钴酸盐类氧化物热电材料的研究进展

氧化物热电材料是半导体热电材料中的一种,具有独特的优点和广阔的应用前景,介绍与其研究相关的基础理论,并讨论了改善热电性能的途径.钴酸盐类氧化物中的NaCo2O4、Ca3Co4O9和Ca3Co2O6处于氧化物热电材料的研究前沿,综述了它们的晶体结构、制备方法、元素掺杂、热电性能及影响因素,探讨了其进一步的发展方向.     

氧化物热电材料研究进展

介绍了氧化物热电材料的应用前景,重点讨论了以NaCo2O4为代表的氧化物热电材料的基本结构、性能特征与研究进展;评述了NaCo2O4材料Na住、Co位掺杂研究和NaCo2O4材料研究中存在的问题;并介绍了几种其它氧化物热电材料的研究情况.     

Ca3Co4O9热电材料及其Ca位掺杂改性

氧化物热电材料Ca3Co4O9与传统热电材料相比具有其独特优势,因而引起了广泛的关注.评述了Ca3Co4O9热电材料的主要结构、热电特性及其Ca位掺杂研究的进展(掺入Na,Bi,Ag等),并对Ca3Co4O9热电材料的应用前景进行了展望.     

钴酸盐热电材料研究进展

热电材料具有重要而广阔的应用前景.氧化物热电材料可以避免传统热电材料的一些缺点而倍受重视.本文综述了NaCo2O4、Ca3Co4O9和Ca3Co2O6等系列的晶体结构、制备方法、元素掺杂与改性、电子结构计算与理论分析等,并探讨了钴酸盐热电材料的进一步发展方向.     

Ca3Co4O9基热电材料的研究进展

Ca3Co4O9是一种很有潜力的氧化物热电材料。本文从Ca3Co4O9的结构出发,讨论了利用不同工艺制备Ca3Co4O9的粉体材料、块体材料和薄膜材料的方法。并针对块体材料和薄膜材料的热电性能进行了一定的分析,提出了提高热电材料性能的途径。     

钴酸盐热电材料研究进展

热电材料具有重要而广阔的应用前景。氧化物热电材料可以避免传统热电材料的一些缺点而倍受重视。本文综述了NaCo2O4、Ca3Co4O9和Ca3Co2o6等系列的晶体结构、制备方法、元素掺杂与改性、电子结构计算与理论分析等．并探讨了钴酸盐热电材料的进一步发展方向。     

钴基氧化物热电材料掺杂研究进展

氧化物热电材料是近年研究的热点之一,钴氧化物因具有优良的高温稳定性、抗氧化性、低成本和易于大规模生产等优点而受到人们的广泛关注,被认为是很有使用价值的热电材料,很多学者在此方面进行了大量的研究。详细介绍了元素掺杂对热电性能的影响,从物理机制上分析了掺杂元素的半径和价态对Ca3Co4O9和NaxCo2O4热电性能的影响,为热电材料的进一步研究提供了依据。     

Ce掺杂Ca3Co4O9的高温热电性能

利用二次固相反应方法制备了Ce掺杂的Ca3Co4O9热电材料(CexCa3-xCo4O9,x=0、0.1、0.3),并测试了样品的微观结构和高温热电性能。测试结果表明,Ce替代Ca可有效调制Ca3Co4O9的热电参数;随着温度的升高,样品的电阻率和热导率降低,See-beck系数增大。在973K的温度下,Ce0.1Ca2.9Co4O9具有最高的热电性能(ZT=0.23)。     

不同环境下烧结的Ca3Co4O9的热电性能

采用传统的固相反应法在不同的氧压下烧结制得Ca3Co4O9样品,并对其进行了结构和热电性能表征.经研究发现,在氧气环境下烧结样品可以抑制Ca3Co4O9在高温下分解,提高其烧结温度.在氧气环境中烧结的样品成相优于在空气中烧结的样品.一定氧压下烧结样品的电阻率比常压下烧结样品的电阻率大,但是Seebeck系数明显提高,因而改善了Ca3Co4O9的热电性能.     

Ca3Co4O9的电子结构、化学键及热电性能

Ca3Co4O9是一类很有希望的新型氧化物热电材料,用离散变分密度泛函方法(DFT-DVM)计算了失配层钴酸盐Ca3Co4O9的电子结构和化学键,讨论了它们与热电性能之间的关系.结果表明,Ca3Co4O9属于窄带半导体,在费米能级附近Co 3d主要对导带贡献,O 2p主要对价带贡献.Ca2CoO3层中Co-O键表现出明显的各向异性特征,在c轴方向上化学键比ab-面方向上强.Ca连接了CoO2和Ca2CoO3层的相互作用,Ca与周围O原子的弱结合有可能导致材料的低热导率.     

Improvement in high-temperature thermoelectric properties by adding Mn for Co in Ca3Co4O9

Nano-sized Ca3Co(4-x)Mn(x)O9 (0 < or = x < or = 0.6) thermoelectric powders were synthesized by solution combustion method, using aspartic acid as fuel. The microstructure and high-temperature (500-800 degrees C) thermoelectric properties of the Ca3Co(4-x)Mn(x)O9 were investigated. The addition of Mn for Co in Ca3Co(4-x)Mn(x)O9 resulted in a decrease of the electrical conductivity and a significant increase of the Seebeck coefficient. Consequently, the power factor was remarkably enhanced by the addition of Mn. Ca3Co(3.7)Mn(0.3)O9 sample showed the highest value of the power factor (1.24 x 10(-4) Wm(-1) K(-2)) at 800 degrees C. We believe that the Ca3Co(4-x)Mn(x)O9 is strongly desirable as a novel high-temperature thermoelectric material for power generation.     

EDTA络合溶胶-凝胶法制备Ca3Co4O9粉体

钴基氧化物Ca3Co4O9是一种新型的中高温热电材料。本文以金属醋酸盐和乙二胺四乙酸(EDTA)为原料,利用EDTA络合溶胶-凝胶法制备了Ca3Co4O9粉体,通过X射线衍射(XRD)、热重-差示扫描量热分析(TG-DSC)、傅利叶变换红外光谱(FT-IR)、X射线能谱仪(EDX)和扫描电子显微镜(SEM)等手段对Ca3Co4O9进行表征。实验结果表明,干凝胶在700-900℃条件下恒温煅烧2h,即可获得纯相Ca3Co4O9片状晶体,其晶粒尺寸约为1-2μm。     

Microstructure and Thermoelectric Properties of Bi- and Cu-Substituted Ca3Co4O9 Oxides

Bi- and Cu-substituted Ca3Co4O9 samples were prepared by conventional solid-state reaction method and the effect of element substitution on the microstructures and thermoelectric properties was investigated. Partial substitution of Cu for Co leads to an increase in electrical conductivity and a decrease in Seebeck coefficient due to the rise of hole concentration. The microstructure of Cu-substituted sample is almost unchanged compared with undoped Ca3Co4O9. On the other hand, partial substitution of Bi for Ca gives rise to a significant increase in the grain size, and c-axis-oriented structure can be formed in Ca2.7Bi0.3Co4O9, resulting in an obvious increase in electrical conductivity. Cu and Bi co-substitution further increases the grain growth and the electrical conductivity of Ca2.7Bi0.3Co3.7Cu0.3O9. Thus, Cu and Bi co-substitution samples possess the optimal thermoelectric performance at high temperature and the highest value of power factor can reach 3.1×10-4 Wm-1·K-2 at 1000 K.     

High-temperature thermoelectric properties of Na(Co0.91, Ni0.09)2O4 fabricated by solution combustion method for power generation

High-quality nano-sized Na(Co0.91Ni0.09)2O4 powders, i.e., 27 nm in average size, were synthesized by the solution combustion route. The magnitude of the electrical conductivity, the Seebeck coefficient, and the power factor for Na(Co0.91Ni0.09)2O4 depended strongly on the fuel used and followed the order of aspartic acid > glutamic acid > alanine > glycine. The order of the thermoelectric characteristics was consistent with that of the density of Na(Co0.91Ni0.09)2O4. The maximal power factor (1.06 x 10(-3) Wm(-1) K(-2)) was achieved for aspartic acid-processed Na(Co0.91 Ni0.09)2O4 twice-sintered at 800 degrees C. We believe that the solution combustion route was highly effective for fabricating high-efficiency thermoelectric materials.     

PbS插层K4Nb6O17复合物的制备及其光催化制氢活性

采用固相法合成层状半导体K4Nb6O17,通过层间离子交换反应、胺插入反应以及硫化反应制备了纳米PbS插层的K4Nb6O17复合光催化剂(记作K4Nb6O17/PbS).利用X射线衍射(XRD),场发射扫描电镜(SEM),X射线荧光光谱仪(XRF),紫外可见漫反射(UV-Vis)和分子荧光光谱(PL)等技术对其进行表征.考察了催化剂在Na2SO3和Na2S为牺牲剂的光催化制氢活性.结果表明,PbS的插层拓展了K4Nb6O17对可见光的响应,催化制氢活性也有明显提高.在紫外光和可见光下3 h产氢量分别达到123.94和0.66 mmol/(g cat).最后讨论了插层复合催化剂光生电荷转移的机理.     

Thermoelectric Characterization of （Na1-yMy）1.6Co2O4 （M=K, Ca, Sr）

Oxide materials NaCo2O4 and (Na1-yMy)1.6Co2O4 (M=K, 0.05≤y≤0.35; M=Ca, Sr, 0.10≤y≤0.40) were prepared by a sol-gel method. Experimental results indicated that the Seebeck coefficient and the Powerfactor of NaCo2O4 were improved by doping Ca and Sr but not by K. The Power-factor of NaCo2O4 is in its maximum, 1.68×10-4 W·m-1·K-2 and 11% bigger than that of the original one when the dopant fraction of Ca was 0.1. Doping Sr makes NaCo2O4 have the biggest Power-factor, 1.68×10-4 W·m-1·K-2 that is 50% bigger than the non-doping oxide. The experimental results indicate that suitable dopants and addition amounts could improve the thermoelectric properties of NaCo2O4 greatly.     

NaCo2O4及其Na位掺杂热电材料的制备研究

NaCo2O4是氧化物热电材料的典型代表,也是目前人们研究较多的一种热电材料,本文采用固相反应法和溶胶-凝胶法对NaCo2O4以及Na位掺杂K、Ca、Sr、Ce试样进行制备研究.选择合适的工艺参数,采用快速升温法,可获得纯度较高(大于94%)的NaCo2O4,并使掺杂元素K、Ca、Sr进入到NaCo2O4晶格中,而Ce由于原子半径太大,难以掺杂入NaCo2O4晶格.实验结果表明采用柠檬酸溶胶-凝胶法比固相反应法制备的试样晶粒尺寸更细小,增加声子散射,使晶格热导率降低,由此提高材料的热电优值,进一步改善材料的热电性能.