………77
6.2 Results and Discussion……………………………………………………………………………………78
6.3 Summary……………………………………………………………………………………………………………………………86
Chapter 7 Significant Improvements in the Thermoelectric Performance of the BiCuTeO System by Oxygen Reduction……………87
7.1 Preparation of BiCuTeOx(x=0.84-1.00)………………………………………………87
7.1.1 Flow Chart of the Synthesis…………………………………………………………87
7.1.2 Calculation of the Stoichiometric Ratio of BiCuTeOx(x=0.84-1.00)………………………………………………………………………………………………………………………88
7.2 Results and Discussion……………………………………………………………………………………88
7.3 Summary……………………………………………………………………………………………………………………………95
Chapter 8 Conclusions…………………………………………………………………………………………………97
References……………………………………………………………………………………………………………………………98
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