WO2008149910A1 - Procédé de production d'élément de conversion thermoélectrique - Google Patents

Procédé de production d'élément de conversion thermoélectrique Download PDF

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Publication number
WO2008149910A1
WO2008149910A1 PCT/JP2008/060320 JP2008060320W WO2008149910A1 WO 2008149910 A1 WO2008149910 A1 WO 2008149910A1 JP 2008060320 W JP2008060320 W JP 2008060320W WO 2008149910 A1 WO2008149910 A1 WO 2008149910A1
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WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
conversion material
thermal conductivity
thermoelectric
particles
Prior art date
Application number
PCT/JP2008/060320
Other languages
English (en)
Japanese (ja)
Inventor
Junya Murai
Takuji Kita
Original Assignee
Toyota Jidosha Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyota Jidosha Kabushiki Kaisha filed Critical Toyota Jidosha Kabushiki Kaisha
Publication of WO2008149910A1 publication Critical patent/WO2008149910A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C11/00—Alloys based on lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • 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
    • H10N10/01—Manufacture or treatment
    • 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

Definitions

  • the present invention relates to a method for manufacturing a thermoelectric conversion element that converts heat into electricity or electricity into heat.
  • thermoelectric conversion material is a material that can mutually convert heat energy and electric energy, and is a material constituting a thermoelectric conversion element used as a thermoelectric cooling element or a thermoelectric power generation element.
  • This thermoelectric conversion material uses the Zeebeck effect to perform thermoelectric conversion, and its thermoelectric conversion performance is expressed by the following equation (1) called the figure of merit Z T.
  • thermoelectric conversion material in order to improve the thermoelectric conversion performance of the thermoelectric conversion material, it is necessary to increase the Seebeck coefficient ⁇ and the electric conductivity ⁇ of the material to be used, and to decrease the thermal conductivity ⁇ . Recognize.
  • Journal of Applied Physics, 97, 044317 (2005) proposes miniaturizing the thermoelectric conversion material. That is, by miniaturizing the thermoelectric conversion material particles, the phonon, which is the main factor of heat conduction in the thermoelectric conversion material, is scattered at the interface of the fine particles, and the thermal conductivity / can be reduced.
  • the oxide of the metal constituting the thermoelectric conversion material is 2 5 Since heat treatment was performed at 0 to 3500 and further alloyed at 3500 to 4500, the grain size of the crystal grains in the final thermoelectric conversion element was coarsened to 1 ⁇ 0 to 2500 nm. If the particle size is so coarse, phonon scattering at the grain boundary is insufficient, the effect of reducing thermal conductivity is considered insufficient, and the performance improvement is also insufficient. Accordingly, an object of the present invention is to solve the above-mentioned conventional problems and provide a method for manufacturing a thermoelectric conversion element having an excellent figure of merit. Disclosure of the invention
  • thermoelectric conversion thermoelectric element After preparing a solution containing a salt of an element constituting a thermoelectric conversion material, the solution is dropped into a solution containing a reducing agent to obtain raw material particles of the thermoelectric conversion material.
  • a method for producing a thermoelectric conversion thermoelectric element is provided, which includes the steps of precipitation, heat treatment, and sintering.
  • thermoelectric conversion material by adding a solution containing a salt of an element constituting the thermoelectric conversion material to a solution containing a reducing agent, the raw material particles of the thermoelectric conversion material having an average particle size of 10 to 100 nm
  • the raw material particles are heat-treated and sintered to obtain a thermoelectric conversion element composed of crystal particles of a thermoelectric conversion material having an average particle diameter of 10 to 100 nm. It shows phonon scattering at the grain boundaries, reduces thermal conductivity reduction, and improves the figure of merit ZT.
  • Fig. 1 is a graph showing the relationship between the structural dimensions of the thermoelectric conversion material, the Seebeck coefficient, the electrical conductivity ⁇ , or the thermal conductivity /.
  • FIG. 2 is an image of the thermoelectric conversion element of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
  • the thermal conductivity ⁇ of the thermoelectric conversion material gradually decreases as the microstructure size of the thermoelectric conversion material becomes smaller starting from the length of the mean free path of phonon. Therefore, the figure of merit Z T is improved by designing the structure size to be smaller than the phonon mean free path.
  • thermoelectric conversion material even if the microstructure size of the thermoelectric conversion material becomes smaller than the mean free path of phonon, the electrical conductivity of the thermoelectric conversion material does not decrease, and the particle size is generally less than the mean free path of the carrier. When it becomes, it decreases. In this way, by utilizing the fact that the structural dimension of the thermoelectric conversion material where the thermal conductivity K begins to decrease and the structural dimension of the thermoelectric conversion material where the electrical conductivity ⁇ begins to decrease, the rate of decrease in electrical conductivity is determined.
  • thermoelectric conversion material At least some of the microstructure dimensions of the thermoelectric conversion material should be greater than the mean free path of the carrier and less than the mean free path of the phonon so that the structure size of the thermoelectric conversion material has a larger reduction rate of the thermal conductivity ⁇ than
  • the figure of merit ⁇ ⁇ represented by the above formula (1) can be further increased.
  • the particle size of the particles constituting the thermoelectric conversion material that defines the tissue size of the thermoelectric conversion material. Therefore, according to the method of the present invention, the particle size of at least a part of the particles constituting the thermoelectric conversion material is made equal to or less than the mean free path of the phonon of the thermoelectric conversion material.
  • the mean free path (M F P) is calculated using the following formula.
  • the carrier MFP and phonon MFP are determined by the material and temperature.
  • the thermoelectric conversion element obtained by the present invention at least a part of the structure size is the power factor of the thermoelectric conversion material.
  • thermoelectric conversion element In order to manufacture such a thermoelectric conversion element, in the present invention, first, a solution containing a salt of an element constituting the thermoelectric conversion material is prepared.
  • thermoelectric conversion material to be formed may be saddle type or saddle type.
  • ⁇ type thermoelectric conversion material for example, ⁇ i 2 T e 3 based, P b T e system, Z n 4 S b 3 system, C o S b 3 system, Hafuho Chrysler system, full-Heusler System, SiGe system, etc. can be used.
  • known materials can be applied without any particular limitation.
  • the thermoelectric conversion material formed in the present invention preferably has an output factor larger than 1 mWZK 2, more preferably 2 mWZK 2 or more, and further preferably 3 mWZK 2 or more. If the output factor is 1 mWZK 2 or less, a significant performance improvement cannot be expected.
  • the thermal conductivity K of the thermoelectric conversion material is preferably larger than 5 WZmK, more preferably 7 W / mK or more, and further preferably 10 W mK or more. When the thermal conductivity ⁇ is larger than 5 WZ m K, the effect of the present invention is particularly remarkable.
  • the effect of controlling the microstructure dimensions of the thermoelectric conversion material with the nano-order specified in the present invention is that the lower the thermal conductivity ⁇ , the more the thermoelectric conversion material with higher thermal conductivity c is used.
  • the effect of reducing the thermal conductivity ⁇ is significant.
  • thermoelectric conversion material when the thermoelectric conversion material is Co S b 3 , the salt of the element constituting such a thermoelectric conversion material is cobalt chloride hydrate and antimony chloride, and in the case of Co ⁇ N ix S bs Means cobalt hydrate, nickel chloride and antimony chloride. Then, considering the composition of the thermoelectric conversion material to be formed, the salt of the element constituting the thermoelectric conversion material to be used and the amount thereof are selected.
  • Water or alcohol can be used as the solvent of the salt solution of the elements constituting the thermoelectric conversion material, and ethanol is preferred.
  • this dispersion liquid is dripped at the solution containing a reducing agent.
  • a reducing agent Any element that can reduce the ions of the elements constituting the thermoelectric conversion material, such as Na BH hydrazine, can be used.
  • thermoelectric conversion material In the dispersion containing the salt of the element constituting the thermoelectric conversion material, raw material ions of the thermoelectric conversion material, such as Co ions and Sb ions, are present. Therefore, when mixed with a solution containing a reducing agent, these ions are reduced, and raw material particles of the thermoelectric conversion material, such as Co particles and Sb particles, are precipitated. In this reduction, in addition to the C o particles and S b particles, by-product thereof, for example N a C 1 and N a BO 3 generates. In order to remove this by-product, it is preferable to perform filtration. Furthermore, after filtration, it is preferable to add alcohol to the water to wash away by-products.
  • thermoelectric conversion material particles are synthesized from the raw material particles of the thermoelectric conversion material, washed and dried as necessary, and then subjected to a general sintering method.
  • the thermoelectric conversion element of the present invention can be obtained by performing SPS sintering at 580.
  • the method for producing a thermoelectric conversion material of the present invention makes it possible to control the structure size (particle diameter of thermoelectric conversion material particles) in the nano-order. That is, by reducing the salt of the element constituting the thermoelectric conversion material, raw material particles of the thermoelectric conversion material having a particle size of 10 to 100 nm are formed, and the thermoelectric conversion material particles are formed therefrom.
  • thermoelectric conversion element particle diameter of thermoelectric conversion material particles
  • the dimension of the thermoelectric conversion element (particle diameter of thermoelectric conversion material particles) force is less than the mean free path of the phonon, preferably more than the mean free path of the carrier and less than the mean free path of the phonon, Scattering of phonons in the thermoelectric conversion element occurs sufficiently, and the thermal conductivity / c can be reduced.
  • a thermoelectric conversion element having a large figure of merit ZT represented by the equation (1) is obtained.
  • an excellent thermoelectric conversion element exhibiting a high figure of merit ZT, and the figure of merit ZT, which has been difficult to manufacture in the past exceeds 2.
  • a thermoelectric conversion element can also be obtained.
  • Cobalt chloride (1.0 g) and antimony chloride (3.06 g) were added to ethanol (10 O mL) and dissolved, and then nickel chloride (0.064 g) was added to the solution and mixed uniformly.
  • This solution was added dropwise to a reducing agent solution prepared by dissolving 2.0 g of sodium borohydride in 10 mL of ethanol.
  • hydrothermal synthesis was performed at 20 00 for 48 hours, and the thermoelectric conversion material Co e . 94 Ni Q. Q 6 S b 3 compounds formed.
  • thermoelectric conversion element of the present invention was obtained by the thermoelectric conversion element of the present invention.
  • a T EM image of this device is shown in FIG. 2.
  • the crystal grain size was 10 to 100 nm.
  • the thermal conductivity of this thermoelectric conversion element was measured by the flash method. It was 1.
  • SWZmZK which was the conventional product (crystal grain size: 1550 to 2500 nm, thermal conductivity: 3.5 W / m / K) was reduced by 60%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un procédé de production d'élément de conversion thermoélectrique qui consiste :à préparer une solution contenant un sel d'un élément constituant un matériau de conversion thermoélectrique, à ajouter la solution goutte à goutte à une solution contenant un agent de réduction afin d'entraîner la précipitation d'une particule de matière brute de ce matériau de conversion thermoélectrique, à chauffer la solution et à faire cuire le produit résultant.
PCT/JP2008/060320 2007-06-06 2008-05-29 Procédé de production d'élément de conversion thermoélectrique WO2008149910A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-150696 2007-06-06
JP2007150696A JP2008305918A (ja) 2007-06-06 2007-06-06 熱電変換素子及びその製造方法

Publications (1)

Publication Number Publication Date
WO2008149910A1 true WO2008149910A1 (fr) 2008-12-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017014578A (ja) * 2015-07-01 2017-01-19 トヨタ自動車株式会社 ＢｉとＴｅとを含む合金粒子の製造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011129832A (ja) * 2009-12-21 2011-06-30 Denso Corp 熱電変換素子及びその製造方法
EP2959989B1 (fr) * 2014-06-23 2017-08-02 Belenos Clean Power Holding AG Nanocristaux Sb ou nanocristaux d'alliage de Sb pour anodes de batterie Li-on et Na-ion à charge/décharge rapide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002012427A (ja) * 2000-06-21 2002-01-15 National Institute Of Advanced Industrial & Technology 遷移金属固溶型導電性ニオブ酸塩とその製造法
JP2005343782A (ja) * 2004-05-06 2005-12-15 Tokyo Univ Of Science テルル化ビスマスナノ粒子の製造方法及びテルルナノ粒子の製造方法
WO2007066820A1 (fr) * 2005-12-07 2007-06-14 Toyota Jidosha Kabushiki Kaisha Matériau de conversion thermoélectrique et son procédé de production

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002012427A (ja) * 2000-06-21 2002-01-15 National Institute Of Advanced Industrial & Technology 遷移金属固溶型導電性ニオブ酸塩とその製造法
JP2005343782A (ja) * 2004-05-06 2005-12-15 Tokyo Univ Of Science テルル化ビスマスナノ粒子の製造方法及びテルルナノ粒子の製造方法
WO2007066820A1 (fr) * 2005-12-07 2007-06-14 Toyota Jidosha Kabushiki Kaisha Matériau de conversion thermoélectrique et son procédé de production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017014578A (ja) * 2015-07-01 2017-01-19 トヨタ自動車株式会社 ＢｉとＴｅとを含む合金粒子の製造方法

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