WO2011059185A2 - Méthode de production d'un nanocomposite d'efficacité thermoélectrique supérieure, et nanocomposites produits à l'aide d'une telle méthode - Google Patents

Méthode de production d'un nanocomposite d'efficacité thermoélectrique supérieure, et nanocomposites produits à l'aide d'une telle méthode Download PDF

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Publication number
WO2011059185A2
WO2011059185A2 PCT/KR2010/007244 KR2010007244W WO2011059185A2 WO 2011059185 A2 WO2011059185 A2 WO 2011059185A2 KR 2010007244 W KR2010007244 W KR 2010007244W WO 2011059185 A2 WO2011059185 A2 WO 2011059185A2
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WO
WIPO (PCT)
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mte
nte
nanocomposite
thermoelectric
bulk
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PCT/KR2010/007244
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English (en)
Korean (ko)
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WO2011059185A3 (fr
Inventor
김성진
한미경
김희진
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이화여자대학교 산학협력단
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Publication of WO2011059185A2 publication Critical patent/WO2011059185A2/fr
Publication of WO2011059185A3 publication Critical patent/WO2011059185A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y99/00—Subject matter not provided for in other groups of this subclass
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G21/00—Compounds of lead
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention relates to a method for producing a nanocomposite having improved thermoelectric efficiency and to a nanocomposite prepared accordingly.
  • Thermoelectric elements are semiconductor devices having a function of mutually converting heat into electricity and electricity into heat using a thermoelectric material, and include heat pumps for performing heat absorption and cooling through electricity, and It is applied to the field of power generation (thermoelectric power generation) that can convert solar heat or wasted heat into electricity.
  • thermoelectric power generation thermoelectric power generation
  • the energy conversion efficiency of a thermoelectric element is determined by the thermoelectric figure of merit (ZT).
  • thermoelectric performance index if we can double the conductivity, we can expect the thermal performance index to double, but according to Wiedemann-Franz law, the thermal conductivity is approximately proportional, As it increases, the thermal conductivity also increases proportionally, which does not have an effect of improving the thermoelectric performance index. Therefore, although it is difficult to artificially adjust the value of the thermoelectric performance index, in general, a narrow band gap semiconductor material having an optimal mobility and carrier concentration simultaneously has a Seebeck constant and a thermal conductivity. It is known to be high.
  • thermoelectric materials that exhibit high thermoelectric properties include bismuth telluride (Bi 2 Te 3 ) -based alloys, lead telluride (PbTe) -based alloys, and silicon germanium (SiGe) -based alloys. It is necessary to select a material suitable for the application because of the dependence and the temperature at which the maximum thermoelectric performance index is also different.
  • PbTe lead telluride
  • PbTe -based alloys exhibit the maximum thermoelectric performance index in the medium temperature range (200 to 500 °C) as well as the reasons for high melting point, low vapor pressure, chemical stability, and so on.
  • Research is being actively conducted on power generation technology materials.
  • PbTe based materials are added to p-type impurities such as K and Na or n-type impurities such as PbI 2 to change their electrical conductivity, or to reduce thermal conductivity by adding SnTe or GeTe. It is becoming.
  • One of the latest research trends is to control thermoelectric efficiency by making nanostructured materials using a variety of nanotechnology, including low-dimensional quantum dots and superlattices.
  • thermoelectric performance index by increasing the lattice scattering (phonon) responsible for heat transfer to minimize thermal conductivity or to modify the density of states of the Fermi level (Fermi level) to increase the Seebeck constant.
  • phonon lattice scattering
  • a recent study has shown that nanoparticles are produced on bulk PbTe substrates to improve the thermoelectric performance index by 100% higher than PbTe itself. This is made possible by the Ag-Sb nanostructures generated in the bulk to increase the lattice scattering (phonon) to minimize the thermal conductivity.
  • thermoelectric performance index 1.4. It is powdered into tens of nanometers, then compressed into a hot press and hardened back to bulk. Therefore, the size and shape of the nanoparticles in the resulting bulk thermoelectric material can be considered to be obtained by accident.
  • the method has a bulk electrical conductivity by forming nanosize domain lattice while lowering thermal conductivity to half the bulk.
  • the method may also be called a method of reducing thermal conductivity by increasing lattice scattering by nanoparticles.
  • the domain boundary of each nanoparticle of this material can be removed, it is expected that the thermoelectric performance index can be further increased.
  • thermoelectric performance index As a method of increasing the thermal performance index using nanotechnology, a method of controlling the electrical conductivity by modifying the state density (DOS) as well as the thermal conductivity has been proposed.
  • DOS state density
  • a thermoelectric performance index of 2.4 was obtained. This is an example of a new direction in the study of thermoelectric semiconductors.
  • problems such as lower productivity of the superlattice and rising manufacturing costs.
  • thermoelectric semiconductors As seen in the above studies, researches to improve the performance of thermoelectric semiconductors have been conducted in various directions, but most of the existing methods are mostly limited to one part of thermal or electrical characteristics, and the size of nanostructures in each study. There is a lack of research on the change of physical properties of b.
  • thermoelectric performance index 3 or more.
  • a material that is good in electricity transfer like crystals but does not transmit heat like glass that is, a bulk material having a phonon glass electron crystal (PGEC15).
  • PGEC15 phonon glass electron crystal
  • the inventors of the present invention while developing a method for increasing the thermoelectric performance index by fusing the nanostructures in the form of full crystals in bulk, CdTe or ZnTe as a core, PbTe or SnTe into a cell to produce nanoparticles and the nanoparticles Fused to the bulk as a complete crystal to develop a thermoelectric element with improved thermoelectric efficiency, and completed the present invention.
  • An object of the present invention is to provide a method for producing a nanocomposite with improved thermoelectric efficiency.
  • Another object of the present invention is to provide a nanocomposite having improved thermoelectric efficiency.
  • thermoelectric efficiency in the method of manufacturing a nanocomposite having improved thermoelectric efficiency according to the present invention, a core-cell nanoparticle having a uniform size can be prepared by using a high temperature injection method, and mixed with a bulk sized PbTe or SnTe to produce a nanocomposite,
  • thermoelectric efficiency since the thermoelectric efficiency is improved by controlling the electrical characteristics at the same time, it can be usefully used as a thermoelectric material in the field of thermoelectric cooling and thermoelectric power generation.
  • FIG. 1 is a flow chart showing a method for producing a nanocomposite according to the present invention
  • Figure 2 is a photograph showing a nanocomposite prepared by the production method of the present invention.
  • thermoelectric material of a nanocomposite is a transmission electron microscope (TEM) photograph of a thermoelectric material of a nanocomposite according to the present invention.
  • the present invention is a.
  • thermoelectric efficiency comprising the step (step 3) of heat-treating and heat-treating the MTe-NTe nanoparticles prepared in step 2 and NTe bulk.
  • the surfactant of step 1 may be used, such as oleic acid (oleic acid), octadecene (octadecene) and oleyamin (oleyamine).
  • oleic acid oleic acid
  • octadecene octadecene
  • oleyamin oleyamine
  • the high temperature injection of the step 1 is preferably carried out in a temperature range of 250-350 °C. If the high temperature injection temperature is less than 250 °C, there is a problem that the product is present in the Cd or Te state rather than the MO state because the reaction temperature is low, and when the temperature exceeds 350 °C, the size of the MO compound is large, there is a bulk MO compound There is a problem.
  • Pb precursor of the step 2 may be used, such as PbCl 2 and Pb (Ac) 2 , Sn precursor is Sn (CH 3 CO 3 ) 4 , Tin (IV) acetate and SnCl 4 (Tin (IV) Chloride) and the like Can be used.
  • step 2 is preferably performed at a temperature range of 150-250 °C. If the injection temperature is less than 150 °C, there is a problem that the thickness of the cell is formed too thin, if it exceeds 250 °C there is a problem that the thickness of the cell is too thick or not formed into a cell.
  • step 3 is a step of heat-treating and heat-treating the MTe-NTe nanoparticles prepared in step 2 and NTe bulk.
  • the electrothermal treatment of step 3 is a process for removing the organic material generated in the steps 1 and 2 and can be produced a dense bulk material through the electrothermal treatment.
  • heat treatment is preferably performed in nitrogen or argon atmosphere, and the heat treatment is preferably performed at a temperature range of 300 to 400 ° C. If the electrothermal treatment temperature is less than 300 °C, there is a problem that the organic material is present, if the temperature exceeds 400 °C there is a problem that the oxidation reaction occurs.
  • the heat treatment of step 3 is preferably performed at a temperature range of 900 to 1000 °C. If the heat treatment temperature is less than 900 °C, there is a problem that the crystallinity of the nanocomposite is deteriorated and the core-cell nanoparticles are not mixed with the bulk, and if the heat treatment temperature exceeds 1000 °C, the structure of the nanoparticles having a core-cell structure There is a problem that is changed.
  • thermoelectric efficiency in the method of manufacturing a nanocomposite having improved thermoelectric efficiency according to the present invention, a core-cell nanoparticle having a uniform size can be prepared by using a high temperature injection method, and mixed with a bulk sized PbTe or SnTe to produce a nanocomposite,
  • thermoelectric efficiency since the thermoelectric efficiency is improved by controlling the electrical characteristics at the same time, it can be usefully used as a thermoelectric material in the field of thermoelectric cooling and thermoelectric power generation.
  • Step 1 preparing CdTe
  • oleic acid octatecin or oleyamin
  • Te metal powder dissolved in TOP (Trioctylphosphine) or TOPO (Trioctylphosphine oxide) was injected at high temperature to 300 ° C. to prepare CdTe.
  • Step 2 preparing CdTe-PbTe of core-cell structure
  • CdTe-PbTe having a core-cell structure was prepared by injecting PbCl 2 (or Pb (Ac) 2 ) precursor added with oleic acid to CdTe prepared in Step 1 at 200 ° C.
  • Step 3 preparing a nanocomposite
  • the CdTe-PbTe nanoparticles prepared in step 2 and the bulk PbTe were mixed and subjected to an electrothermal treatment in an argon or nitrogen atmosphere at 300-400 ° C., and then placed in a quartz tube and heat-treated at 900-1000 ° C. in a vacuum atmosphere (see FIG. 2). .
  • thermoelectric material Pb metal powder and Te metal powder were heat-treated at 1050 ° C. in a vacuum furnace to prepare a thermoelectric material.
  • thermoelectric material was manufactured by hot pressing at about 600 ° C. for 2 to 24 hours.
  • thermoelectric material prepared in Example 1 In order to determine the internal structure of the nanocomposite thermoelectric material prepared in Example 1 according to the present invention, a transmission electron microscope (TEM, JEOL, JEM-2010F) was analyzed, and the results are shown in FIG. 3.
  • TEM transmission electron microscope
  • thermoelectric properties of the nanocomposite thermoelectric materials prepared in Example 1 according to the present invention and the thermoelectric materials prepared in Comparative Examples 1 and 2 were compared, and the results are shown in Table 1.
  • Example 1 -60 One 0.05 1.96 Comparative Example 1 -60 to 80 1 ⁇ 1.4 0.5-0.7 0.2-0.4 Comparative Example 2 -50 to 70 0.8 ⁇ 1.2 0.25-0.35 0.4-0.6
  • the thermal conductivity of the nanocomposite thermoelectric material prepared in Example 1 according to the present invention is 0.05 W / K ⁇ m it can be seen that lower than the thermoelectric materials prepared in Comparative Examples 1 and 2 As the thermal conductivity is low, the thermoelectric performance index is increased, and the thermoelectric efficiency is improved.

Abstract

La présente invention concerne une méthode de production d'un nanocomposite d'efficacité thermoélectrique supérieure ainsi que les nanocomposites produits à l'aide d'une telle méthode, et plus spécifiquement une méthode de production d'un nanocomposite d'efficacité thermoélectrique améliorée, ladite méthode comprenant les étapes suivantes : production d'un Mte (M = Cd ou Zn) par ajout d'un tensioactif à un MO traité en surface et portant un ligand de coordination, puis injection de poudre métallique de Te à haute température (Étape 1) ; production d'un MTe-NTe (N = Pb ou Sn) de structure noyau-enveloppe par injection d'un précurseur de N dans le MTe produit à l'Étape 1 (Étape 2) ; et mélangeage du NTe en masse au MTe-NTe nanoparticulaire produit à l'Étape 2 et mise en œuvre d'un traitement thermique préliminaire, puis d'un traitement thermique (Étape 3) ; et la présente invention concerne également des nanocomposites obtenus par le mélangeage de NTe en masse (N = Pb ou Sn) à des nanoparticules de MTe-NTe (M = Cd ou Zn) présentant une structure noyau-enveloppe d'une forme dans laquelle le NTe forme une sphère entourant la circonférence du MTe sphérique nanoparticulaire. La méthode de production d'un nanocomposite présentant une efficacité thermoélectrique supérieure selon la présente invention peut être employée avantageusement dans des matériaux thermoélectriques dans le domaine du refroidissement thermoélectrique et de la production thermoélectrique d'énergie électrique, car elle permet d'utiliser une méthode d'injection à haute température pour produire des nanoparticules de type noyau-enveloppe de taille uniforme, et PbTe ou SnTe sous forme massive y est mélangé pour produire un nanocomposite, ce qui permet de maîtriser à la fois les propriétés thermiques et les propriétés électriques, et ainsi présenter une efficacité thermoélectrique améliorée.
PCT/KR2010/007244 2009-11-11 2010-10-21 Méthode de production d'un nanocomposite d'efficacité thermoélectrique supérieure, et nanocomposites produits à l'aide d'une telle méthode WO2011059185A2 (fr)

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KR1020090108590A KR101094458B1 (ko) 2009-11-11 2009-11-11 열전효율이 향상된 나노복합체의 제조방법 및 이에 따라 제조되는 나노복합체
KR10-2009-0108590 2009-11-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9287483B2 (en) 2012-04-27 2016-03-15 Samsung Electronics Co., Ltd. Thermoelectric material with improved in figure of merit and method of producing same

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
KR101409404B1 (ko) 2012-10-09 2014-06-20 한양대학교 에리카산학협력단 열전재료의 제조방법 및 그에 따라 제조된 열전재료
KR102138527B1 (ko) * 2014-01-20 2020-07-28 엘지전자 주식회사 상분리를 이용한 열전소재, 상기 열전소재를 이용한 열전소자 및 그 제조방법
KR102284963B1 (ko) * 2019-11-18 2021-08-04 울산과학기술원 텔루라이드 기반 고성능 열전 박막을 이용한 열전 박막 소재 및 이의 제조방법
CN112670394B (zh) * 2020-12-24 2022-11-08 合肥工业大学 一种通过引入稳定的纳米异质结提高p型SnTe基材料热电性能的方法

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US20050268956A1 (en) * 2004-03-31 2005-12-08 Seiji Take Thermoelectric conversion materials
JP2007021670A (ja) * 2005-07-19 2007-02-01 Dainippon Printing Co Ltd コアシェル型ナノ粒子および熱電変換材料
KR20070108853A (ko) * 2004-10-29 2007-11-13 메사추세츠 인스티튜트 오브 테크놀로지 열전 성능 지수가 높은 나노 복합재
US20080087314A1 (en) * 2006-10-13 2008-04-17 Tulane University Homogeneous thermoelectric nanocomposite using core-shell nanoparticles

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US20050268956A1 (en) * 2004-03-31 2005-12-08 Seiji Take Thermoelectric conversion materials
KR20070108853A (ko) * 2004-10-29 2007-11-13 메사추세츠 인스티튜트 오브 테크놀로지 열전 성능 지수가 높은 나노 복합재
JP2007021670A (ja) * 2005-07-19 2007-02-01 Dainippon Printing Co Ltd コアシェル型ナノ粒子および熱電変換材料
US20080087314A1 (en) * 2006-10-13 2008-04-17 Tulane University Homogeneous thermoelectric nanocomposite using core-shell nanoparticles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9287483B2 (en) 2012-04-27 2016-03-15 Samsung Electronics Co., Ltd. Thermoelectric material with improved in figure of merit and method of producing same

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WO2011059185A3 (fr) 2011-11-03
KR101094458B1 (ko) 2011-12-15
KR20110051814A (ko) 2011-05-18

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