Development of next generation Peltier materials by means of misfit-layered sulfides

通过失配层状硫化物开发下一代珀耳帖材料

• 批准号: 15560582
• 负责人: MIYAZAKI Yuzuru
• 金额: $ 2.24万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15560582/
• 关键词: Thermoelectric conversion; Peltier materials; Misfit; Sulfides; Composite crystals; Thermoelectric power; Thermoelectric properties; Structure analyses; 結晶構造

We have focused on preparing misfit-layered sulfides [Ln_2S_2]_pTS_2 (Ln:lanthanide ions, T:transition metal ions), in which a large thermoelectric power factor and a low lattice thermal conductivity can be simultaneously realized, to design novel Peltier materials. First of all, a T=Nb system has been explored to prepare new p-type materials. Except for Ln=Eu and Lu, all the lanthanides ions including Y are found to form [Ln_2S_2]_pNbS_2 phases. Three-types of structure with different superspace group are discovered depending on their ionic radii. Larger ions with Ln=La,Ce and Pr form orthorhombic Fm2m(p00)00s, while the samples with Ln=Nd and Sm form Fm2m(p00)000. For smaller ions with Ln=Gd,Tb,Dy,Ho,Er,Tm,Yb and Y, monoclinic F2(p0q) phases are obtained. The sample with Ln=Yb exhibits the highest thermoelectric figure-of-merit Z=3.2 x 10^<-4> K^<-1>, with the Seebeck coefficient S=60μVK^<-1>, resistivity ρ=1.4 mΩcm and κ=0.80 WK^<-1>m^<-1>, at around 300 K, yielding the dimensionles … More s figure-of-merit ZT〜0.1. The Z value still increases with increasing temperature, but the maximum value of Z as well as the highest limit temperature to be utilized are not determined in detail. Next, we have fabricated a thermoelectric pn junction (1 pair) using a Yb-Nb-S compound as a p-type leg and a Sn-Ti-S compound as an n-type leg. The pn uncouple was attached to an Al sheet on its top with silver paste and then was subjected to the Peltier property measurements. At the beginning, a small temperature difference with several kelvin was in fact observed but the difference became small and reached zero with further applying an electric current. This behavior can be ascribed to the fact that the Seebeck coefficient of the both legs was not enough (〜70μVK^<-1>) to keep generating temperature difference because the generated Joule heat easily overcame the temperature difference. Hence, further study is necessary to design sulfide thermoelectric materials which have larger figure-of-merit. Less

本论文的主要工作是制备错配层状硫化物[Ln_2S_2]_pTS_2（Ln：镧系元素离子，T：过渡金属离子），使其同时具有高的热电功率因数和低的晶格热导率，以设计新型的Peltier材料。首先，探索了T=Nb体系来制备新的p型材料。除Ln=Eu和Lu外，所有镧系离子（包括Y）均形成[Ln_2S_2]_pNbS_2相。根据离子半径的不同，发现了具有不同超空间群的三种结构。较大的Ln=La、Ce和Pr离子形成正交晶系的Fm2 m（p00）00 s，而Ln=Nd和Sm离子形成正交晶系的Fm2 m（p00）000。对于较小的离子（Ln=Gd、Tb、Dy、Ho、Er、Tm、Yb和Y），获得单斜F2（p0 q）相。具有Ln=Yb的样品在300 K附近表现出最高的热电优值Z=3.2 x 10^<-4>K^<-1>，具有塞贝克系数S=60μVK^<-1>，电阻率ρ=1.4 mΩcm和κ=0.80 WK^<-1>m^<-1>，得到尺寸 ...更多信息 的品质因数ZT为0.1。Z值仍然随温度的升高而增加，但Z的最大值以及所使用的最高极限温度没有详细确定。接下来，我们使用Yb-Nb-S化合物作为p型腿和Sn-Ti-S化合物作为n型腿制造热电pn结（1对）。pn解偶联器在其顶部用银膏附着到Al片上，然后进行珀耳帖特性测量。开始时，实际上观察到几开尔文的小温差，但随着进一步施加电流，该温差变小并达到零。这种行为可以归因于两个腿的塞贝克系数不足以（170 μVK^<-1>）保持产生温度差的事实，因为产生的焦耳热容易克服温度差。因此，有必要对硫化物热电材料进行进一步的研究，以设计出具有更大优值的硫化物热电材料。少

项目成果

Compounds and subsolidus phase relations in the CaO-Co_3O_4-CuO system

CaO-Co_3O_4-CuO体系中的化合物和亚固相线相关系

• 发表时间: 2005
• 期刊: J.Solid State Chem. 178
• 作者: 兵道哲;西原直枝;田中麻子;早川真由美;羽田正沖;田辺新一;岩本正和;Y.Miyazaki
• 通讯作者: Y.Miyazaki

複合結晶[(Ca_<1-x>Sr_x)_2CoO_3]_pCoO_2の結晶構造と熱電特性

复合晶体[(Ca_<1-x>Sr_x)_2CoO_3]_pCoO_2的晶体结构及热电性能

• 发表时间: 2003
• 期刊: 粉体および粉末冶金 50
• 作者: Mayumi Hayakawa;Naoe Nishihara;Masaoki Haneda;Asako Tanaka;Shin-ichi Tanabe;Nagamura et al.;M.Tokunaga;宮崎 譲
• 通讯作者: 宮崎 譲

Preparation and Thermoelectric Properties of Misfit-Layered Sulfides [Ln_2S_2]_pNbS_2

错配层状硫化物[Ln_2S_2]_pNbS_2的制备及其热电性能

• 发表时间: 2004
• 期刊: Proceedings of the 23^<rd> International Conference on Thermoelectrics (ITC 2004) (CD-ROM#081)
• 作者: M.Baba;Y.Ono;R.O.Suzuki;Toshihiko Nagamura;Y.Miyazaki
• 通讯作者: Y.Miyazaki

Modulated Structure of Misfit-Layered Cobalt Oxide [Ca2(Co0.65Cu0.35)2O4]0.63CoO2

• DOI: 10.1143/jjap.42.7467
• 发表时间: 2003-12
• 期刊: Japanese Journal of Applied Physics
• 影响因子: 1.5
• 作者: Y. Miyazaki;T. Miura;M. Onoda;M. Uchida;Y. Ishii;Y. Ono;Y. Morii;T. Kajitani

環境調和型新材料シリーズ「熱電変換材料」2.2章

环保新材料系列《热电转换材料》第2.2章

• 发表时间: 2006
• 作者: S.Watanabe;et al.;Yuzuru Miyazaki;S.Watanabe 他5名;宮崎 譲
• 通讯作者: 宮崎 譲