臺灣博碩士論文加值系統

　　本研究應用乙二胺四乙酸為螯合劑，硼氫化納為還原劑，氯化鉍和碲作為起始原料，純水為溶劑，在水熱系統中，經由中高溫及高壓之過程合成碲化鉍粉末，再以燒結技術製備碲化鉍塊材並量測其熱電性質。
利用XRD、SEM、TEM、BET等探討水熱反應之製備參數如合成時間、合成溫度、pH值、乙二胺四乙酸對氯化鉍之莫爾比等對合成碲化鉍粉末之穩定性，並探討製程參數對碲化鉍粉末結構等性質的影響。
研究發現，pH值12.47，乙二胺四乙酸對氯化鉍之莫爾比0.2，於XRD分析圖譜中已發現皆有(015)、(1010)、(110)三個主要晶面，顯示已有碲化鉍形成。由TEM分析可以得知，隨著合成溫度的提升，Bi2Te3 粉末的粒徑有增大的趨勢，粒徑分布約在50~200nm。由BET粉末比表面積分析中得知，水熱反應過程中其合成溫度越高，則比表面積有越小的趨勢，比表面積範圍分佈在14-29 m2/g。而在電阻率量測方面，水熱合成溫度越高，電阻率也愈小，其中電阻值最小為合成溫度240℃，電阻率為8.54 ohm-cm，seebeck係數為-102μv/k2，功率因子(power factor)為1218μw/cmk2。
關鍵詞: 水熱法,碲化鉍 , 熱電材料

In the study, BiCl3 and Te were used as raw materials, and water, EDTA and NaBH4 were used as solvent, chelating agent and reducing agent, respectively. Under medium-high temperature and high pressure conditions, the Bi2Te3 powders were synthesized by hydro-thermal method. And then, the Bi2Te3 bulks were prepared by sintering technology.
The effect of various preparation factors including the synthesis time, the synthesis temperature, the molar ratio of EDTA/BiCl3 and others on the stability, the microstructure and other properties of the Bi2Te3 powders was studied by XRD, SEM, TEM, BET and so on.
The results of XRD suggests that the Bi2Te3 is formed because of the main three planes (015)、(1010) and (110). The results of TEM imply that the particle size of the Bi2Te3 powders trends to increase with increasing the synthesis temperature. And the distribution range of the particle size is 50-200nm. The results of BET reveal that the specific surface area of the Bi2Te3 powders trends to increase with increasing the synthesis temperature. And the distribution range of specific surface area is 14-29m2/g.
Furthermore, the electrical resistivity of the Bi2Te3 bulks was measured. The results show that the electrical resistivity decreases with increasing the synthesis temperature. The lowest electrical resistivity is 8.54ohm-cm as the temperature is about 240℃. Meanwhile, the value of the seebeck coefficient is -102μv/k and the powerfactor is 1218μw/cmK2.
Key words: Hydrothermal ,Bi2Te3 , Thermoelectric

目錄
頁次
致謝 ------------------------------------------------------------------------ I
中文摘要 ------- II
英文摘要 ---------------------------------------------------------------------- III
目錄 ------- V
表目錄 ---------------------------------------------------------------------- VIII
圖目錄 ------- X
第一章 緒論-------------------------------------------------------------------- 1
1.1 前言---------------------------------------------------------------------- 1
1.2 文獻回顧---------------------------------------------------------------- 1
1.2.1 螯合劑--------------------------------------------------------- 2
1.2.2 金屬還原劑--------------------------------------------------- 3
1.2.3 Bi2Te3之簡介------------------------------------------------- 3
1.3 研究目的---------------------------------------------------------------- 5
第二章 理論基礎---------------------------------------------------------------- 6
2.1 水熱合成法之簡介 ------- 6
2.1.1 水熱反應的原理--------------------------------------------- 7
2.1.2 水熱法合成粉體之優點------------------------------ 7
2.1.3 高壓反應釜反應容積與溫度之關係介紹--------------- 9
2.1.4 水熱製程的改進--------------------------------------------- 11
2.2 結晶理論與機制------------------------------------------------------ 12
2.3 固態燒結過程與理論------------------------------------------------ 13
2.4 熱電現象之簡介------------------------------------------------------ 15
2.4.1 Seebeck效應------------------------------------------------- 18
2.4.2 Peltier 效應-------------------------------------------------- 20
2.4.3 Thomson效應------------------------------------------------ 21
2.4.4 ZT值----------------------------------------------------------- 22
2.5.5 目前改善ZT值之方式------------------------------------- 23
第三章 實驗方法與步驟------------------------------------------------------- 27
3.1 實驗藥品---------------------------------------------------------------- 27
3.2 粉末製備流程--------------------------------------------------------- 28
3.3 分析儀器---------------------------------------------------------------- 34
3.3.1 碲化鉍粉末分析---------------------------------------------- 34
3.3.2電性之量測----------------------------------------------------- 35
第四章 結果與討論------------------------------------------------------------- 37
4.1 碲化鉍粉末的合成--------------------------------------------------- 38
4.1.1 XRD粉末分析----------------------------------------------- 38
4.1.2 掃描式電子顯微鏡分析結果------------------------------ 47
4.1.3 穿透式電子顯微鏡分析結果------------------------------ 52
4.1.4 BET分析結果------------------------------------------------ 54
4.2 碲化鉍塊材之研究--------------------------------------------------- 52
4.2.1 碲化鉍塊材之SEM與EDS分析--------------------------- 55
4.3 碲化鉍塊材之電性量測--------------------------------------------- 59
4.3.1 合成溫度對電阻率的影響--------------------------------- 59
4.3.2 不同量測溫度對電阻率的影響--------------------------- 61
4.3.3 Seebeck值之量測------------------------------------------- 63
第五章 結論---------------------------------------------------------------------- 66
參考文獻---------------------------------------------------------------------------- 68








表目錄
頁次
表 2-1 比較各合成粉體方法------------------------------------------------ 9
表 2-2 燒結過程中原子的不同傳送途徑表------------------------------ 14
表 2-3 熱電材料在各方面的應用------------------------------------------ 22
表 4-1 Bi2Te3 之Database-------------------------------------------------- 46
表 4-2 不同EDTA/BiCl3莫爾比之起始原料所製得鍗化鉍粉末之
SEM粒徑分布------------------------------------------------------- 48
表 4-3 不同pH值之起始原料之碲化鉍粉末之SEM粒徑分布----- 48
表 4-4 TEM粒徑分佈----------------------------------------------------- 52
表 4-5 不同反應溫度之碲化鉍粉末比表面積分析------------------ 54
表 4-6 合成溫度150℃下所製得碲化鉍塊材之Bi與Te元素比例
--------------------------------------------------------------------------- 58
表 4-7 合成溫度180℃下所製得碲化鉍塊材之Bi與Te元素比例
--------------------------------------------------------------------------- 58
表 4-8 合成溫度210℃下所製得碲化鉍塊材之Bi與Te元素比例
--------------------------------------------------------------------------- 59
表 4-9 合成溫度240℃下所製得碲化鉍塊材之Bi與Te元素比例
--------------------------------------------------------------------------- 59
表 4-10 不同合成溫度下之電阻率----------------------------------------- 61
表 4-11 不同量測溫度下所測得之電阻率--------------------------------- 64
表 4-12不同合成溫度下之Seebeck係數--------------------------------- 65

















圖目錄
頁次
圖 1-1 EDTA 與重金屬離子螯合之結構圖------------------------------ 2
圖 1-2 Bi2Te3化合物的結晶結構-------------------------------------------- 5
圖 2-1 水熱合成法之析出反應示意圖-------------------------------------- 9
圖 2-2 水熱反應容積與溫度之關係----------------------------------------- 10
圖 2-3 壓力釜內液體體積與壓力間的關係示意圖----------------------- 11
圖 2-4 燒結理論之反應圖----------------------------------------------------- 14
圖 2-5 各類熱電材料之優值與溫度關係圖-------------------------------- 17
圖 2-6 熱電效應簡圖----------------------------------------------------------- 18
圖 2-7 Seebeck效應示意圖--------------------------------------------------- 19
圖 2-8 Peltier效應示意圖----------------------------------------------------- 20
圖 2-9 Thomson效應產生的非對稱性溫度梯度------------------------ 22
圖 2-10 載子濃度與S、ρ與Z值之關係---------------------------------- 25
圖 2-11 聲子散射圖------------------------------------------------------------ 26
圖 3-1 Bi2Te3粉末製備流程圖----------------------------------------------- 29
圖 3-2 粉末與塊材之特性分析流程圖------------------------------------- 30
圖 3-3 儀器裝置示意圖-------------------------------------------------------- 31
圖 3-4 四點探針示意圖-------------------------------------------------------- 32
圖 3-4 量測seebeck係數之裝置示意圖---------------------------------- 33
圖 4-1 不同pH值之起始原料於水熱反應溫度150℃所製得碲化鉍
粉末之XRD分析圖(A)9.3， (B)9.7， (C) 12.47 和(D)13.8。 39
圖 4-2 不同EDTA/BiCl3莫爾比之起始原料於合成溫度150℃反應
24小時所製得碲化鉍粉末之XRD分析圖(A)0 ，(B) 0.2，
(C) 0.4 和(D) 0.8。--------------------------------------------------- 40
圖 4-3 不同合成時間於150℃所製得碲化鉍粉末之XRD分析圖(A)
4hr(B) 16hr和(C) 24hr。--------------------------------------------- 41
圖 4-4 不同合成溫度反應24小時所製得碲化鉍粉末之XRD分析圖
(A)150℃，(B)180℃，(C)210℃和(D)240℃。--------------------- 42
圖 4-5 不同EDTA/BiCl3莫爾比之起始原料於合成溫度150℃反應24
小時所製得碲化鉍粉末之XRD-繞射峰(2θ = 27°)半高寬(FW
HM)。-------------------------------------------- 44
圖 4-6 不同合成時間於150℃所製得碲化鉍粉末之XRD-繞射峰(2θ
=27°)半高寬 (FWHM) 。------------------------------------------- 45
圖 4-7 不同合成溫度反應24小時所製得碲化鉍粉末之XRD-繞射峰
(2θ = 27°)半高寬 (FWHM)。----------------------------------------- 46
圖 4-8 不同pH值之起始原料於合成溫度150℃反應24小時所製得
碲化鉍粉末之之SEM分析圖(A) 9.3，(B) 9.7，(C) 12.47和
(D) 13.8。--------------------------------------------------------------- 50
圖 4-9 不同EDTA/BiCl3莫爾比之起始原料於合成溫度150℃反應
24小時所製得碲化鉍粉末之SEM分析圖(A) 0，(B) 0.2，
(C) 0.4和(D)0.8。---------------------------------------------------- 51
圖 4-10 不同合成時間，反應溫度150℃下所製得鍗化鉍粉末之
SEM分析圖 (A) 4hrs，(B) 16hrs和(C) 24hrs。-------------- 52
圖 4-11 不同合成溫度反應24小時下所製得鍗化鉍粉末之TEM分
析圖 (A) 150℃(B) 180℃，(C) 210℃和(D) 240℃---------- 54
圖4-12 經燒結之碲化鉍塊材之外觀-------------------------------------- 57
圖 4-13 不同合成溫度反應24小時下所製得鍗化鉍塊材之SEM 分
析圖(A)150℃ (B) 180℃，(C) 210℃和 (D) 240℃。-------- 58
圖 4-14 合成溫度150℃下所製得鍗化鉍塊材之表面之EDS分析圖 59
圖 4-15 合成溫度180℃下所製得鍗化鉍塊材之表面之EDS分析圖 59
圖 4-16 合成溫度210℃下所製得鍗化鉍塊材之表面之EDS分析圖 60
圖 4-17 合成溫度240℃下所製得鍗化鉍塊材之表面之EDS分析圖 60
圖 4-18 電阻率對合成溫度之關係----------------------------------------- 62
圖 4-19 不同量測溫度下之電阻率關係圖-------------------------------- 63
圖 4-20 不同合成溫度下經燒結製得Bi2Te3塊材之Seebeck係數----- 66
圖 4-21 不同合成溫度下經燒結製得Bi2Te3塊材之功率因子-------- 67

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