纳米SiC分散的Bi2Te3热电材料的制备与性能研究

用机械合金化工艺（MA）和放电等离子烧结工艺（SPS），制备出纳米SiC（平均直径约30nm）弥散分布的Bi2Te3热电材料，并研究了纳米SiC颗粒弥散对Bi2Te3性能的影响。实验采用MA合成纳米SiC分散Bi2Te3粉末，用SPS制备块体材料。XRD分析表明用MA和SPS成功制备了Bi2Te3合金，随着纳米SiC含量的增加，材料的颗粒尺寸减小，表明纳米SiC有抑制颗粒长大的作用。电学性能测试发现少量（体积分数≤1．0％）纳米SiC的加入对Bi2Te3电学性能有很大影响：虽然随着SiC含量的增加电导率有所降低，但Seebeck系数得到了提高。当加入0．1％SiC时，Seebeck系数和功率因子达到最大值，均高于纯Bi2Te3试样，随着SiC含量进一步增加，Seebeck系数和功率因子降低。显微硬度随着纳米SiC含量的增加也得到提高。综合实验结果表明极少量纳米SiC颗粒的加入可以提高Bi2Te3的电学性能和力学性能。     

溶剂热合成Bi2Te3基合金的结构与电学性能

用溶剂热法合成了二元Bi2Te3和三元Bi1.3Sn0.7Te3合金纳米粉末,并采用热压技术制备了块状热电材料.XRD分析结果表明:Bi-Sn-Te三元固溶体合金可以直接通过溶剂热合成获得单相产物,而非掺杂Bi2Te3合金需要通过热压等后热处理来实现产物的单一化;热压过程有助于促进反应的完全和晶型的完整,但会导致晶粒的长大.对试样电导率σ和Seebeck系数α的测量结果显示,Bi-Sn-Te三元固溶体合金比二元Bi-Te合金具有更好的电学性能.     

Bi2Te3纳米颗粒和纳米线的溶剂热合成及组织特征

分别以吡啶、无水乙醇为反应介质,以NaBH4为还原剂,采用溶剂热合成方法,在150℃下反应24 h制备了平均晶粒尺寸为15～20 nm的Bi2Te3纳米粒子.采用相同的合成方法,以去离子水为反应介质,合成了直径为30～80 nm,长径比大于100的Bi2Te3纳米线.XRD和TEM分析表明,随着溶剂介电常数和极性增加,所生成产物的物相纯度、结晶度增高,晶粒尺寸增大.     

两元P—型梯度结构热电材料FeSi2／Bi2Te3的制备与性能

采用热浸焊法用纯Sn作为过渡层制备了P－型FeSi2/Bi2Te3梯度结构热电材料并对其热电性能进行了测试,发现当热端温度在510℃以下时,梯度结构热电材料的平均Seebeck系数保持恒定,达220uV/K至250uV/K左右,显著高于单一均质材料（Bi2Te3和β－FeSi2)在相同温度范围内的平均Seebeck系数,梯度结构热电材料的输出功率较单种材料高1．5至2倍以上,且当材料经190℃,100h与200h的真空退火后,输出功率几乎不变,金相观察表明,在Sn层与两半导体界面处,没有明显的Sn 扩散迹象,说明在所试验的条件下,用Sn作为过渡层热稳定性较好。     

Bi2Te3片式阵列的制备及生成机理

以Bi（NO3）3和Te为反应物，在乙二胺四乙酸二钠（EDTA-2Na）、N，N-二甲基甲酰胺（DMF）与乙醇组成的混合溶剂以及过量强碱KOH的作用下，通过溶剂热反应，制得Bi2Te3热电材料的片式阵列纳米结构。利用XRD、SEM、EDX对产物的物相、形貌及成分进行了表征和研究。通过实验研究推断这种BizTe，片式阵列的形成过程可能是一个络合-成核-生长-脱离-组装的过程。     

SPS法制备的赝二元合金（Ga2Te3）x-（Bi0．5Sb1．5Te3）1-x（x=0～0．2）电学性能

采用放电等离子烧结（SPS）方法制备了赝二元合金（Ga2Te3）（Bi0.5Sb1.5Te3）1-x（x=0—0．2），并研究其电学性能。结果表明，在318K时（Ga2Te3）x-（Bi0.5Sb1.5Te3）1-x（x=0．1）合金的电导率为3．7×10^4Ω^-1·m^-1，是三元合金Bi0.5Sb1.5Te3的2倍，而Seebeck系数没有明显下降。从所测得的a和σ值可知，赝二元（Ga2Te3）x-（Bi0.5Sb1.5Te3）1-x（x=0．1）合金的功率因子最大，为2．1×10^-3（W·K^-2·m^-1），是三元Bi0.5Sb1.5Te3合金的1．5倍。     

Bi5Ti3FeO15多铁陶瓷的制备与表征

以TiO2、Fe2O3和Bi2O3为原始组分,采用固相烧结法制备了Bi5Ti3FeO15多铁陶瓷.借助XRD和SEM分析了相组成及显微结构.结果表明:经750℃×2h预合成后,粉体由Bi5Ti,FeO1,、Bi4Ti3O12和Bi2O3相组成;经成型、二次烧结后,主晶相基本为Bi5Ti3FeO1,,其衍射峰强度和位置随温度升高发生明显变化;在850℃烧结后,形成1～3μm细小晶粒.并有大量气孔存在;随着烧结温度的升高,晶粒长大、气孔减少;在1000℃烧结后,形成了典型的片状晶粒,尺寸约10μm.     

Ti基非晶及准纳米晶材料制备技术研究

用Al、B取代Ti50Ni15Cu25Sn3Be7中有毒的Be元素,采用真空甩带及铜模吸铸法制备名义成分为Ti50Ni15Cu25-Sn3Al6.9B0.1的非晶合金。对制得的合金经热处理制备准纳米晶体。采用SEM观察组织及晶粒大小。XRD分析结果表明,铜模吸铸法所制得的合金为晶态加少量非晶。DTA分析表明,合金存在三个相变转变点,转变温度分别为Te1=350℃、Te2=430℃和Te3=510℃。合金经800℃油淬10min、350℃回火12h后晶粒细化,晶粒尺寸在1μm以下,其中析出相的晶粒尺寸已是准纳米级或纳米级尺度。回火24h后晶粒明显长大,晶粒平均尺寸在10μm左右。     

MA法制备Fe83Nb7B9Cu1纳米晶粉末及其热稳定性

利用高能球磨法在Fe Nb B Cu体系中获得纳米晶粉末 ,研究了机械球磨过程中产物的组织结构、α Fe相平均晶粒尺寸及其热稳定性。结果表明 :采用Fe 2 0B中间合金粉末代替B粉并未明显影响机械合金化动力学过程 ;球磨至 5h时 ,即可获得平均晶粒尺寸约 18nm的α Fe单相过饱和固溶体 ,其后延长球磨时间 ,晶粒尺寸缓慢减小 ,至 45h后 ,平均晶粒尺寸减小到 9nm。退火处理后的XRD分析表明 ,α Fe过饱和固溶体从 10 0℃开始发生结构弛豫现象 ,738.8℃后则发生了相转变 :α Fe过饱和固溶体→α Fe固溶体 Fe3 B FeB ,在 5 5 0℃以内退火 ,纳米晶粒长大不明显 ,在 770～ 95 0℃范围内退火 ,晶粒开始明显长大 ,但晶粒尺寸仍处于纳米级范围。     

退火对高压烧结Gd掺杂Bi_2Te_(2.7)Se_(0.3)纳米晶热电性能的影响

以Bi粉、Te粉、Se粉、Sb I3粉、Gd粉为原料,用高压烧结法制备了Gd掺杂的n型Bi2Te2.7Se0.3热电材料,对制备的样品分别在573、603、633 K真空退火36 h。用粉末XRD和FE-SEM研究了样品的物相及显微形貌;在298~473K范围内测定了样品的热电性能。建立了Bi2Te3基材料的禁带宽度与压力和体积的近似关系式,利用此关系式较好解释了高压烧结样品在退火前后热电性能的变化特性。研究结果表明制备的样品在退火前后均为纳米结构。高压烧结和Gd掺杂使样品晶胞尺寸变大,禁带宽度减小。退火使高压烧结样品的电导率提高,塞贝克系数增大,热导率降低。样品于633 K退火36 h后具有较好的热电性能,在423 K时其ZT达到最大值为0.74。     

Optimization of thermoelectric properties of n-type Bi_2(Te,Se)_3 with optimizing ball milling time

The thermoelectric properties at elevated temperature were investigated for n-type Bi2(Te,Se)3 which is obtained from ball milling processed powder with various milling times. Electrical properties such as electrical resistivity and Seebeck coefficient are clearly dependent on milling time, in which the carrier concentration is attributed to the change of the electrical properties. The concentrations of the defects are also varied with the ball milling time, which is the origin of the carrier concentration variation. Even though finer grain sizes are obtained after the long ball milling time, the temperature dependence of the thermal conductivity is not solely understood with the grain size, whereas the electrical contribution to the thermal conductivity should be also considered. The highest figure of merit value of ZT = 0.83 is achieved at373 K for the optimized samples, in which ball milling time is 10 h. The obtained ZT value is 48% improvement over that of the 0.5-h sample at 373 K.     

Thermoelectric properties of Bi_(0.5)Sb_(1.5)Te_3/polyaniline composites prepared by mechanical blending and in-situ polymerization

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定向生长Bi2Te3-Sb2Te3三元合金热电材料的组织与性能

利用Bridgman定向凝固法,在大凝固速率范围内5～1000μm/s制备出Bi2Te3-Sb2Te3三元合金块体热电材料,并对其凝固组织和不同凝固速率下合金的热电性能进行研究。结果表明:高温度梯度和大凝固速率范围内制备的25%Bi2Te3-75%Sb2Te3合金定向凝固组织由Bi0.5Sb1.5Te3单相组织组成;在较低凝固速率5μm/s下,熔体生长平界面失稳形成胞状组织,而随定向凝固速率的增加,胞状组织减少,组织细化。不同定向凝固速率下25%Bi2Te3-75%Sb2Te3合金的Seebeck系数和电阻率随着凝固速率的增加而增大。50μm/s下300～450K范围内获得功率因子(PF)在4.6×10-3～5.01×10-3W/(K2.m),并在350K时PF值达到最大值5.01×10-3W/(K2.m);而在高凝固速率500μm/s下,其功率因子也可达4.5×10-3W/(K2.m),表明高温度梯度和大凝固速率制备热电材料是一种有效的制备工艺方法。     

无机有机复合材料Bi2Te3／PAn电化学嵌锂性能研究

采用机械共混法制备了复合材料Bi2Te3/PAn,并对其电化学嵌锂性能进行了研究.研究发现Bi2Te3/PAn快速充放电性能良好,在以100 mA·g-1的电流密度充放电时首次可逆容量为480 mAh·g-1,到第20个循环时容量保持在200mAh·g-1.通过非原位X射线衍射方法研究其嵌锂机理,发现Bi2Te3在首次放电时分解,在随后的循环中以Te和Bi为嵌锂中心进行可逆储锂.     

Preparation and characterization of nanostructured Bi_2Se_3 and Sn_(0.5)-Bi_2Se_3

Nanostructured Bi2Se3 and Sn0.5·Bi2Se3 were successfully synthesized by hydrothermal coreduction from SnCl2-H2O and the oxides of Bi and Se. The products were characterized by X-ray diffraction (XRD),transmission electron microscopy (TEM),and field emission scanning electron microscope (FESEM). Bi2Se3 powders obtained at 180°C and 150°C consist of hexagonal flakes of 50-150 nm in side length and nanorods of 30-100 nm in diameter and more than 1 μm in length. The product obtained at 120°C is composed of thin...     

La_(0.7)Mg_(0.3)Ni_(2.8)Co_(0.5-x)Fe_x系列合金的制备及其储氢性能

在制备La-Ni-Co-Fe中间合金的基础上,采用机械合金化方法制备La0.7Mg0.3Ni2.8Co0.5-xFex(x=0,0.1,0.2,0.3,0.4,0.5)系列储氢合金,研究在不同球磨时间下储氢合金的物相、微观形貌和电化学性能及元素置换对其储氢性能的影响。结果表明:La0.7Mg0.3Ni2.8Co0.5合金的主相为LaNi5相,La0.7Mg0.3Ni2.8Co0.5-xFex系列储氢合金球磨40 h和80 h后,主相为LaNi5相和少量LaMg2Ni9相;且随着球磨时间的增加,合金晶粒变细小,La0.7Mg0.3Ni2.8Co0.5合金的最大放电容量呈变大的趋势,从142.4 mA.h/g增加到157.5 mA.h/g,La0.7Mg0.3Ni2.8Co0.2Fe0.3合金的最大放电容量从150.7mA.h/g增加到162.1mA.h/g,合金具有较好的循环稳定性能。     

PREPARING NANO-CRYSTALLINE La DOPED WC/Co POWDER BY HIGH ENERGY BALL MILLING

The La doped WC/Co powder was prepared by high energy ball milling. The changes of crystal structure, micrograph and defect of the powder were investigated by means of XRD (X-ray diffraction), SEM (scanning electron microscope) and DTA (differential thermal analysis). The results show that adding trace La element into carbides is effective to minish the grain size of WC/Co powder. The La doped carbides powder with grain size of 30nm can be obtained after 10h ball milling. The XRD peak of Co phase disappeared after 20h ball milling, which indicated solid solution (or secondary solid solution) of Co phase in WC phase. The La doped powder with grain size of 10nm is obtained after 30h ball milling. A peak of heat release at the temperature of 470℃ was emerged in DTA curve within the range of heating temperature, which showed that the crystal structure relaxation of the powder appeared in the process of high energy ball milling. After consolidated the La doped WC/Co alloy by high energy ball milling exhibits     

急冷甩带过程和过量Te对p型Bi0.5Sb1.5Te3化合物热电性能的影响

采用感应熔炼制备得到了P型Bi0.5 Sb1.5Te3+x％(质量)Te(x=0、2、4和6)合金.将合金均匀分成R和S两组,R组不作处理,S组通过急冷甩带过程获得厚度约为5～15 μm的薄带,然后将两组样品分别粉碎过筛后,热压烧结成块体材料.利用扫描电镜(SEM)观察了薄带和烧结块体的形貌结构,在室温下测量其电性能....     

Enhancing room-temperature thermoelectric performance of n-type Bi_2Te_3-based alloys via sulfur alloying

Bismuth-telluride-based alloys are the best thermoelectric materials used in commercial solid-state refrigeration near room temperature.Nevertheless,for n-type polycrystalline alloys,their thermoelectric figure of merit(zT) values at room temperature are often less than1.0,due to the high electron concentration originating from the donor-like effect induced by the mechanical deformation process.Herein,carrier concentration for better performance near room temperature was optimized through manipulating intrinsic point defects by sulfur alloying.Sulfur alloying significantly decreases antisite defects concentration and suppresses donor-like effect,resulting in optimized carrier concentration and reduced electronic thermal conductivity.The hot deformation process was also applied to improve carrier mobility due to the enhanced texture.As a result,a high zT value of 1 at 300 K and peak zT value of 1.1 at 350 K were obtained for the twice hot-deformed Bi_2 Te_(2.7)Se_(0.21)S_(0.09) sample,which verifies sulfur alloying is an effective method to improve thermoelectric performance of n-type polycrystalline Bi2 Te3-based alloys near room temperature.