Electronic Structure and Thermoelectric Properties of Ca3 Co4O9

The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co4 O9 was studied using density function and discrete variation method （DFT-DVM）. The gap between the highest valence band （HVB） and the lowest conduction band （LCB） shows a semiconducting property. Ca3 Co4 O9 consists of CoO2 and Ca2 CoO3 two layers. The HVB and LCB near Fermi level are only mainly from O（ 2 ） 2p and Co （2） 3d in Ca2 CoO3 layer. Therefore, the semiconducting or thermoelectric property of Ca3 Co4 O9 should be mainly from Ca2 CoO3 layer, but it seems to have no direct relation to the CoO2 layer, which is consistent with that binary oxides hardly have a thermoelectric property, but trinary oxide compounds have quite a good thermoelectric property. The covalent and ionic bonds of Ca2 CoO3 layer are both weaker than those of CoO2 layer. Ca plays the role of connections between CoO2 and Ca2 CoO3 layers in Ca3 Co4 O9, decrease the ionic and covalent bond strength, and improve the thermoelectric property.     

Thermoelectric Properties and Electronic Structure of Ca_3Co_2O_6

1　IntroductionIthasbeengenerallyacceptedthatthethermoelectricefficiencyofoxidesislowerthanthatoftheconventionalthermoelectricmaterialbecauseoftheirhighioniccharacter,whichgenerallycausesastronglocalizationofelectronsandhenceleadstoaverylowcarriermobility…     

Electronic Structures and Chemical Bonds of Cobaltite and Ni-Doped

The relation among electronic structure, chemical bond and thermoelectric property of Ca3 Co2 O6 and Ni-doped was studied by density function theory and discrete variation method（DFT-DVM）. The results indicate that the highest valence band（ HVB ）attd the lowest conduction band（ LCB ） are mainly attribuled to Co3d, Ni3d and O2p atomic orbitals. The property of a semiconductor is shown from the gap between HVB and LCB. The gap of Ni-doped one is less than that of Ca3 Co2 O6. The non-metal bond or ceramic characteristic of Ni-doped one is weaker than that of Ca3 Co2 O6, but the metal characteristics of Ni-doped one are stronger than those of Ca3 Co2 O6. The thermoelectric property should be improved by adding Ni element into the system of Ca3 Co2 O6 .     

Electronic Structure and Chemical Bond of Titanium Diboride

1　IntroductionTitaniumdiboride (TiB2 )hasattractedmuchatten tionrecentlybecauseofitshighmeltingpoint,hardnessandchemicalstability .Ontheotherhand ,TiB2 hasfineelectricalproperty ,soitmaybeusedinwide rangingfields[1-3 ] .Aswellknown ,thepropertiesofmaterialsaredecidedbythestructures .Obviously ,thespecialpropertyofTiB2 isrelatedtoitsstructuresofcrystalandelectrons .However ,thereislessstudyonstructuresofvalenceelec tronsandtypeofchemicalbondofTiB2 .JiJia mingetal[4] studiedtheelectronicst…     

Thermoelectric Properties and Electronic Structure of Ca3Co2O6

The nanosized Ca3Co2O6 powder was synthesized via sol-gel process.The phase composition was characterized by means of X-ray diffraction.Polycfrystalline swnples of Ca3Co2O6 were prepared by a sintering procedure of nanosized power.The seebeck cofficient and electrical conductivity of the samples were measured from 450K up to 750 K.The results show that the Seebeck coefficient increases with the increasing temperature.The electronic structures were calculated using the self-cwtsistent full-potential linearized augmentedc plane-wave (LAPW) method within the density functional theory.The relationship between thermoelectric property and electronic structures was discussed.     

高压制备Ce掺杂Ca3CO4O9陶瓷的热电性能

Ca3Co4O9是一种具有广泛应用前景的热电功能材料,为了提高其热电性能,利用高压成型方法及常规二次固相反应技术,制备了稀土ce掺杂的氧化物热电陶瓷材料ca3-xcexCo4O9（z=0,0．1,0．3,0．5）,在室温条件下对其微观结构和热电性能进行了测试分析．经扫描电镜测试发现,高压方法制备样品的致密度较高．热电性质测试表明,Ca3CO4O9的电阻率及See—beck系数随Ce掺杂量（z）的增加而增大,x=0．1时得到最大的功率因子;与常规二次固相反应制备的样品相比,高压制备的样品具有更高的热电性能．     

Sol-gel preparation and characterization of Co_3O_4 nanocrystals

A new citrate acid-hydrazine sol-gel route for preparation of Co3O4 nanoparticles has been developed. Co3O4 nanoparticles with different particle-sizes and morphology were prepared at different heat-treatment temperatures and the pure cubic nanocrystals of Co3O4 were obtained at 600℃. The synthesis process was monitored by infrared spectroscopy (IR), thermal gravimetric and differential thermal analysis (TG-DTA). The structure and morphology of Co3O4 nanocrystals were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray-photoelectron spectroscopy (XPS). The infrared absorption bands blue-shifted with particle size decreasing, which could be attributed to increasing surface effect. XPS results showed that predominant species at surface layers of Co3O4 nanocrystals are octahedral Co (Ⅲ).     

Thermoelectric properties of porous (Bi_(0.15)Sb_(0.85))_2Te_3 thermoelectric materials

In order to obtain thermoelectric materials with high figure of merit, the concept of Hollow (Vacuum) Quantum Structure or Effect and related thermoelectric materials design were proposed. To demonstrate the theory, the materials of (Bi0.15Sb0.85)2Te3 with porous structure have been fabricated. Their thermoelectric properties and the microstructure were investigated and compared with their density structure. It was found that the porous structure could improve their properties greatly.     

Electronic Structure and Chemical Bond of Ti3SiC2 and Adding Al Element

The relation among electronic structure, chemical bond and property of Ti3SiC2 and Al-doped was studied by density function and discrete variation （ DFT- DVM） method. When Al element is added into Ti3 SiC2 , there is a less difference of ionic bond, which does not play a leading role to influent the properties. After adding Al, the covalent bond of Al and the near Ti becomes somewhat weaker, but the covalent bond of Al and the Si in the same layer is obviously stronger than that of Si and Si before adding. Therefore, in preparation of Ti3 SiC2 , adding a proper quantity of Al can promote the formation of Ti3 SiC2 . The density of stnte shows that there is a mixed conductor character in both of Ti3 SiC2 and adding Al element. Ti3 SiC2 is with more tendencies to form a semiconductor. The total density of state near Fermi lever after adding Al is larger than that before adding, so the electric conductivity may increase after adding Al.     

微波合成Ca_3Co_4O_9热电材料的微观结构和性能

利用微波技术合成了Ca3Co4O9化合物,考察了微波加热时间对产物纯度和微观结构的影响;再利用微波及常规烧结技术制备了Ca3Co4O9热电陶瓷片,考察了烧结时间、烧结方式对材料微观结构和热电性能的影响.结果表明:二次微波烧结30 min制备的热电陶瓷片在所测试温度范围内具有低电阻率、高塞贝克系数及最佳功率因子,其中966 K时微波产物的最大功率因子为0.141 m W/m K2,而常规高温烧结产物的功率因子为0.120 m W/m K2.     

多孔Co3O4纳米片的制备及其电化学性能研究

采用溶剂热法制备片状Co(CO3)0.5(OH).0.11H2O前驱物,经400℃煅烧2 h即可得到多孔Co3O4纳米片.通过场发射扫描电镜(FESEM)和透射电镜(HRTEM)观测了纳米片的形貌,利用X射线衍射(XRD)分析了纳米片的结构,通过循环伏安、恒流充放电和交流阻抗测试了材料的电化学电容性能.结果表明:多孔Co3O4纳米片厚度约为50 nm,孔径主要分布在10 nm左右;0.5 A/g恒流充放电情况下,比容量高达707 F/g,当电流密度高达8 A/g时比容量依然高达547 F/g;同时,该材料循环1 000次后,容量保持率为97.4%.     

Structure and Chemical Bond of Thermoelectric Ce-Co-Sb Skutterudites

The correlations among composition, structure, chemical bond and thermoelectric property of skutterudites CoSb3 and CeCo5Fe3Sb12 have been studied by using density function and discrete variation (DFT-DVM) method. Three models for this study were proposed and calculated by which the "rattling" pattern was described. Model 1 is with Ce in the center, model 2 is with Ce away the center and near to Sb, and model 3 is also with Ce away the center but near to Fe. The calculated results show that in model 3, the ionic bond is the strongest, but the covalent bond is the weakest. Due to the different changes between ionic and covalent bond, there is less difference in the stability among the models 1, 2 and 3. Therefore, these different models can exist at the same time, or can translate from one to another more easily. In other words, the "rattling" pattern has taken place. Unfilled model of CoSb3, without Ce and Fe, is called model 4. The covalent bond of Co-Sb or Fe-Sb in models 1, 2 and 3 is weaker than that of     

The Quantum Chemistry Calculation and Thermoelectrics of Bi-Sb-Te Series

The density function theory and discrete variation method ( DFT- DVM ) was used to study correlation between composition, structure, chemical bond, and property of thermoelectrics of Bi-Sb-Te series. 8 models of Bi2o-xSbxTe32( x = 0,2,6,8,12, 14,18 and 20) were ca/zulated. The resu/ts show that there is less difference in the ionic bonds between Te(I)-Bi( Sb ) and Te(Ⅱ)-Bi( Sb ) , but the covalent bond of Te( I )-Bi( Sb ) is stronger than that of Te(Ⅱ)-Bi( Sb ). The interaction between Te( I ) and Te( I ) in different layers is the weakest and the interaction should be Van Der Waals power. The charge of Sb is lower than that of Bi , and the ionic bond of Te- Sb is weaker than that of Te- Bi . 7he covalent bond of Te- Sb is also weaker than that of Te-Bi. Therefore, the thermoelectric property may be improved by adjusting the electrical conduaidty and thermal conductivity through changing the composition in the compounds of Bi-Sb- Te. The calculated results are consistent with the experiments.     

Ca3Co4O9热电材料的固相制备及其分析

实验采用固相合成方法成功的制备了Ca3Co4O9热电材料。通过对不同烧成温度和时间的样品微观结构的分析研究,从而得到最佳的制备工艺。实验结果表明:二次研磨烧结有利于Ca3Co4O9片状组织的生长;900℃二次研磨烧结能够制备出较纯的Ca3Co4O9热电材料。     

金团簇二维到三维的结构转变和电子特性的理论研究

基于密度泛函PW91/TZVPP理论级别,研究Aun团簇的平衡结构和电子性质。结构优化显示:在n=3~13范围内,Aun团簇的基态构型均为二维结构,当n=14时,开始从二维结构转变成三维结构。原子平均结合能、二阶能量差分、能级间隙、电子亲和势和垂直电离势分析表明:较大金团簇原子之间的结合力强于较小金团簇;偶数金团簇比奇数金团簇具有较高的稳定性;奇数金团簇的化学活性比偶数金团簇高且在化学反应中容易得电子。     

Electronic structure and properties of pure cobalt

According to one-atom theory of pure metals,the electronic structure of hcp α-Co has been determined to be [Ar](3dn)0.46(3dm)1.86(3dc)5045(3se)0.03(4sf)1.30.The potential curve,cohesiw energy,lattice parameter,magnetism,elasticity and temperature dependences of specific heat and linear thermal expansion coefficient of the hcp α-Co are calculated.The theoretical values of these properties are compared with those obtained from experiments and calculated by LSDA and GGA methods.Three possible states ψβ(dn→dc),ψβ(dm→dc) and ψβ(sf→dc) for fcc β-Co are designed.The conversion of hcp α-Co→fcc β-Co occurs due to the increase of covalent electrons in state t2g Because the differences in the states,bond parameters and properties between hcp α-Co and fcc β-Co are very small,the two forms normally coexist at room temperature.     

Electronic Structures and Bonding Properties of Ti_2AlC and Ti_3AlC_2

The relation among electronic structure, chemical bond and property of Ti2AlC, Ti3AlC2 and doping Si into Ti2AlC was studied by density function and the discrete variation (DFT-DVM) method. After adding Si into Ti2AlC, the interaction between Si and Ti is weaker than that between Al and Ti, and the strengths of ionic and covalent bonds decrease both. The ionic and covalent bonds in Ti3AlC2, especially in Ti-Al, are stronger than those in Ti2AlC. Therefore, in synthesis of Ti2AlC, the addition of Si enhances the Ti3AlC2 content instead of Ti2AlC. The density of state (DOS) shows that there is mixed conductor characteristic in Ti2AlC and Ti3AlC2. The DOS of Ti3AlC2 is much like that of Ti2AlC. Ti2SixAl1-xC has more obvious tendency to form a semiconductor than Ti2AlC, which is seen from the obvious difference of partial DOS between Si and Al 3p.     

Electrodeposition and characterization of thermoelectric Bi_2Se_3 thin films

Bi2Se3 thin films were electrochemically deposited on Ti and indium tin oxide-coated glass substrates,respectively,at room temperature,using Bi(NO3)3·5H2O and SeO2 as starting materials in diluted HNO 3 solution.A conventional three-electrode cell was used with a platinum sheet as a counter electrode,and a saturated calomel electrode was used as a reference electrode.The films were annealed in argon atmosphere.The influence of cold isostatic pressing before annealing on the microstructure and thermoelectric...     

温度对V2O3系材料电子结构的影响

采用自洽场离散变分Xα（SCC-DV-Xα）方法对（V0.9950Cr0.0025Al0.0025）2O3体系分别处于25℃及200℃时的电荷分布、态密度、能级结构等进行了研究。结果表明,温度对电子结构的影响导致材料的电导率发生显著变化,变化趋势与实验结果相一致,对钒系PTC材料的进一步研制具有理论指导意义。