掺杂金属离子对Ca3Co4O9的热电性能的影响

采用溶胶-凝胶法,在常压空气中,经850℃烧结4h制备了Ca3Co4O9掺杂不同金属离子M(Na ,Ag ,La2 )的(Ca1-xMx)3Co4O9热电材料.通过X射线衍射、扫描电镜等对材料的微结构进行了表征,重点考察了掺杂不同金属离子对Ca3Co4O9中温热电性能参数Seebeck系数、电导率和功率因子的影响.结果表明:金属掺杂的(Ca1-xMx)3Co4O9热电材料具有致密的内部结构,并能够明显改善Ca3Co4O9的热电性能,尤其是掺杂Na 样品的热电性能有较为明显的提高,并且掺杂离子浓度对改善热电性能也有一定影响,组成为(Ca0.90Na0.10)3Co4O9时的功率因子提高最明显.     

制备工艺对La改性的Ca3Co4O9基陶瓷热电性能的影响

利用常压烧结、冷等静压成型后常压烧结及热等静压烧结3种不同制备工艺,合成了(Ca0.9La0.1)3Co4O9热电材料。XRD分析表明：不同工艺制备的样品均为Ca3Co4O9相。样品的SEM照片显示：晶粒为片状结构;热等静压烧结制备的样品,其片状结构不明显,但致密度较之另外两种工艺大幅度提高,其相对密度为95％。制备工艺对(Ca0.9La0.1)3Co4O9热电材料Seebeck系数影响不大,但热压烧结样品能大幅度提高(Ca0.9La0.1)3Co4O9电导率。在一定温度范围内,随温度升高,功率因子大幅度增加,对于热压烧结的样品尤为显著。     

Ca_(2.7)Sr_(0.3)Co_4O_9 和 Ca_(0.95)Sm_(0.05)MnO_3 热电材料的性能及器件(英文)

为了构造具有一定实用性能的氧化物热电器件,对 p 型 Ca3Co4O9和 n 型 CaMnO3过渡金属氧化物半导体进行研究,结果表明:Ca2.7Sr0.3Co4O9和 Ca0.95Sm0.05MnO3的热电性能良好。Ca2.7Sr0.3Co4O9陶瓷的微观形貌呈片层状及尖锐的(00?)相,说明具有高度织构,Ca0.95Sm0.05MnO3陶瓷为单一相正交晶系。分析了样品形成的化学反应过程。热电参数测试结果表明:Ca2.7Sr0.3Co4O9为 p 型半导体,空穴导电机制,Ca0.95Sm0.05MnO3为 n 型半导体,电子导电机制。两种材料的电阻均较低,在 870 K,Seebeck 系数分别为 170 μV/K 和–167 μV/K。在测量温度范围内,热导率变化很小,并计算出热电优值。利用此两种材料构造热电器件,并对其性能进行测试。     

氟掺杂对Ca3Co4O9化合物微观结构和热电性能的影响

采用固相合成法及放电等离子烧结制备了Ca3Co4(FxO1-x)9(x=0,0.01,0.02)块体样品,系统研究了氟(F)掺杂对Ca3Co4O9微观结构和热电性能的影响。结果表明:F掺杂样品均为单一化合物。在300～900K,与纯样相比,F掺杂样品的Seebeck系数变化较小,电导率显著增大,热导率先减小后随F掺量的增加而增大。x=0.01时,样品具有最高电导率和最低热导率,分别为14×103S/m和2.16W/(m·K)。在900K,样品最大热电优值(ZT值)为0.16,较纯样品的提高了近100%。     

烧结工艺对Ca3Co4O9基热电氧化物电性能的影响

采用溶胶-凝胶化学法合成了Ca3Co4O9热电氧化物粉末,分别采用陶瓷烧结工艺方法和放电等离子烧结(Spark Plasma Sintering,SPS)的方法制备了Ca3Co4O9热电氧化物块体材料.利用X射线衍射XRD、扫描电子显微镜SEM和电输运参数测试仪分析了所得样品的物相、微观组织结构、晶粒取向度和电输运性能.结果表明,不同制备方法均可得到纯相的Ca3Co4O9热电氧化物块体材料;通过陶瓷烧结工艺方法制备的Ca3Co4O9热电氧化物块体晶粒取向度较低,但随着成型压力的增加而提高;SPS烧结的方法制备的Ca3Co4O9热电氧化物块体晶粒取向度最高;试样电性能随着晶粒取向度的提高逐渐提高,其中SPS烧结方法制备的块体材料电性能最高,在测试温度最高点700℃时功率因子达3.85 μWmK-2,远高于普通烧结试样.     

放电等离子烧结制备Ca3Co4O9陶瓷及其电学性能

采用化学共沉淀与放电等离子烧结相结合的方法制备了Ca3Co4O9陶瓷.通过X射线衍射,红外光谱仪,扫描电镜等表征手段,探讨了Ca3Co4O9的形成过程,研究了不同制备工艺对陶瓷的物相,显微结构和性能的影响.实验结果表明共沉淀前驱物800℃预烧6 h或8 h后,再经放电等离子850℃,压力30 MPa下烧结5 min,可以获得纯相Ca3Co4O9陶瓷;800℃预烧6 h的烧结体密度为4.53 g/cm3,800℃预烧8 h的烧结体密度为4.78 g/cm3;前驱物预烧8 h后再经放电等离子烧结的块体具有较好的电学性能.700℃时,电阻率为8.30×10-5 Ωm,Seebeck系数为182μV/K.电导率和Seebeck系数在目前Ca-Co-O材料中是较高的.     

Ca3Co4O9基氧化物热电材料研究进展

详细综述了提高Ca3Co4O9基氧化物热电性能的主要途径,包括制备工艺的改进、掺杂改性研究、热电性能的结构调控等,着重从Ca位掺杂和Co位掺杂两个方面介绍了Ca3Co4O9在掺杂改性方面的研究进展,并提出了该材料存在的问题和今后的发展方向。     

Ca3Co4O9陶瓷的固相法制备及分析

本实验采用固相合成法成功地制备了Ca3Co4O9热电材料。通过对样品的显微结构与物相组成等进行分析研究,优化了制备工艺。实验结果表明:由固相法制得的Ca3Co4O9为取向无规则的片状组织;适当提高煅烧温度、延长保温时间有利于片状组织的生长。     

Enhancement of Thermoelectric Performance in Hierarchical Mesoscopic Oxide Composites of Ca3Co4O9 and La0.8Sr0.2CoO3

The natural contradiction in enhancing electrical conductivity and thermopower in thermoelectric oxides makes it hard to improve the performance of a single thermoelectric oxide material. We report a facile method to construct a unique architecture of thermoelectric oxides that is promising to realize a simultaneous improvement of overall electrical conductivity and thermopower. Here, a series of two‐phase nanocomposites comprising of Ca₃Co₄O₉ (CCO) and La_0.8Sr_0.2CoO₃ (LSCO) has been synthesized through ball milling followed by spark plasma sintering (SPS) method. The electron microscope images reveal that the two constituents form the unique composites while retaining their individual crystalline and morphological identities. Owing to the hierarchical mesoscopic structure with nanoscale particles and submicrometer scale grain boundaries, an external strain is induced into the CCO grains by the LSCO nanoparticles to enhance the thermopower. The mesoscopic structure is also favorable for improving the electrical conductivity. Moreover, the long‐wavelength phonons can be scattered effectively from LSCO nanoparticles and the thermal conductivity is further suppressed. With compromises between power factor and thermal conductivity, the largest ZT achieved is up to 0.41 at 1000 K for the composites with 25 wt% of LSCO.     

Fabrication of highly textured Ca3Co4O9 ceramics with controlled density and high thermoelectric power factors

Ca₃Co₄O₉ ceramics have been studied as an alternative p-type thermoelectric material. Thermoelectric properties of the ceramics would be improved by either orientation of grains or introduction of pores. In this study, we fabricated textured Ca₃Co₄O₉ ceramics with controlled density by a reactive-templated grain growth method combined with a hot-forging technique. A powder precursor obtained by mixing β-Co(OH)₂ as a template and CaCO₃ as a matrix was uniaxially pressed into pellets and sintered under hot-forging pressures up to 5.0 MPa. The relative density of the resulting ceramics was varied between 41.0 and 83.8 % while all the ceramics showed excellent c-axis orientation. The in-plane electrical conductivity of our ceramics could be kept relatively higher than that ever reported previously due to the orientation. Because Seebeck coefficient did not depend on the relative density, the higher electrical conductivity of our ceramics led directly to improved thermoelectric power factors between 67.0 and 409 μW·m⁻¹ K⁻².     

Sr掺杂对Ca3Co4O9热电性能的影响与理论分析

通过实验研究了Ca位掺杂对Ca3CoaO9热电性能的影响,并用密度泛函离散变分法从理论和计算上寻求支持,从化学键角度对此现象进行解释。结果发现：与未掺杂体系相比较,x=0．05有利于降低材料的电阻率,但Seebeck系数有所减弱;z=0．10对降低电阻率不利;体系在473～773K范围内具有hopping电导的特征。建...     

Synthesis of single-phase Ca3Co4O9 ceramics and their processing for a microstructure-enhanced thermoelectric performance

Single-phase Ca₃Co₄O₉ with a high porosity, having a ZT of 0.09 at 627 °C, was successfully prepared by a simple solid-state reaction using fine powders of CaCO₃ and Co₃O₄ after a calcination at 760 °C for 12 hours. It was excellent either for the preparation of the starting powder for the processing of the Ca₃Co₄O₉ ceramics or for direct processing. The influence of already-reported processing methods (classic sintering, hot pressing, free-edge spark-plasma sintering (SPS) of a sintered pellet) and new methods, such as free-edge SPS of a pellet from just-compacted powder, cold pressing of a sintered pellet without post annealing, and free-edge cold pressing of a sintered pellet with post-annealing, on the preparation of Ca₃Co₄O₉ ceramics was studied. The results showed how the density, the grain morphology and the microstructural anisotropy can all influence the thermoelectric characteristics of Ca₃Co₄O₉ ceramics measured in directions parallel and perpendicular to the applied pressure. While the fully dense (99%) and perfectly textured ceramics prepared by the free-edge SPS of a pellet from just-compacted powder had a ZT of 0.17, the highest ZT of 0.31 was obtained for the free-edge cold-pressed and annealed ceramics with modest texturing and low density (65%), having a very low κ of 0.47 W/mK. The results also showed that thin and irregular-shaped plate-like grains with sharp edges are preferred, while their thickening accompanied by rounding of their shape resulted in a reduced thermoelectric performance. The study revealed both the possibilities and the limitations for enhancing the TE characteristics of Ca₃Co₄O₉ ceramics just through microstructure optimisation.     

Significant enhancement of the thermoelectric performance in Ca3Co4O9 thermoelectric materials through combined strontium substitution and hot-pressing process

This work explores the possibilities for a further enhancement of the thermoelectric properties of Ca₃Co₄O₉ by Sr-doping combined with hot-pressing. Modified hot-pressing process resulted in highly-textured and dense ceramics. Sr-doping significantly improves electrical properties, resulting in extremely large power factor (1.2 mW/K²m at 800 °C) due to simultaneous electrical resistivity decrease and Seebeck coefficient increase. The main effect on cumulative electrical performance is provided by the Seebeck coefficient, reaching 270μV/K at 800 °C. XPS revealed relatively high average cobalt oxidation state at room temperature (+3.3), compared to materials produced by conventional sintering. The results of combined XPS and Auger electron spectroscopy emphasize the importance of high densification in Ca₃Co₄O₉-based ceramics for preventing phase decomposition and interaction with CO₂ and moisture. Still, despite the exceptional electrical performance, the calculated figure-of-merit (estimated as 0.29 at 800 °C) is around the best reported in the literature due to a high thermal conductivity (4.4 W/K m at room temperature).     

Low-cost preparation of La4Co3O9 perovskite thin films with distinct absorbance ability and ferromagnetic behaviour

La₄Co₃O₉ perovskite thin film was grown on a glass substrate using spray pyrolysis technique at 460 °C. X-ray diffraction (XRD) pattern indicates a high orthorhombic structure in Ruddlesden-Popper phase along (040) orientation. A nanometric scale size varying between 10 and 20 nm of the La₄Co₃O₉ films were proved via Transmission Electron Microscopy (TEM). The High-Resolution Transmission Electron Microscopy (HRTEM) specifically displayed the lattice fringe among the (040) and (1 10 0) planes. A direct transition band was revealed in the synthesized La₄Co₃O₉ films through transmittance and reflectance spectra, with a band gap of 1.42 eV. Urbach effect as well as a relatively high absorptivity were evidenced. The prepared thin films exhibit a ferromagnetic behaviour. The saturated magnetization (M_S) and coercive field (H_C) were equal to M_S = 4.69810^?4 emu/g and an H_C = 45.56 Oe, respectively, at room temperature. The revealed ferromagnetic behaviour was due to the non-stoichiometry of La₄Co₃O₉ constituents. The present work emphasizes the specificity and suitability of La₄Co₃O₉ thin film perovskite for magneto-optical applications.