WO2019168029A1 - Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, module de conversion thermoélectrique et procédé de production de matériau de conversion thermoélectrique - Google Patents

Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, module de conversion thermoélectrique et procédé de production de matériau de conversion thermoélectrique Download PDF

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Publication number
WO2019168029A1
WO2019168029A1 PCT/JP2019/007563 JP2019007563W WO2019168029A1 WO 2019168029 A1 WO2019168029 A1 WO 2019168029A1 JP 2019007563 W JP2019007563 W JP 2019007563W WO 2019168029 A1 WO2019168029 A1 WO 2019168029A1
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Prior art keywords
thermoelectric conversion
conversion material
powder
magnesium
compounds
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PCT/JP2019/007563
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English (en)
Japanese (ja)
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中田　嘉信
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三菱マテリアル株式会社
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Priority claimed from JP2019022732A external-priority patent/JP7251187B2/ja
Application filed by 三菱マテリアル株式会社 filed Critical 三菱マテリアル株式会社
Priority to CN201980014342.XA priority Critical patent/CN111771290A/zh
Priority to KR1020207023203A priority patent/KR20200124224A/ko
Priority to EP19761165.0A priority patent/EP3761381A4/fr
Priority to US16/975,268 priority patent/US11380831B2/en
Publication of WO2019168029A1 publication Critical patent/WO2019168029A1/fr

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    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/12—Metallic powder containing non-metallic particles
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • 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

Definitions

  • the present invention relates to a thermoelectric conversion material composed of a sintered body of a magnesium-based compound, a thermoelectric conversion element including the thermoelectric conversion material, a thermoelectric conversion module, and a method for manufacturing the thermoelectric conversion material.
  • thermoelectric conversion element made of a thermoelectric conversion material is an electronic element capable of mutually converting heat and electricity, such as Seebeck effect and Peltier effect.
  • the Seebeck effect is an effect of converting thermal energy into electric energy, and is a phenomenon in which an electromotive force is generated when a temperature difference is generated between both ends of the thermoelectric conversion material. Such electromotive force is determined by the characteristics of the thermoelectric conversion material.
  • thermoelectric power generation utilizing this effect has been actively developed.
  • the thermoelectric conversion element described above has a structure in which electrodes are formed on one end side and the other end side of a thermoelectric conversion material.
  • thermoelectric conversion material As an index representing the characteristics of such a thermoelectric conversion element (thermoelectric conversion material), for example, the power factor (PF) expressed by the following formula (1) or the dimensionless figure of merit expressed by the following formula (2) (ZT) is used.
  • PF S 2 ⁇ (1)
  • ZT S 2 ⁇ T / ⁇ (2)
  • T absolute temperature (K)
  • ⁇ thermal conductivity (W / (m ⁇ K))
  • thermoelectric conversion material for example, as shown in Patent Documents 1 and 2, materials obtained by adding various dopants to magnesium silicide have been proposed.
  • thermoelectric conversion material which consists of magnesium silicide shown in patent document 1, 2 it manufactures by sintering the raw material powder adjusted to the predetermined composition.
  • thermoelectric conversion material elements such as Sb and Bi used as dopants in the thermoelectric conversion material described above correspond to chemical substances specified by, for example, the chemical substance management promotion method (PRTR method), and therefore, it is necessary to strictly manage them. And handling was very complicated. In addition, since other dopant elements such as Al may be deteriorated by oxidation of the dopant element, the handling becomes complicated and there is a problem of oxidation during production.
  • magnesium silicide does not have a stable and low resistance, and generally has a very high electrical resistance, a large variation in electrical resistance depending on manufacturing conditions, and is important for thermoelectric materials. Since the electric resistance greatly fluctuates from a low temperature to a middle temperature, it could not be used as a thermoelectric conversion material.
  • the present invention has been made in view of the above-described circumstances, and can reduce the electric resistance value without adding a dopant element that is complicated to handle, and uses a thermoelectric conversion material excellent in thermoelectric characteristics. It is an object of the present invention to provide a thermoelectric conversion element, a thermoelectric conversion module, and a method for manufacturing the thermoelectric conversion material.
  • thermoelectric conversion material of the present invention is a thermoelectric conversion material made of a sintered body of a non-doped magnesium-based compound and has an electric resistance value of 1.0 ⁇ 10 ⁇ 4 ⁇ ⁇ m or less. It is characterized by being.
  • thermoelectric conversion material comprising the sintered body of the non-doped magnesium compound of the present invention has an electrical resistance value of 1.0 ⁇ 10 ⁇ 4 without intentionally adding a dopant of a metal element such as Sb, Bi, or Al. It is a thermoelectric conversion material having a low power of ⁇ ⁇ m or less and a high power factor (PF) and dimensionless figure of merit (ZT).
  • PF power factor
  • ZT dimensionless figure of merit
  • the thermoelectric conversion material of the present invention is particularly excellent in thermoelectric characteristics in a relatively low temperature region from room temperature to about 300 ° C.
  • the magnesium compound is preferably one or more selected from MgSi compounds, MgSn compounds, MgSiSn compounds, and MgSiGe compounds.
  • the magnesium compound is one or more selected from MgSi compounds, MgSn compounds, MgSiSn compounds, and MgSiGe compounds, it is possible to obtain a thermoelectric conversion material having further excellent thermoelectric characteristics. it can.
  • thermoelectric conversion material of the present invention is characterized by being n-type.
  • n-type thermoelectric power can be used without intentionally adding a dopant of a metal element such as Sb, Bi, or Al, which is difficult to handle. It can be a conversion material.
  • thermoelectric conversion element of the present invention is characterized by including the above-described thermoelectric conversion material and electrodes bonded to one surface of the thermoelectric conversion material and the other surface facing each other. According to the thermoelectric conversion element of this structure, since it consists of the thermoelectric conversion material mentioned above, the thermoelectric conversion element excellent in the thermoelectric characteristic can be obtained.
  • thermoelectric conversion module of the present invention is characterized by including the above-described thermoelectric conversion element and terminals respectively joined to the electrodes of the thermoelectric conversion element. According to the thermoelectric conversion module having this configuration, since the thermoelectric conversion element made of the thermoelectric conversion material described above is provided, a thermoelectric conversion module having excellent thermoelectric characteristics can be obtained.
  • the manufacturing method of the thermoelectric conversion material of the present invention is a manufacturing method of the thermoelectric conversion material for manufacturing the above-described thermoelectric conversion material, in which silicon oxide powder is mixed with non-doped magnesium-based compound powder and sintered raw material powder is mixed. It is characterized by comprising a sintered raw material powder forming step to be obtained and a sintering step in which the sintered raw material powder is heated while being pressed to form a sintered body.
  • thermoelectric conversion material having this configuration
  • non-doped magnesium compound powder that is, magnesium compound powder to which no dopant is intentionally added
  • silicon oxide powder Since it has a sintering raw material powder forming step to be obtained, it becomes possible to keep the electrical resistance value of the sintered body of the magnesium-based compound low by adding silicon oxide without adding a dopant element. . Therefore, the thermoelectric conversion material mentioned above can be manufactured. Further, since silicon oxide is a chemically stable substance, it is easy to handle silicon oxide at the time of manufacture, and it becomes possible to efficiently manufacture a thermoelectric conversion material.
  • the amount of the silicon oxide powder added in the sintering raw material powder forming step is in the range of 0.1 mass% to 10.0 mass%. Is preferred. In this case, since the addition amount of the silicon oxide powder is in the range of 0.1 mass% or more and 10.0 mass% or less, the electrical resistance value of the magnesium compound sintered body can be reliably reduced. .
  • thermoelectric conversion material excellent in thermoelectric characteristics, a thermoelectric conversion element using the thermoelectric conversion element, a thermoelectric conversion module, and It is possible to provide a method for producing the thermoelectric conversion material.
  • thermoelectric conversion material which is one Embodiment of this invention, a thermoelectric conversion element using the same, and a thermoelectric conversion module. It is a flowchart which shows an example of the manufacturing method of the thermoelectric conversion material which is one Embodiment of this invention. It is sectional drawing which shows an example of the sintering apparatus used with the manufacturing method of the thermoelectric conversion material shown in FIG.
  • thermoelectric conversion material a thermoelectric conversion element, a thermoelectric conversion module, and a method of manufacturing a thermoelectric conversion material according to an embodiment of the present invention
  • a thermoelectric conversion material a thermoelectric conversion material, a thermoelectric conversion element, a thermoelectric conversion module, and a method of manufacturing a thermoelectric conversion material according to an embodiment of the present invention
  • a thermoelectric conversion material a thermoelectric conversion material, a thermoelectric conversion element, a thermoelectric conversion module, and a method of manufacturing a thermoelectric conversion material according to an embodiment of the present invention.
  • thermoelectric conversion material 11 which is embodiment of this invention, the thermoelectric conversion element 10 using this thermoelectric conversion material 11, and the thermoelectric conversion module 1 are shown.
  • a thermoelectric conversion module 1 shown in FIG. 1 includes a thermoelectric conversion material 11 according to the present embodiment, electrodes 12a and 12b formed on one surface 11a of the thermoelectric conversion material 11 and the other surface 11b opposite to the surface 11a. And terminals 13a and 13b connected to the electrodes 12a and 12b.
  • a thermoelectric conversion element 10 includes the thermoelectric conversion material 11 and the electrodes 12a and 12b.
  • the electrodes 12a and 12b are made of nickel, silver, cobalt, tungsten, molybdenum or the like.
  • the electrodes 12a and 12b can be formed by current sintering, plating, electrodeposition, or the like.
  • the terminals 13a and 13b are formed of a metal material having excellent conductivity, for example, a plate material such as copper or aluminum. In this embodiment, an aluminum rolled plate is used.
  • the electrodes 12a and 12b of the thermoelectric conversion element 10 and the terminals 13a and 13b can be joined by Ag brazing, Ag plating, or the like.
  • the thermoelectric conversion material 11 in the present embodiment is composed of a magnesium compound sintered body.
  • the magnesium compound constituting the sintered body is preferably one or more selected from MgSi compounds, MgSn compounds, MgSiSn compounds, and MgSiGe compounds.
  • the compound constituting the sintered body is magnesium silicide (Mg 2 Si).
  • the thermoelectric conversion material 11 according to the present embodiment is a non-doped thermoelectric conversion material and has an electric resistance value of 1.0 ⁇ 10 ⁇ 4 ⁇ ⁇ m or less in a temperature range of 100 ° C. to 550 ° C.
  • the electric resistance value of the thermoelectric conversion material 11 in the temperature range of 100 ° C. or more and 550 ° C. or less is preferably 6.0 ⁇ 10 ⁇ 5 ⁇ ⁇ m or less.
  • the lower limit value of the electric resistance value of the thermoelectric conversion material 11 in the temperature range of 100 ° C. or higher and 550 ° C. or lower is preferably 1.0 ⁇ 10 ⁇ 5 ⁇ ⁇ m.
  • the thermoelectric conversion material 11 according to the present embodiment is an n-type thermoelectric conversion material in which electrons are carriers.
  • non-doped means that a metal element dopant is not added intentionally.
  • a dopant element such as Sb, Bi, or Al may be included.
  • the Sb content is less than 0.001 mass%
  • the Bi content is less than 0.001 mass%
  • the Al content is 0.25 mass% or less.
  • elements such as Na, K, B, Ga, In, P, As, Cu, and Y may be included as inevitable impurities, but even in that case, the content of each element Is preferably 0.01 mass% or less.
  • thermoelectric conversion material 11 in this embodiment since the electric resistance value is 1.0 ⁇ 10 ⁇ 4 ⁇ ⁇ m or less, the dopant element mixed as an unavoidable impurity is very small. Therefore, the electrical resistance value is suppressed to be sufficiently low.
  • the electrical resistance value is suppressed low by adding silicon oxide. Oxygen constituting the added silicon oxide reacts with the magnesium compound Mg during sintering to form magnesium oxide, while Si constituting the silicon oxide segregates to the magnesium compound grain boundary. It is considered that dangling bonds at the interface are formed to reduce the resistance, or diffuse into the Mg compound and enter the Mg lattice sites to emit electrons and lower the electrical resistance. Of the added silicon oxide, unreacted silicon oxide may be contained in the thermoelectric conversion material 11.
  • thermoelectric conversion material 11 Accordingly, an example of a method for manufacturing the thermoelectric conversion material 11 according to the present embodiment described above will be described with reference to FIGS. 2 and 3.
  • the magnesium-based compound powder preparation step S01 First, powder of a non-doped magnesium-based compound (magnesium silicide) serving as a parent phase of a sintered body that is the thermoelectric conversion material 11 is manufactured.
  • the magnesium-based compound powder preparation step S01 includes a magnesium-based compound ingot forming step S11 for obtaining an ingot of a non-doped magnesium-based compound (magnesium silicide), and pulverizing the magnesium-based compound ingot (magnesium silicide) to form magnesium. And a pulverizing step S12 to make a system compound powder.
  • the dissolved raw material powder is weighed and mixed.
  • the melting raw material is silicon grains and magnesium grains.
  • the Sb content is less than 0.001 mass%
  • the Bi content is less than 0.001 mass%
  • the Al content is 0.25 mass% or less. It is preferable that the content of each element of Na, K, B, Ga, In, P, As, Cu, and Y be 0.01 mass% or less.
  • this mixture is charged into a crucible in an atmosphere melting furnace and melted, and then cooled and solidified. Thereby, the ingot of a magnesium type compound (magnesium silicide) is manufactured.
  • a magnesium type compound magnesium silicide
  • it is preferable to add a large amount of magnesium, for example, about 5 at% with respect to the stoichiometric composition of Mg: Si 2: 1 when the raw materials are weighed.
  • the obtained magnesium-based compound (magnesium silicide) ingot is pulverized by a pulverizer to form magnesium-based compound powder (magnesium silicide powder) (pulverization step S12).
  • the average particle size of the magnesium-based compound powder (magnesium silicide powder) is preferably in the range of 0.5 ⁇ m to 100 ⁇ m, and more preferably in the range of 1 ⁇ m to 75 ⁇ m.
  • magnesium silicide powder magnesium silicide powder
  • the magnesium compound ingot forming step S11 and the pulverizing step S12 can be omitted.
  • silicon oxide powder is mixed with the obtained magnesium-based compound powder (magnesium silicide powder) to obtain sintered raw material powder.
  • the amount of silicon oxide powder added is preferably in the range of 0.1 mass% to 10.0 mass%, and more preferably in the range of 0.3 mass% to 5.0 mass%.
  • the average particle diameter of the silicon oxide powder is preferably in the range of 0.1 ⁇ m to 100 ⁇ m, and more preferably in the range of 0.5 ⁇ m to 50 ⁇ m.
  • the sintering apparatus (electric current sintering apparatus 100) shown in FIG. 3 includes, for example, a pressure-resistant housing 101, a vacuum pump 102 that depressurizes the inside of the pressure-resistant housing 101, and a hollow cylinder disposed in the pressure-resistant housing 101.
  • the carbon mold 103 having a shape, a pair of electrode portions 105a and 105b for applying a current while pressurizing the sintering raw material powder Q filled in the carbon mold 103, and a voltage is applied between the pair of electrode portions 105a and 105b.
  • a power supply device 106 Further, a carbon plate 107 and a carbon sheet 108 are disposed between the electrode portions 105a and 105b and the sintering raw material powder Q, respectively.
  • a thermometer, a displacement meter, etc. are provided.
  • the heater 109 is disposed on the outer peripheral side of the carbon mold 103.
  • the heater 109 is disposed on four side surfaces so as to cover the entire outer peripheral side of the carbon mold 103.
  • a carbon heater a nichrome wire heater, a molybdenum heater, a Kanthal wire heater, a high frequency heater, or the like can be used.
  • the raw material powder Q is filled into the carbon mold 103 of the electric current sintering apparatus 100 shown in FIG.
  • the carbon mold 103 is covered with a graphite sheet or a carbon sheet.
  • a direct current is passed between the pair of electrode portions 105a and 105b, and the current is passed through the sintered raw material powder Q to raise the temperature by self-heating (energization heating).
  • the movable electrode portion 105a is moved toward the sintering raw material powder Q, and the sintering raw material powder Q is moved to a predetermined pressure with the fixed electrode portion 105b. Pressurize.
  • the heater 109 is heated.
  • the sintered raw material powder Q is sintered by self-heating of the sintered raw material powder Q, heat from the heater 109, and pressurization.
  • the sintering condition in the sintering step S03 is that the heating temperature of the sintering raw material powder Q is in the range of 850 ° C. or more and 1030 ° C. or less, and the holding time at this heating temperature is 0 minute or more and 3 minutes or less. It is within the range. Further, the pressurizing load is in the range of 15 MPa or more and 60 MPa or less.
  • the atmosphere in the pressure-resistant casing 101 is preferably an inert atmosphere such as an argon atmosphere or a vacuum atmosphere. In a vacuum atmosphere, the pressure is preferably 5 Pa or less.
  • the minimum of the heating temperature of sintering raw material powder is 850 degreeC or more.
  • the upper limit of the heating temperature of the sintered raw material powder is preferably 1030 ° C. or less.
  • the lower limit of the holding time at the heating temperature is preferably 0 minutes or more.
  • the upper limit of the holding time at the heating temperature is preferably 3 minutes or less.
  • the lower limit of the pressure load is preferably 15 MPa or more.
  • the upper limit of the pressure load is preferably 60 MPa or less.
  • the polarities of the one electrode portion 105a and the other electrode portion 105b may be changed at predetermined time intervals. That is, the state in which one electrode part 105a is energized with the anode and the other electrode part 105b as the cathode and the state in which one electrode part 105a is energized with the cathode and the other electrode part 105b as the anode are alternately performed. It is.
  • the predetermined time interval is set within a range of 10 seconds to 300 seconds.
  • the predetermined time interval is preferably in the range of 30 seconds to 120 seconds.
  • thermoelectric conversion material 11 which is this embodiment is manufactured according to the above process.
  • the Sb content is less than 0.001 mass%
  • the Bi content is less than 0.001 mass%
  • the Al content is 0.25 mass% or less
  • Na , K, B, Ga, In, P, As, Cu, and Y the content of each element is 0.01 mass% or less
  • thermoelectric conversion comprising a sintered body of a magnesium-based compound
  • the Sb content is less than 0.001 mass%
  • the Bi content is less than 0.001 mass%
  • the Al content is 0.25 mass% or less
  • Na, K, B, Ga, In, P, Content of each element of As, Cu, and Y will be 0.01 mass% or less.
  • thermoelectric conversion material 11 of the present embodiment configured as described above, a dopant element, in particular, Sb, Bi, Al, which is difficult to handle, is not used as a dopant element, and it is relatively easy to manufacture. can do.
  • the electrical resistance value is kept low at 1.0 ⁇ 10 ⁇ 4 ⁇ ⁇ m or less, the power factor (PF) and the dimensionless figure of merit (ZT) are high, and the thermoelectric characteristics are excellent.
  • the magnesium compound constituting the thermoelectric conversion material 11 is one or more selected from MgSi compounds, MgSn compounds, MgSiSn compounds, and MgSiGe compounds. Therefore, the thermoelectric conversion material 11 having further excellent thermoelectric characteristics can be obtained.
  • thermoelectric conversion material 11 of the present embodiment an n-type thermoelectric conversion material can be obtained without intentionally adding a dopant of a metal element such as Sb, Bi, or Al that is difficult to handle.
  • thermoelectric conversion material 11 according to the method for manufacturing a thermoelectric conversion material according to the present embodiment, a sintering raw material powder forming step of obtaining a sintering raw material powder by mixing silicon oxide powder with non-doped magnesium-based compound powder (magnesium silicide powder). Since S02 and the sintering step S03 in which the sintered raw material powder Q is heated while being pressed to form a sintered body, the thermoelectric conversion material 11 according to the present embodiment described above can be manufactured. it can.
  • silicon oxide it is possible to keep the electrical resistance value of the sintered body of the magnesium compound (magnesium silicide) low without adding a dopant element. Further, since silicon oxide is a relatively stable substance, it can be easily handled during production, and the thermoelectric conversion material 11 can be produced efficiently.
  • thermoelectric conversion element 10 and the thermoelectric conversion module 1 include the thermoelectric conversion material 11 described above, the thermoelectric characteristics are excellent. Therefore, it is possible to configure a thermoelectric conversion device having excellent thermoelectric conversion efficiency.
  • thermoelectric conversion element and thermoelectric conversion module of a structure as shown in FIG. 1 it is not limited to this, thermoelectric conversion material of this invention may be used.
  • the structure and arrangement of the electrodes and terminals are not particularly limited.
  • the magnesium-based compound constituting the sintered body has been described as magnesium silicide (Mg 2 Si).
  • Mg 2 Si magnesium silicide
  • the present invention is not limited to this, and any other composition may be used as long as it has thermoelectric properties.
  • the magnesium-based compound may be used.
  • the above-mentioned raw material particles weighed were charged into a crucible in an atmosphere melting furnace and melted, and then cooled and solidified. This produced the magnesium compound (magnesium silicide) ingot. Next, the ingot was crushed and classified to obtain a non-doped magnesium-based compound powder (magnesium silicide powder) having an average particle size of 30 ⁇ m.
  • silicon oxide powder SiO 2 powder having an average particle size of 15 ⁇ m was prepared, and magnesium silicide powder and silicon oxide powder were mixed to obtain sintered raw material powder. At this time, as shown in Table 1, the content of silicon oxide powder was adjusted. In the comparative example, no silicon oxide was added.
  • thermoelectric conversion material of this invention example and the comparative example was obtained.
  • thermoelectric conversion material Sb, Bi, Al, Na, K, B, Ga, In, P, As, Cu, Y content, electric resistance (R), Seebeck coefficient (S), power factor (PF), thermal conductivity ( ⁇ ), dimensionless figure of merit (ZT) were evaluated.
  • the electrical resistance value R and the Seebeck coefficient S were measured with ZEM-3 manufactured by Advance Riko. The measurement was performed at 100 ° C, 200 ° C, 300 ° C, 400 ° C, 500 ° C, and 550 ° C.
  • the thermal conductivity ⁇ was determined from thermal diffusivity ⁇ density ⁇ specific heat capacity.
  • the thermal diffusivity was measured using a thermal constant measuring device (TC-7000 model manufactured by Vacuum Riko), the density was measured using Archimedes method, and the specific heat was measured using a differential scanning calorimeter (DSC-7 model manufactured by PerkinElmer). The measurement was performed at 100 ° C, 200 ° C, 300 ° C, 400 ° C, 500 ° C, and 550 ° C.
  • the dimensionless figure of merit (ZT) was obtained from the following equation (2).
  • the dopant element was not contained, and the electric resistance value R was very high. Further, the value of the Seebeck coefficient S is relatively unstable, the power factor (PF) is low, the dimensionless figure of merit ZT is also low, and it is confirmed that the thermoelectric characteristics are inferior. In the example of the present invention to which silicon oxide was added, the electric resistance value R was sufficiently low even without containing a dopant element. It is also confirmed that the Seebeck coefficient S is stable, the power factor (PF) is sufficiently high, the dimensionless figure of merit ZT is sufficiently high, and the thermoelectric characteristics are excellent.
  • thermoelectric conversion material having excellent thermoelectric properties. It was.

Abstract

Ce matériau de conversion thermoélectrique est caractérisé en ce qu'il est formé d'un corps fritté d'un composé de magnésium non dopé et en ce qu'il présente une résistance électrique inférieure ou égale à 1,0 × 10-4 Ω·m. Il est préférable que le composé de magnésium soit composé d'un ou de plusieurs composés qui sont choisis parmi des composés de MgSi, des composés de MgSn, des composés de MgSiSn et des composés de MgSiGe.
PCT/JP2019/007563 2018-02-27 2019-02-27 Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, module de conversion thermoélectrique et procédé de production de matériau de conversion thermoélectrique WO2019168029A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201980014342.XA CN111771290A (zh) 2018-02-27 2019-02-27 热电转换材料、热电转换元件、热电转换模块及热电转换材料的制造方法
KR1020207023203A KR20200124224A (ko) 2018-02-27 2019-02-27 열전 변환 재료, 열전 변환 소자, 열전 변환 모듈, 및 열전 변환 재료의 제조 방법
EP19761165.0A EP3761381A4 (fr) 2018-02-27 2019-02-27 Matériau de conversion thermoélectrique, élément de conversion thermoélectrique, module de conversion thermoélectrique et procédé de production de matériau de conversion thermoélectrique
US16/975,268 US11380831B2 (en) 2018-02-27 2019-02-27 Thermoelectric conversion material, thermoelectric conversion element, thermoelectric conversion module, and method for manufacturing thermoelectric conversion

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JP2018-033664 2018-02-27
JP2018033664 2018-02-27
JP2019022732A JP7251187B2 (ja) 2018-02-27 2019-02-12 熱電変換材料、熱電変換素子、熱電変換モジュール、及び、熱電変換材料の製造方法
JP2019-022732 2019-02-12

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009188368A (ja) * 2007-03-23 2009-08-20 National Institute For Materials Science マグネシウム、珪素、スズからなる熱電半導体およびその製造方法
JP2013179322A (ja) 2006-12-20 2013-09-09 Tokyo Univ Of Science 熱電変換材料、その製造方法および熱電変換素子
WO2016052272A1 (fr) * 2014-10-03 2016-04-07 株式会社ミツバ Matériau thermoélectrique de type p, élément thermoélectrique et procédé de production de matériau thermoélectrique de type p
JP2017152691A (ja) 2016-02-24 2017-08-31 三菱マテリアル株式会社 マグネシウム系熱電変換材料の製造方法、マグネシウム系熱電変換素子の製造方法、マグネシウム系熱電変換材料、マグネシウム系熱電変換素子、熱電変換装置
WO2018012369A1 (fr) * 2016-07-12 2018-01-18 学校法人東京理科大学 Siliciure de magnésium polycristallin et son utilisation
JP2018033664A (ja) 2016-08-31 2018-03-08 セイコーエプソン株式会社 液体噴射装置および液体噴射方法
JP2019012828A (ja) * 2017-06-29 2019-01-24 三菱マテリアル株式会社 熱電変換材料、熱電変換素子、熱電変換モジュール、及び、熱電変換材料の製造方法
JP2019022732A (ja) 2008-11-27 2019-02-14 株式会社三洋物産 遊技機

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013179322A (ja) 2006-12-20 2013-09-09 Tokyo Univ Of Science 熱電変換材料、その製造方法および熱電変換素子
JP2009188368A (ja) * 2007-03-23 2009-08-20 National Institute For Materials Science マグネシウム、珪素、スズからなる熱電半導体およびその製造方法
JP2019022732A (ja) 2008-11-27 2019-02-14 株式会社三洋物産 遊技機
WO2016052272A1 (fr) * 2014-10-03 2016-04-07 株式会社ミツバ Matériau thermoélectrique de type p, élément thermoélectrique et procédé de production de matériau thermoélectrique de type p
JP2017152691A (ja) 2016-02-24 2017-08-31 三菱マテリアル株式会社 マグネシウム系熱電変換材料の製造方法、マグネシウム系熱電変換素子の製造方法、マグネシウム系熱電変換材料、マグネシウム系熱電変換素子、熱電変換装置
WO2018012369A1 (fr) * 2016-07-12 2018-01-18 学校法人東京理科大学 Siliciure de magnésium polycristallin et son utilisation
JP2018033664A (ja) 2016-08-31 2018-03-08 セイコーエプソン株式会社 液体噴射装置および液体噴射方法
JP2019012828A (ja) * 2017-06-29 2019-01-24 三菱マテリアル株式会社 熱電変換材料、熱電変換素子、熱電変換モジュール、及び、熱電変換材料の製造方法

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