本論文主要的目的在於以研製中/高溫(450K~800K)熱電材料之塊材為主及利用數值模擬來最佳化其元件參數，這有助於解決日常生活中所見廢熱問題，諸如：工業廢熱、散熱岐管等，特別是在汽車上的觸煤轉換器上之廢熱利用。實驗中的主要研製的材料是具半赫勒斯結構之(Ti/Zr/Hf)1-xMxNi1-yPdySn1-zSbz (M= V,Nb,Ta)的多元(高熵)合金，原材經由熔煉鑄造之方式合成，並加入過渡金屬、半金屬/半導體等元素，且藉由多元合金易於趨近奈米化之特性，或利用原位析出法生成奈米相，最後再經由XRD繞射儀、SEM、TEM 等儀器來佐證。此熱電材料性能的提升方法是藉由(1)利用半金屬或半導體材料調控電性(荷)；(2)利用重原子/大原子之部份取代，降低熱傳導係數；(3)藉由奈米析出物或過飽和析出物與點缺陷，以增加聲子散射；(4)利用熱處理方式，調整材料性質。
經由實驗結果，N-Type材料之最佳熱電優值及其合成條件分別如下：(1)Ti0.3(ZrHf)0.69V0.01Ni0.9Pd0.1Sn0.99Sb0.01 在溫度820K時，可得到最佳ZT值為0.92，並發現具有奈米結構析出物，奈米粒徑約為60nm；(2) Ti0.5(ZrHf)0.49Nb0.01Ni0.9Pd0.1Sn0.98Sb0.02 在溫度900K時，可得到最佳ZT值為0.66；(3) Ti0.5Zr0.25Hf0.22Ta0.03NiSn0.98Sb0.02在溫度879K時，可得到最佳ZT值為0.77；(4) (ZrHf)0.99V0.01NiSn0.98Sb0.02 在溫度746K時，可得到最佳ZT值為0.81，並具有奈米結構析出物。
另外在P-Type材料方面，以ZrCoSb為基材，並在Sb的位置上加上微量的Sn，可得到在升溫下之熱電功率因子，其研究結果為：(1) (Zr0.9Sc0.05)CoSb0.9Sn0.1 在溫度800K下，可得到39.1μW/cm-K2 ；(2) (Zr0.9Sc0.05)CoSb0.98Sn0.02 在800K下，可達44.5μW/cm-K2。
而在數值模擬分析的部分，是利用方向性凝固來製備高性能碲化鉍化合物Bi2Te3(Se,Sb)之熱電材料(P type ZT值~1.25；N Type ZT值~0.95)，經由有限元素法模擬之非線性分析可得知： (1)當外部熱沉溫差達100K且內部熱電材料溫差為82.1K時，在不同的熱電對數目下，可繪出所對應的輸出電力與輸出功率曲線分佈圖，此圖可再串聯成一條最佳線性關係，可得知熱電對高度與最高的輸出電力與效率；(2)熱電對密度增加時亦可輸出較多的電力，但仍有其最佳之數量，而焊料容許應力將會超過設計值，可能會造成元件的損壞。

High-temperature thermoelectric bulk materials are developed in this study. They can help to recycle the waste heat of daily life, such as the heat from industrial waste gas, heat dissipation manifold, heat exchanger, and especially from the catalyst converter of a car.
In this dissertation, the development is based on the high entropy alloy system of (Ti/Zr/Hf)1-xMxNi1-yPdySn1-zSbz (M = V, Nb, Ta), which is synthesized by using a designed melting and solidifying scheme. Transition metals and elemental semi-metal/semiconductor materials are added into the manufactured materials. The structure of high entropy alloy tends to be nanolized or use in-situ precipitation methods, which can be verified by applying X-ray diffraction, scanning electron microscopy, transmission electron microscopy etc. In the developed materials, the formation of Half-Heusler FCC phases is found, which could significantly increase the thermoelectric property.
In the research, the primary matrix material is TiNiSn of Half-Heusler alloy. The investigated methods for material development are (1) using semi-metal or semiconductor materials to control the electrical characteristics, (2) partially replacing the matrix atoms by heavy or big atoms to reduce the thermal conductivities, (3) increasing the phonon scattering by the nano-precipitates and point defects, (4) utilizing heat treatment to adjust the thermoelectric property.
From the experimental results, single phase N-Type Half-Heusler compound has the following peroformances of thermoelectric figure of merit: (1) the ZT value of 0.92 is obtained at 820K for Ti0.3(ZrHf)0.69V0.01Ni0.9Pd0.1Sn0.99Sb0.01 and the size of nano structure is about 60 nm; (2) for Half-Heusler compounds of Nb-doped (Zr/Hf) sites, the high ZT value is obtained, which is 0.66 at 900K for Ti0.5(ZrHf)0.49Nb0.01Ni0.9Pd0.1Sn0.98Sb0.02; (3) for Half-Heusler compounds of Ta-doped Hf sites, the maximum value of ZT for Ti0.5Zr0.25Hf0.22Ta0.03NiSn0.98Sb0.02 compounds is 0.77 at 879K; (4) with V-doped ZrNiSn base, the ZT of (ZrHf)0.99V0.01NiSn0.98Sb0.02 compounds is 0.81 at 746K, which have the nano phase of In Situ forming nano structure. Besides, for ZrCoSbSn Half-Heusler compounds in which Sn substitutes for Sb, the maximu values of the power factor of (Zr0.9Sc0.05)CoSb0.9Sn0.1 and (Zr0.9Sc0.05)CoSb0.98Sn0.02 are 39.1 and 44.5 μWcm-1K-2 at 800K, respectively.
The behavior of thermoelectric modules is simulated numerically with the finite element analysis for the high-performance Bi2Te3(Se,Sb) alloys manufctured by using a directional solidification method, whose maximum values of ZT for P and N Types are 1.25 and 0.95 at 300K. The results based on the geometrical configuration can be summarized as follows: (1) under the operating conditions that the temperature differences of the heat sink and the TE leg surfaces are about 100K and 82.1K respectively, the profiles of output power versus thermoelement length for the different number of thermoelectric leg pairs present a linear relationship, indicating the maximun efficiency for each thermoelectric leg pair; (2) the module output power increases with the number of leg pairs. However, the maximum stresses observed on the solder located at the module corner will exceed its allowable value, which could damage the module.

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