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研究生：	顏宏盛 Yen, Hung-Sheng
論文名稱：	兩段燒結Bi-Se-Te三元熱電材料整合光伏發電系統之研究 Research on the Integration of Two-Stage Sintering Bi-Se-Te Ternary Thermoelectric Materials with Photovoltaic Power Generation System
指導教授：	施士塵 Shih, Shih-Chen
共同指導教授:	林仁輝 Lin, Jen-Fin
學位類別：	碩士 Master
系所名稱：	工學院 - 機械工程學系 Department of Mechanical Engineering
論文出版年：	2023
畢業學年度：	111
語文別：	中文
論文頁數：	121
中文關鍵詞：	碲化鉍基熱電材料、火花電將燒結、二段式燒結、熱電優值、透明導電薄膜、光伏發電
外文關鍵詞：	Bi2Te3-based thermoelectric materials, Spark plasma sintering(SPS), Two-stage sintering, Figure of merit, Transparent conductive films (TCF), Photovoltaic
相關次數：	點閱：65 下載：0
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近年來所經歷的各種能源危機，影響範圍、程度只增不減，對全球發展增添了需多的不穩定因素。穩定且環保的能源供應已成為能源發展的必經之路。太陽能所帶來的能量不僅可用於光電轉換效應，熱電效應也可以將大部分被浪費的廢熱進行回收利用，甚至是鍋爐、發動機或是交通運輸工具所產生的廢熱，皆可進行有效的回收。既增加光伏打電池的發電效率，也可以將浪費的熱能進行更有效地再度利用，達到在能源發展上開源節流的目的。本論文針對以下三個部分進行研究，分別是二階段火花電漿燒結Bi2Se0.45Te2.55塊材、應用遠紅外高穿透導電薄膜於鈣鈦礦太陽能元件、光伏系統直接耦合熱電系統提升發電效率。Bi2Se0.45Te2.55塊材利用火花電漿燒結(spark plasma sintering, SPS)二階段燒結製備，經不同燒結溫度、時間、壓力條件後，探討本研究中第二次燒結ZT值最高的燒結參數，結果顯示500℃ /50 MPa /5 min，相較優異於其他參數之ZT值，燒結時間及溫度增加會讓晶界密度降低，晶界散射發生機率也減少。而運作溫度提高容易使缺陷產生，使晶界密度增加，晶界散射發生機率大幅提升，載子遷移率受限。上述兩部分皆會影響Seebeck係數、電導率、熱傳導率，從而影響功率因子和熱電優值。以共濺鍍製程沉積ITO:Zr透明導電薄膜，在ITO濺鍍功率80W、Zr濺鍍功率35W下，獲得最低的元件電阻，顯示此低溫製程之透明導電薄膜無法有效提升鈣鈦礦太陽能元件的發電效率。直接耦合光伏系統與熱電系統，因為兩系統之間的最佳發電效率溫度區間不同，且光伏電池的發電效率會隨溫度升高而降低，因此光伏系統與熱電系統直接耦合於冷端後即可有效提升發電效率。

The Bi2Se0.45Te2.55 materials were fabricated by spark plasma sintering (SPS) in a two-step sintering process. Different sintering temperatures, times, and pressure conditions were investigated to determine the parameters that resulted in the highest ZT value in the second sintering stage. The results showed that 500°C /50 MPa /5 min resulted in an excellent ZT value compared to other parameters. Increasing the sintering time and temperature reduced the grain boundary density and the occurrence of grain boundary scattering. However, operation at higher temperatures increased the probability of defects and resulted in increased grain boundary density, which significantly increased the probability of grain boundary scattering and limited charge carrier mobility. These factors affect the Seebeck coefficient, electrical conductivity, thermal conductivity, and consequently the power factor and thermoelectric coefficient.Zirconium doped indium tin oxide (ITO:Zr) was deposited as a transparent conductive layer by a co-sputtering method. The lowest resistance was obtained at a sputtering power of ITO of 80 W and a Zr sputtering power of 35 W, indicating that this low-temperature process for transparent conductive layers does not effectively improve the power generation efficiency of perovskite solar cells.Direct coupling of photovoltaic and thermoelectric systems is challenging because they have different optimal temperature ranges for power generation efficiency. In addition, the power generation efficiency of photovoltaic cells decreases with increasing temperature. Therefore, direct coupling of photovoltaic and thermoelectric systems does not effectively improve the power generation efficiency.

摘要 I
Abstract III
目錄 X
圖目錄 XIV
第一章 緒論 1
1-1 前言 1
1-2 文獻回顧 2
1-2-1 熱電材料 2
1-2-2 提升材料熱電性能之方法 3
1-2-3 塊材材料 7
1-2-4 碲化鉍化合物簡介 10
1-2-5 碲硒化鉍化合物簡介 11
1-2-6 太陽能電池發展 12
1-2-7 透明導電薄膜 13
1-2-8 氧化銦錫 14
1-2-9 光伏熱電混和系統 14
1-3 研究動機 26
第二章 基本理論 27
2-1 熱電效應 27
2-1-1 Seebeck效應 27
2-1-2 Peltier效應 27
2-1-3 Thomson效應 28
2-1-4 熱電效應 28
2-2 熱電材料傳輸理論 29
2-2-1 電子電傳導與電子熱傳導 29
2-2-2 Seebeck效應與電子電傳導 30
2-2-3 載子遷移率與載子有效質量 30
2-2-4 聲子熱傳導與電子電傳導 31
2-3 布拉格定律(Bragg's law) 31
2-4 晶粒大小理論 32
2-5 霍爾量測原理 32
2-6 太陽能電池量測參數與原理 34
2-7 熱電光伏發電系統整合 35
第三章 實驗方法與設備 42
3-1 Bi-Se-Te粉末冶金製程之粉末製作 42
3-1-1 Bi-Se-Te粉末球磨合金化 42
3-1-2 球磨時間參數調整 43
3-1-3 粉末粒徑量測 43
3-2 二段式火花電漿燒結Bi-Se-Te熱電材料 43
3-2-1火花電漿燒結(spark plasma sintering, SPS) 43
3-2-2 燒結溫度、壓力、時間調整 44
3-3 熱電性值量測 44
3-3-1 比熱性質量測 44
3-3-2 熱傳導性質量測 45
3-3-3 Seebeck係數量測 45
3-3-4電導性質量測 46
3-3-5 Ｘ光繞射儀 46
3-3-6 微結構觀察 46
3-4鈣鈦礦太陽能元件製作 47
3-4-1 溶液工程 47
3-4-2 共濺鍍沉積 48
3-4-3 測量元件效率 48
3-5 熱電光伏系統整合 48
3-5-1 直接耦合 49
3-5-2 模擬光伏系統置於熱端 49
3-5-3 模擬光伏系統置於冷端 49
3-6 實驗設備 49
第四章 結果與討論 60
4-1 Bi-Se-Te粉末製作 60
4-1-1機械合金化時間調整 60
4-1-2粉末結構與結晶分析 60
4-2  第二次火花電漿燒結 66
4-2-1晶體結構與結晶分析 66
4-2-2電導性質量測 71
4-2-3 Seebeck係數量測 75
4-2-4熱傳導性質量測 80
4-2-5 熱電優值(ZT) 84
4-3  第一次與第二次燒結微結構觀察與比較 87
4-3-1晶體結構與熱電性質分析 87
4-3-2熱電性質分析 91
4-3-3 SEM分析 95
4-3-4 TEM分析 98
4-4鈣鈦礦太陽能元件效率量測 102
4-4-1 共濺鍍ITO:Zr透明電極元件之光學特性分析 102
4-5熱電光伏混和系統 105
4-5-1 PV-TIM-TEG系統 105
4-5-2 PV-TEG系統效率評估 109
第五章 結論與未來展望 111
5-1 結論	 111
5-2 未來展望 112
第六章 參考文獻 114
                                    

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