WO2011148686A1 - Procédé de fabrication d'un module de conversion thermoélectrique, et module de conversion thermoélectrique - Google Patents

Procédé de fabrication d'un module de conversion thermoélectrique, et module de conversion thermoélectrique Download PDF

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WO2011148686A1
WO2011148686A1 PCT/JP2011/055075 JP2011055075W WO2011148686A1 WO 2011148686 A1 WO2011148686 A1 WO 2011148686A1 JP 2011055075 W JP2011055075 W JP 2011055075W WO 2011148686 A1 WO2011148686 A1 WO 2011148686A1
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semiconductor element
type semiconductor
thermoelectric conversion
metal oxide
conversion module
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Japanese (ja)
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圭史 西尾
努 飯田
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学校法人東京理科大学
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Definitions

  • the present invention relates to a method for manufacturing a thermoelectric conversion module and a thermoelectric conversion module.
  • Thermoelectric conversion refers to the mutual conversion of thermal energy and electrical energy using the Seebeck effect or Peltier effect. If thermoelectric conversion is used, it is possible to extract electric power from the heat flow using the Seebeck effect.
  • thermoelectric conversion is direct conversion, it has characteristics such that excess waste products are not discharged during energy conversion, and effective use of exhaust heat is possible. For this reason, research on thermoelectric conversion modules has been actively conducted.
  • thermoelectric conversion modules have a so-called ⁇ -type structure.
  • the ⁇ -type structure includes an n-type semiconductor element, a p-type semiconductor element (hereinafter, the n-type semiconductor element and the p-type semiconductor element may be collectively referred to as “semiconductor element”), one end of the n-type semiconductor element, A common electrode to which one end of the p-type semiconductor element is joined, and an electrode to be joined independently to the other end of the n-type semiconductor element and the other end of the p-type semiconductor element (hereinafter, the common electrode and the electrode are combined) It may be referred to as “electrode etc.”).
  • thermoelectric conversion module having a ⁇ -type structure In the manufacture of a thermoelectric conversion module having a ⁇ -type structure, a method using a paste (see Patent Document 1) and a method using solder (see Patent Document 2) are employed as a bonding method between a semiconductor element and an electrode. Neither the method using paste nor the method using solder is satisfactory in terms of productivity because it is necessary to bond a semiconductor element and an electrode for each ⁇ -type thermoelectric conversion module. Therefore, in order to increase the productivity of the thermoelectric conversion module having a ⁇ -type structure, a method of manufacturing a plurality of thermoelectric conversion modules having a ⁇ -type structure at the same time is desired. However, there is currently no such method. is there.
  • thermoelectric conversion module in the power generation by the thermoelectric conversion module, it is desirable to use the waste heat from the incinerator or industrial furnace as it is.
  • the heat resistance of the thermoelectric conversion module becomes a problem, and when the waste heat reaches about 600 ° C., it is difficult to generate power.
  • thermoelectric conversion module that can be used in a high temperature environment of about 600 ° C. requires improvement of heat resistance of p-type semiconductor elements and n-type semiconductor elements. Although development of a thermoelectric conversion module with high heat resistance is underway (see Patent Document 3), no thermoelectric conversion module having sufficient heat resistance and high power generation performance has been developed.
  • the present invention has been made to solve the above-described problems, and has as its object to provide a method for manufacturing a thermoelectric conversion module with high productivity, and a thermoelectric conversion that can be used in a high temperature environment and has high power generation performance. To provide a module.
  • thermoelectric conversion module n-type conductive metal oxide powder or p-type conductive metal oxide powder
  • the productivity of the thermoelectric conversion module is increased by joining the electrodes and the like by a specific method, and further, the power generation performance of the thermoelectric conversion module is improved by using the metal powder and the conductive metal oxide powder in combination. I also found a dramatic improvement.
  • thermoelectric conversion module can be used in a high temperature environment. It has also been found that this is possible, and further, it has also been found that the power generation performance of the thermoelectric conversion module is drastically improved by selecting the material constituting the thermoelectric conversion module.
  • the present invention has been made on the basis of such findings, and is specifically as follows.
  • thermoelectric conversion module comprising: an electrode that is independently joined to the other end of the type semiconductor element; and a metal powder and / or between the n type semiconductor element and the common electrode and the electrode An n-type conductive metal oxide powder is disposed, a metal powder and / or a p-type conductive metal oxide powder is disposed between the p-type semiconductor element and the common electrode, and the n-type semiconductor element.
  • thermoelectric conversion module of joining between the common electrode and the electrode and the p-type semiconductor element.
  • thermoelectric conversion module (2)
  • the metal powder and / or the n-type conductive metal oxide powder and the metal powder and / or the p-type conductive metal oxide powder are green compacts of the thermoelectric conversion module according to (1). Production method.
  • thermoelectric conversion module as described in (1) or (2) which arrange
  • the p-type semiconductor element is a sintered body mainly composed of a metal oxide different from the p-type conductive metal oxide used for joining the common electrode and the electrode, and the n-type semiconductor
  • the element is any one of (1) to (3) which is a sintered body containing magnesium silicide as a main component or containing magnesium silicide as a main component and containing at least one element selected from Sb and Al as a dopant.
  • the p-type semiconductor element applies a DC pulse current parallel to the pressing direction while uniaxially pressing a mixture of the metal oxide powder and the metal oxide plate crystal.
  • thermoelectric conversion module comprising a bonded body, a sintered body of a mixture of a metal and an n-type conductive metal oxide, or a sintered body of an n-type conductive metal oxide.
  • thermoelectric conversion module according to (6), wherein a joint between the common electrode and the electrode is formed of a sintered body of a mixture of a metal and an n-type conductive metal oxide.
  • the p-type semiconductor element is a sintered body whose main component is a metal oxide different from the p-type conductive metal oxide constituting the junction, and the n-type semiconductor element is mainly made of magnesium silicide.
  • thermoelectric conversion module according to (8), wherein the sintered body containing magnesium silicide as a main component includes a dopant.
  • thermoelectric conversion module according to (9), wherein the dopant is at least one element selected from Sb and Al.
  • the metal oxide constituting the p-type semiconductor element is selected from Na x CoO 2 , CaCo 2 O 4 , CuYO 2 , SrRuO 3 , and Sr 2 RuO 4 (8) to (10)
  • the thermoelectric conversion module of any one is selected from Na x CoO 2 , CaCo 2 O 4 , CuYO 2 , SrRuO 3 , and Sr 2 RuO 4 (8) to (10)
  • the p-type conductive metal oxide constituting the sintered body of the joint is selected from SrRuO 3 , ReO 3 , Cu 2 O and CuO, according to any one of (6) to (11) Thermoelectric conversion module.
  • the n-type conductive metal oxide constituting the sintered body of the joint is In 2 O 3 , SnO 2 , In 2 O 3 —SnO 2 , or Nb or La-doped SrTiO 3 , ZnO (6
  • the thermoelectric conversion module according to any one of (12) to (12).
  • thermoelectric conversion module of the present invention According to the method for manufacturing a thermoelectric conversion module of the present invention, a plurality of ⁇ -type thermoelectric conversion modules can be manufactured at a time. For this reason, compared with the manufacturing method of the conventional thermoelectric conversion module of the above-mentioned pi type structure, the manufacturing method of the thermoelectric conversion module of the present invention has high productivity.
  • thermoelectric conversion module having high power generation performance is obtained.
  • a conductive metal oxide is used in combination, the performance is dramatically improved.
  • thermoelectric conversion module of the present invention preferably uses a p-type semiconductor element and an n-type semiconductor element that have high heat resistance, and thus the obtained thermoelectric conversion module can be used in a high temperature environment.
  • thermoelectric conversion module of the present invention when a specific metal oxide is used as the p-type semiconductor element of the thermoelectric conversion module of the present invention, the power generation performance of the thermoelectric return module is greatly enhanced.
  • thermoelectric conversion module of Example 1 It is a figure which shows typically the thermoelectric conversion module manufactured with the method of this invention. It is a figure which shows the evaluation result of the electric power generation performance of the thermoelectric conversion module of Example 1.
  • FIG. It is a figure which shows the evaluation result of the electric power generation performance of the thermoelectric conversion module of Example 2.
  • FIG. It is a figure which shows the evaluation result of the electric power generation performance of the thermoelectric conversion module of Example 3.
  • FIG. It is a figure which shows the evaluation result of the electric power generation performance of the thermoelectric conversion module of Example 4.
  • FIG. It is a figure which shows the evaluation result of the electric power generation performance of the thermoelectric conversion module of Example 5.
  • FIG. It is a figure which shows the evaluation result of the electric power generation performance of the thermoelectric conversion module of Example 6.
  • FIG. 1 is a schematic diagram of a thermoelectric conversion module according to the present invention, in which an n-type semiconductor element 10, a p-type semiconductor element 11, a common electrode at which one end of an n-type semiconductor element and one end of a p-type semiconductor element are joined. 12 and an electrode 13 that is independently joined to the other end of the n-type semiconductor element and the other end of the p-type semiconductor element.
  • an n-type semiconductor element 10 a p-type semiconductor element 11
  • a common electrode at which one end of an n-type semiconductor element and one end of a p-type semiconductor element are joined.
  • 12 and an electrode 13 that is independently joined to the other end of the n-type semiconductor element and the other end of the p-type semiconductor element.
  • thermoelectric conversion module ⁇ N-type semiconductor element> It does not specifically limit as an n-type semiconductor element which comprises the thermoelectric conversion module of this invention, The conventionally well-known n-type semiconductor element used for a thermoelectric conversion module can be used.
  • magnesium silicide Mg 2 Si
  • WO2011 / 013609A1 it is preferable to use those disclosed in WO2011 / 013609A1.
  • Magnesium silicide shown in the international number WO2011 / 002035A1 has a melting point of 1358K, a linear expansion coefficient of 15.5 ⁇ 10 ⁇ 6 / K (293 ° C.), is thermally stable, and has high thermoelectric conversion efficiency.
  • magnesium silicide has a Young's modulus of about 120 GPa and has excellent rigidity.
  • Magnesium silicide can contain a dopant selected as necessary. Although it does not specifically limit as a dopant contained in magnesium silicide, For example, when Sb, Al, etc. are used, it is effective in reducing an electrical resistivity or improving durability.
  • the content of the dopant is not particularly limited, but is preferably 0.1 to 1% by mass. It is particularly preferable to use magnesium silicide containing Sb as a dopant as the n-type semiconductor element.
  • the method for producing magnesium silicide is not particularly limited, but, for example, the method described in the above-mentioned international publication proposed by the present inventors is preferable, and can be performed by the following procedure. First, using magnesium (Mg) and silicon (Si) as raw materials, both are mixed, melted and reacted to synthesize magnesium silicide, pulverized into powder, and then this powder is sintered to form n-type A desired magnesium silicide useful as a thermoelectric conversion element can be obtained.
  • Mg magnesium
  • Si silicon
  • magnesium silicide powder when magnesium silicide is synthesized using magnesium and silicon as raw materials, the synthesis temperature is higher than the melting point of magnesium silicide (1358 K) (for example, 1370 to 1400 K). A method of synthesizing the whole as a melt is preferred. This is because uniform magnesium silicide can be obtained.
  • the obtained magnesium silicide is pulverized to form magnesium silicide powder.
  • the average particle diameter of the magnesium silicide powder is not particularly limited, but is preferably adjusted to, for example, 25 to 100 ⁇ m.
  • a conventionally known method such as a hot press sintering method, a hot isostatic pressing method, or a discharge plasma sintering method can be employed.
  • a discharge plasma sintering method it is most preferable to employ a discharge plasma sintering method. This is because a dense sintered body can be obtained in a short time.
  • Discharge plasma sintering is a method of obtaining a sintered body by applying a DC pulse current in a direction parallel to the pressing direction while uniaxially pressing magnesium silicide powder.
  • spark plasma sintering can be performed by the following method using a conventionally known apparatus. First, a mold filled with a sample is set on a sintering stage in a chamber, sandwiched between graphite electrodes, and pulsed while conducting pressure. Next, the temperature of the sample is rapidly raised from room temperature to 700 to 2500 ° C. within a few minutes. Finally, the sample is held for several minutes at the temperature after the temperature rise to obtain a sintered body.
  • the rate of temperature rise affects the quality of magnesium silicide. It is preferable to set 600 ° C. or less at a temperature increase rate of 80 to 120 ° C./min, 600 to 700 ° C. at a temperature increase rate of 40 to 60 ° C./min, and 700 ° C. or more at a temperature increase rate of 20 to 40 ° C./min.
  • the other conditions are preferably set such that the pressure is 20 to 70 MPa, the temperature after the temperature rise is 700 to 900 ° C., and the holding time is 30 seconds to 15 minutes.
  • thermoelectric conversion module The p-type semiconductor element which comprises the thermoelectric conversion module of this invention is not specifically limited, The conventionally well-known p-type semiconductor used for a thermoelectric conversion module can be used. In particular, it is preferable to use a sintered body containing a metal oxide as a main component as a p-type semiconductor element.
  • the “main component” means that other components may be contained in the p-type semiconductor element as long as the effects of the present invention are not impaired.
  • the metal oxide examples include Na x CoO 2 , CaCo 2 O 4 , CuYO 2 , SrRuO 3 , and Sr 2 RuO 4 .
  • CuYO 2 may be doped with a divalent alkaline earth metal such as Ca, Mg, Sr, etc., or oxygen may be excessive to form CuYO 2 + x .
  • SrRuO 3 and Sr 2 RuO 4 Nb may be doped.
  • a p-type semiconductor element mainly containing SrRuO 3 is preferable. This is because the junction between the electrode and the p-type semiconductor element tends to be in ohmic contact.
  • metal oxide is excellent in heat resistance, it is preferable as a p-type semiconductor element used in a thermoelectric conversion module used in a high temperature environment.
  • the metal oxide sintered body can be manufactured by the following procedure. First, metal oxide powder is prepared using a metal organic compound or an inorganic compound as a raw material. The powder is then sintered.
  • the metal oxide powder can be prepared by a conventionally known method starting from a solution containing a metal element, such as a sol-gel method, a thermal decomposition method of a metal-organic complex, or a coprecipitation method.
  • the sol-gel method is a solution in which a starting material such as a metal organic compound or inorganic compound is dissolved in a solvent to cause a chemical reaction such as hydrolysis or polycondensation in the solution. This is a method of forming a sol solution in which oxide fine particles are dissolved.
  • a gelled product in which the sol solution is aggregated is formed.
  • the gelled product is heat-treated to remove the solvent remaining inside, an aggregate of metal oxide fine particles is obtained.
  • the aggregate is pulverized to obtain a metal oxide powder.
  • the method for sintering the metal oxide powder is not particularly limited, and examples thereof include a hot press sintering method, a hot isostatic pressing method, and a discharge plasma sintering method.
  • a hot press sintering method a hot press sintering method
  • a hot isostatic pressing method a hot isostatic pressing method
  • a discharge plasma sintering method it is most preferable to employ a discharge plasma sintering method. This is because a dense sintered body can be obtained in a short time.
  • some metal oxide crystals are anisotropic in electrical resistivity.
  • a metal oxide sintered body is manufactured by the following method.
  • a metal oxide powder is prepared using a conventionally known method such as a sol-gel method or a coprecipitation method.
  • a plate-like crystal is produced from the metal oxide powder using, for example, a flux method.
  • the flux refers to a solvent, and is a generic name for substances used as a solvent when a solute does not dissolve in water.
  • the flux method is a method for precipitating a single crystal by, for example, dissolving constituent elements using sodium, sodium chloride, lithium chloride or the like as a flux (flux) and controlling the temperature and pressure.
  • a DC pulse current is applied in a direction parallel to the pressing direction while a mixture of the metal oxide powder and the plate crystal of the metal oxide is uniaxially pressed to obtain a sintered body.
  • structural anisotropy is imparted to the sintered body by the TGG method (Tampled Grain Growth method).
  • TGG method stampled Grain Growth method
  • plate-like crystals with high structural anisotropy are embedded in polycrystalline particles, aligned so that the plate-like crystals are aligned by uniaxial pressing, and heat treatment is performed, whereby the powder becomes plate-like crystals.
  • An oriented sintered body can be obtained by applying a DC pulse current in a direction parallel to the pressing direction.
  • Examples of the oriented sintered body include Na x CoO 2 used in Examples.
  • the p-type semiconductor element fabricated as described above exhibits the same electrical resistivity as that of a metal and the same level of thermoelectromotive force as that of a semiconductor.
  • this p-type semiconductor element exhibits a very high thermoelectromotive force among materials exhibiting a low electrical resistivity equivalent to that of metal, and thus is preferable as a p-type semiconductor element used for a thermoelectric conversion module.
  • the common electrode and the electrode are metal materials.
  • a metal material what is used as an electrode of a general thermoelectric conversion module can be used.
  • transition metal materials such as nickel (Ni), titanium (Ti), copper (Cu), aluminum (Al), and iron (Fe) are exemplified.
  • nickel (Ni) is preferable because it has a high melting point of 1728 K and is excellent in heat resistance.
  • the common electrode and the electrode may be the same type of metal or different types of metals.
  • thermoelectric conversion module In the method for producing a thermoelectric conversion module of the present invention, a metal powder and / or a conductive metal oxide powder (in this specification, a metal powder and / or a conductive metal oxide powder is used between a semiconductor element and an electrode, etc. Sintered by applying a DC pulse current in a direction parallel to the direction in which the pressure is applied, while applying pressure in the direction in which the semiconductor element is sandwiched between electrodes. The semiconductor element is bonded to the electrode or the like. The use of the powder in this manner and the sintering of the powder together can bring about an effect of forming a tightly bonded state with the electrode.
  • the “conductivity” of the conductive metal oxide powder means that the conductivity measured by a four-terminal method is 10 3 S / cm or more using the conductive metal oxide powder as a dense sintered body.
  • the metal constituting the metal powder disposed between the semiconductor element and the electrode has a low electric resistance and is the same metal as the metal constituting the common electrode and / or the electrode, or has an ohmic contact with the semiconductor element. It is necessary to form.
  • the resistance value of the metal powder is preferably 10 ⁇ 6 ⁇ cm or less.
  • the metal constituting the metal powder include transition metal materials such as nickel, titanium (Ti), copper (Cu), aluminum (Al), and iron (Fe).
  • the metal species of the metal powder and the metal species used for the electrode or the like may be the same or different, but are preferably the same.
  • the p-type conductive metal oxide constituting the p-type conductive metal oxide powder disposed between the p-type semiconductor element and the electrode or the like forms an ohmic contact with the common electrode and the electrode.
  • it means a substance whose temperature characteristic of electrical conduction shows metallic behavior.
  • the conductive metal oxide is p-type and exhibits high electrical conductivity, and must be different from the metal oxide constituting the semiconductor.
  • the reason is that since the p-type semiconductor element and the metal cannot form an ohmic contact, the semiconductor element and the electrode are joined via a sintered body made of a conductive metal oxide exhibiting a metallic electric conduction behavior. This is because the resistance at the bonding interface can be reduced. In addition, when the junction between the semiconductor element and the metal is in ohmic contact, the resistance at the junction interface is reduced even when only the metal powder is used.
  • the p-type conductive metal oxide that can be used is not particularly limited, and is appropriately changed according to the type of p-type semiconductor, the type of metal used as a common electrode or an electrode.
  • SrRuO 3 , ReO 3 , Cu 2 O, and CuO can be mentioned.
  • the n-type conductive metal oxide constituting the n-type conductive metal oxide powder disposed between the n-type semiconductor element and the electrode forms an ohmic contact with the common electrode and the electrode.
  • it means a substance whose temperature characteristic of electrical conduction shows metallic behavior.
  • the conductive metal oxide is n-type and exhibits high electrical conductivity, and it is necessary to use a material different from the material constituting the n-type semiconductor. The reason is the same as in the case of a p-type semiconductor.
  • the n-type conductive metal oxide that can be used is not particularly limited, and is appropriately changed depending on the type of the n-type semiconductor, the type of metal used as the common electrode or the electrode.
  • the n-type semiconductor In 2 O 3 , SnO 2 , In 2 O 3 —SnO 2 , or Nb or La-doped SrTiO 3 , ZnO can be used. This is because the junction between the electrode and the n-type semiconductor element tends to be in ohmic contact.
  • the particle size of the metal powder and conductive metal oxide powder affects the density of the sintered body.
  • the particle diameter is not particularly limited as long as a sintered body dense to a desired level can be obtained, but is preferably 20 ⁇ m or less, more preferably 3 ⁇ m or less, and nanoparticles can also be used. .
  • the metal powder is preferably used as a green compact.
  • the green compact refers to a metal powder or the like that is pressed and hardened.
  • the green compact can be produced, for example, by compacting. By sandwiching the green compact between the electrode or the like and the semiconductor element, and sintering and densifying using the discharge plasma method, it becomes easy to join the electrode or the like and the semiconductor element.
  • Adhesion between a sintered body of metal powder or green compact and an electrode or the like easily proceeds because both are metal materials.
  • the adhesion between the sintered body of metal powder or the like or the green compact and the semiconductor element is presumed to proceed by the interaction of the oxide film on the particle surface of the metal powder or the like with the surface of the semiconductor element.
  • the sintered body becomes a part of the electrode.
  • a nickel (Ni) plate is used as an electrode or the like and nickel powder is used as a metal powder
  • the bulk of nickel is formed by sintering, and the sintered body is integrated with the nickel plate.
  • the sintered body of the mixed powder becomes a composite electrode of metal and conductive metal oxide, and a module as an electrode between the electrode and the semiconductor element Part of
  • thermoelectric conversion module of this invention has high productivity.
  • the p-type semiconductor element and the n-type semiconductor element are thermally expanded by heating with the discharge plasma for the above-described bonding. If the thermal expansion coefficient of the p-type semiconductor element and the thermal expansion coefficient of the n-type semiconductor element are different, it is assumed that the semiconductor element that is likely to expand is damaged. However, in the manufacturing method of the present invention, metal powder or the like or the green compact plays a role as a buffer material, and thus is caused by the difference between the thermal expansion coefficient of the p-type semiconductor element and the thermal expansion coefficient of the n-type semiconductor element. Damage to the semiconductor element can be suppressed.
  • p-type conductive metal oxide powder When a sintered body containing a metal oxide as a main component is used as the p-type semiconductor element, the junction between the electrode and the p-type semiconductor element tends not to be in ohmic contact. Therefore, p-type conductive metal oxide powder, or a mixture of metal powder and p-type conductive metal oxide powder can be used so that the junction between the electrode and the p-type semiconductor element is in ohmic contact.
  • the same effect can be obtained by using a green compact formed by compacting a p-type conductive metal oxide powder or a mixture of a metal powder and a p-type conductive metal oxide powder. The same applies to the n-type semiconductor element and the n-type conductive metal oxide.
  • the volume ratio of the metal powder to the p-type conductive metal oxide powder is preferably 3/7 to 9/1. If the volume ratio is 3/7 or more, it is preferable because the degree of sintering of the mixture is increased and the thermoelectric element and the electrode can be joined. If it is 9/1 or less, ohmic contact can be easily obtained. This is preferable. A more preferable range of the volume ratio is 5/5 to 7/3. The same applies to the metal powder and the n-type conductive metal oxide.
  • thermoelectric conversion module of the present invention can be manufactured.
  • thermoelectric conversion module of the present invention is made of a material having excellent heat resistance for both the p-type semiconductor element and the n-type semiconductor element. Therefore, the thermoelectric conversion module of the present invention can be used even in a high temperature environment of about 600 ° C. Moreover, both the p-type semiconductor element and the n-type semiconductor element used in the thermoelectric conversion module of the present invention have high performance as a thermoelectric conversion material.
  • the metal oxide used for the production of the p-type semiconductor element is preferably one selected from Na x CoO 2 , CaCo 2 O 4 , CuYO 2 , SrRuO 3 , and Sr 2 RuO 4 .
  • CuYO 2 is preferably doped with a divalent alkaline earth metal such as Ca, Mg, Sr, etc., and is preferably made into CuYO 2 + x by excess oxygen.
  • SrRuO 3 and Sr 2 RuO 4 are preferably doped with Nb.
  • the dopant contained in magnesium silicide is preferably at least one element selected from Sb and Al.
  • thermoelectric conversion module of this invention may be manufactured by methods other than the manufacturing method of the above-mentioned this invention.
  • the production by the method of the present invention is preferable from the following points.
  • conventional methods using paste and solder often do not allow these materials to withstand use at high temperatures, but use metal powders or conductive metal oxide powders. Therefore, there is almost no problem of heat resistance such as paste and solder.
  • ⁇ Manufacture of n-type semiconductor elements Magnesium silicide containing 0.5% by mass of Sb as a dopant (Union Material Co., Ltd., using Example 5 of WO2011 / 002035) is pulverized in an alumina mortar and using a 75 ⁇ m sieve made by Tokyo Screen Co., Ltd. Classification was performed to obtain a raw material powder.
  • the raw material powder was sintered using a discharge plasma sintering apparatus (Dr. Sinter LabSPS-515, manufactured by Sumitomo Coal Mining Co., Ltd.). Sintering conditions are as follows.
  • Raw material powder is filled in a graphite mold, pre-pressurization shown in Table 1 is applied, electricity is applied while performing uniaxial pressure molding, and raw material powder is shown in Table 1 at a temperature increase rate shown in Table 1.
  • the sintered body was manufactured by heating to the holding temperature and heat treatment at the holding temperature shown in Table 1 for the holding time.
  • the appearance of the sintered body of Condition 1 to the sintered body of Condition 6 was visually observed. It was confirmed that the sintered body of condition 1 was cracked, and the sintered bodies of condition 2 to condition 3 were cracked on the surface. The density of the sintered bodies of Condition 4 to Condition 6 in which no cracks were confirmed on the surface was measured. The density of the sintered body under condition 4 was 94.5%, the density of the sintered body under condition 5 was 97.2%, and the density of the sintered body under condition 6 was 99.7%. It was confirmed that the sintered body of Condition 6 was the most dense.
  • the optimum sintering condition was determined, and an n-type semiconductor element used for manufacturing the thermoelectric conversion module was obtained under this condition.
  • the preliminary pressurizing force is 50 MPa
  • the holding temperature is 800 ° C.
  • the holding time is 1 minute
  • the temperature rising rate is 0 to 600 ° C. in the range of 100 ° C./min
  • the temperature in the range of 600 to 700 ° C. is 50 ° C. / Min
  • the range of 700-800 ° C. is 30 ° C./min.
  • a sample of 5.4 mm (length) ⁇ 10.5 mm (width) ⁇ 8.5 mm (height) was cut out from the sintered body and used.
  • a part of the precursor was taken out and mixed with NaCl and KCl at a weight ratio of 2: 1: 1 (precursor: NaCl: KCl).
  • This mixture was placed in a crucible as a sample, sealed with Aron ceramics and allowed to stand for a day, and then heat treated to cure the Aron ceramics.
  • Temperature conditions temperature rise to 100 ° C in 75 minutes, hold for 2 hours, heat up to 200 ° C in 50 minutes, hold for 2 hours, heat up to 300 ° C in 20 minutes, hold for 1 hour, cool to room temperature in 60 minutes It was.
  • heat treatment for producing plate crystals was performed. As heat treatment conditions, the temperature was raised to 1100 ° C. in 100 minutes, held for 12 minutes, slowly cooled to 700 ° C.
  • a graphite mold is filled with a precursor of Na x CoO 2 sample and a plate-like crystal, a pre-pressurizing pressure of 50 MPa is applied, energized while performing uniaxial pressing, and the temperature is raised to 700 ° C. in 7 minutes. The temperature was raised to ⁇ 850 ° C. in 3 minutes and heated at this temperature for 10 minutes to produce a sintered body.
  • This sintered body was used as a p-type semiconductor element for manufacturing the following thermoelectric conversion module. Specifically, a 4.5 mm (vertical) ⁇ 9.5 mm (horizontal) ⁇ 8.5 mm (height) sample was cut out from the sintered body and used.
  • Example 1 0.5 g of nickel metal powder (2 to 3 ⁇ m, purity 99.9%) is filled into a cylindrical mold having an inner diameter of 20 mm and a height of 40 mm, and a green compact is produced under a pressure of 30 MPa. Cut out to ⁇ 5 mm ⁇ 0.5 mm. Moreover, the nickel plate was used as a common electrode and an electrode. Using the green compact, nickel plate, n-type semiconductor element, and p-type semiconductor element, the thermoelectric conversion module of Example 1 was manufactured by the following method.
  • the green compacts were respectively arranged on the upper surfaces of the two nickel plates.
  • an n-type semiconductor element is arranged so that the surface of 5.4 mm (vertical) ⁇ 10.5 mm (horizontal) is in contact with one green compact, and 4.5 mm (vertical) ⁇ on the other green compact.
  • the p-type semiconductor element was arranged so that the surface of 9.5 mm (horizontal) was in contact.
  • the green compacts were respectively disposed on the back surfaces of the surfaces where the green compacts contact the n-type and p-type semiconductor elements.
  • One nickel plate serving as a common electrode was placed on these green compacts so that the bottom surface of the nickel plate was in contact with the green compact.
  • thermoelectric conversion module was manufactured by processing.
  • thermoelectric property evaluation apparatus manufactured by ULVAC-RIKO. Specifically, a thermocouple was installed on the nickel plate, and the surface temperature on the high temperature side and the surface temperature on the low temperature side were measured. Then, a constant current was applied between the nickel plates of the thermoelectric conversion module, and the voltage drop was measured. Finally, power was calculated from the voltage drop and constant current. The measurement conditions and results are shown in Table 2 and FIG. Note that the surface temperature on the low temperature side is all 100 ° C.
  • thermoelectric conversion module of the present invention can be used in an environment of about 200 to 600 ° C. Further, the thermoelectric conversion module of the present invention has a power generation performance of 6.645 mW under a temperature difference of 500 ° C. Therefore, it was confirmed that the power generation performance is equivalent to a general thermoelectric conversion module. .
  • the SrRuO 3 powder mixed with the nickel metal powder is a p-type conductive metal having a particle size of 10 ⁇ m or less by further heat-treating the SrRuO 3 precursor powder in an atmospheric furnace at 1000 ° C. for 5 hours. An oxide powder was obtained.
  • the thermoelectric conversion module of Example 3 was manufactured.
  • the thermoelectric conversion module of Example 3 was manufactured.
  • thermoelectric conversion module of Example 1 When the power generation performance of the thermoelectric conversion module of Example 1 is compared with the power generation performance of the thermoelectric conversion modules of Examples 2 to 4, metal powder and p-type are used as powders for joining the electrode and the p-type semiconductor element. It was confirmed that the power generation performance of the thermoelectric conversion module was improved by using the mixture with the conductive metal oxide powder.
  • the magnesium silicide used in the examples has a small resistance at the bonding interface even when bonded to the metal electrode, even if n-type conductive metal oxide powder is not used, the power generation performance is not greatly reduced. .
  • the resistance of the bonding interface increases in the bonding between the n-type semiconductor element and the metal electrode, the resistance of the bonding interface can be reduced by using the n-type conductive metal oxide powder. Conceivable.
  • thermoelectric conversion modules of Examples 2 to 4 From Table 1 and Tables 2 to 4, it was confirmed that there was almost no difference in voltage drop between the thermoelectric conversion modules of Examples 2 to 4 and the thermoelectric conversion module of Example 1. On the other hand, regarding the current value, it was confirmed that the current flowing through the thermoelectric conversion modules of Examples 2 to 4 was very high compared to the current flowing through the thermoelectric conversion module of Example 1. From these results, it can be confirmed that the thermoelectric conversion modules of Examples 2 to 4 have very low resistance at the interface between the electrode and the like and the semiconductor element as compared with the thermoelectric conversion module of Example 1.
  • thermoelectric conversion module of Example 5 was manufactured in the same manner as the thermoelectric conversion module of Example 1 except that a SrRuO 3 sintered body was used as the p-type semiconductor element. Specifically, a heat-treated sintered body of SrRuO 3 was manufactured by the following method, and 4.5 mm (length) ⁇ 9.5 mm (width) ⁇ 7.5 mm (height) from the sintered body. 1) was used as a p-type semiconductor element.
  • the graphite mold is filled with the above-mentioned precursor of SrRuO 3 sample, a pre-pressurizing force of 50 MPa is applied, energized while performing uniaxial pressing, and the temperature is raised to 1100 ° C. in 11 minutes, and this temperature is increased for 4 minutes.
  • a sintered body was produced by heating. This sintered body was heat-treated in the atmosphere under the conditions of a processing temperature of 1300 ° C. and a processing time of 12 hours to obtain a SrRuO 3 sintered body.
  • thermoelectric conversion module of Example 5 was evaluated in the same manner as the power generation performance of the thermoelectric conversion module of Example 1.
  • the measurement conditions and evaluation results of Example 5 are shown in Table 6 and FIG. Note that the surface temperature on the low temperature side is all 100 ° C.
  • the power generation of the thermoelectric conversion module can be achieved by changing the type of metal oxide constituting the p-type semiconductor element. It was confirmed that the performance was greatly improved.
  • thermoelectric conversion module of Example 6 was produced in the same manner as in Example 5 except that Nb was added when producing the starting solution so that Nb in the starting solution was 5 mol%.
  • thermoelectric conversion module of Example 6 was evaluated in the same manner as the power generation performance of the thermoelectric conversion module of Example 1.
  • the measurement conditions and evaluation results of Example 6 are shown in Table 7 and FIG. Note that the surface temperature on the low temperature side is all 100 ° C.
  • thermoelectric conversion module of Example 6 When comparing the power generation performance of the thermoelectric conversion module of Example 6 with the power generation performance of the thermoelectric conversion module of Example 5, the metal oxide constituting the p-type semiconductor element is changed to a metal oxide containing a dopant. It was confirmed that the power generation performance of the thermoelectric conversion module was improved.

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Abstract

L'invention concerne un procédé de fabrication d'un module de conversion thermoélectrique avec une productivité élevée, ainsi qu'un module de conversion thermoélectrique qui peut être utilisé dans des environnements à haute température et qui présente des performances élevées de génération d'énergie. L'invention concerne un procédé de fabrication d'un module de conversion thermoélectrique comprenant un élément semi-conducteur de type n, un élément semi-conducteur de type p, une électrode commune à laquelle une extrémité de l'élément semi-conducteur de type n et une extrémité de l'élément semi-conducteur de type p sont connectées, et une électrode à laquelle l'autre extrémité de l'élément semi-conducteur de type n et l'autre extrémité de l'élément semi-conducteur de type p sont connectées indépendamment, une poudre métallique et/ou une poudre d'oxyde métallique électroconducteur (une poudre d'oxyde métallique électroconducteur de type n ou une poudre d'oxyde métallique électroconducteur de type p) étant disposées entre l'élément semi-conducteur et les électrodes et similaires, et l'élément semi-conducteur et les électrodes et similaires étant interconnectés d'une manière spécifique. Un matériau fritté contenant un oxyde métallique en tant que composant principal est utilisé comme élément semi-conducteur de type p et un matériau fritté contenant du siliciure de magnésium en tant que composant principal est utilisé comme élément semi-conducteur de type n.
PCT/JP2011/055075 2010-05-28 2011-03-04 Procédé de fabrication d'un module de conversion thermoélectrique, et module de conversion thermoélectrique WO2011148686A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104465980A (zh) * 2014-11-17 2015-03-25 陕西师范大学 基于铝/纳晶硅/铜薄膜的热电材料及其制备方法
CN104505457A (zh) * 2014-12-08 2015-04-08 陕西师范大学 基于Al/CuO薄膜的热电材料及其制备方法
JP2017528905A (ja) * 2014-07-17 2017-09-28 エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ 熱電素子用の材料および熱電素子用の材料の製造方法
US11165007B2 (en) 2019-01-25 2021-11-02 King Abdulaziz University Thermoelectric module composed of SnO and SnO2 nanostructures
US20220077372A1 (en) * 2012-02-07 2022-03-10 Ethan James Ciccotelli Method and device for the generation of electricity directly from heat
US11637230B2 (en) 2018-06-28 2023-04-25 Nihon Parkerizing Co., Ltd. Thermoelectric conversion element and thermoelectric conversion module having same

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06268264A (ja) * 1993-03-10 1994-09-22 Idemitsu Petrochem Co Ltd ペルチェ素子の製造方法
JPH1074986A (ja) * 1996-06-27 1998-03-17 Natl Aerospace Lab 熱電変換素子、π型熱電変換素子対および熱電変換モジュールの各製造方法
JPH11177156A (ja) * 1997-12-16 1999-07-02 Natl Aerospace Lab 熱電変換材料の加工法と熱電変換素子の製造方法
JP2005276952A (ja) * 2004-03-23 2005-10-06 Japan Science & Technology Agency 二次元酸化物自然超格子を用いた熱電材料とその熱電特性の調整方法
JP2006351754A (ja) * 2005-06-15 2006-12-28 Ricoh Co Ltd 熱電変換材料およびそれを用いた熱電変換装置
WO2008075789A1 (fr) * 2006-12-20 2008-06-26 Showa Kde Co., Ltd. Matériaux de conversion thermoélectrique, leur procédé de production, et élément de conversion thermoélectrique
JP2008306127A (ja) * 2007-06-11 2008-12-18 National Institute For Materials Science 熱電変換材料
JP2009117792A (ja) * 2007-10-19 2009-05-28 Ube Ind Ltd 熱電変換モジュール及びその製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3462462B2 (ja) * 2000-10-11 2003-11-05 独立行政法人産業技術総合研究所 放電プラズマ焼結法により製造した酸化物熱電素子
JP2003332644A (ja) * 2002-05-16 2003-11-21 Komatsu Ltd 熱電モジュール製造方法および熱電モジュール製造用治具
JP4446064B2 (ja) * 2004-07-07 2010-04-07 独立行政法人産業技術総合研究所 熱電変換素子及び熱電変換モジュール
JP2009071252A (ja) * 2007-09-18 2009-04-02 Fuji Electric Device Technology Co Ltd 半導体装置およびその製造方法
JP2009302332A (ja) * 2008-06-13 2009-12-24 Aruze Corp 熱電変換素子及び熱電変換素子用導電性部材

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06268264A (ja) * 1993-03-10 1994-09-22 Idemitsu Petrochem Co Ltd ペルチェ素子の製造方法
JPH1074986A (ja) * 1996-06-27 1998-03-17 Natl Aerospace Lab 熱電変換素子、π型熱電変換素子対および熱電変換モジュールの各製造方法
JPH11177156A (ja) * 1997-12-16 1999-07-02 Natl Aerospace Lab 熱電変換材料の加工法と熱電変換素子の製造方法
JP2005276952A (ja) * 2004-03-23 2005-10-06 Japan Science & Technology Agency 二次元酸化物自然超格子を用いた熱電材料とその熱電特性の調整方法
JP2006351754A (ja) * 2005-06-15 2006-12-28 Ricoh Co Ltd 熱電変換材料およびそれを用いた熱電変換装置
WO2008075789A1 (fr) * 2006-12-20 2008-06-26 Showa Kde Co., Ltd. Matériaux de conversion thermoélectrique, leur procédé de production, et élément de conversion thermoélectrique
JP2008306127A (ja) * 2007-06-11 2008-12-18 National Institute For Materials Science 熱電変換材料
JP2009117792A (ja) * 2007-10-19 2009-05-28 Ube Ind Ltd 熱電変換モジュール及びその製造方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220077372A1 (en) * 2012-02-07 2022-03-10 Ethan James Ciccotelli Method and device for the generation of electricity directly from heat
JP2017528905A (ja) * 2014-07-17 2017-09-28 エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ 熱電素子用の材料および熱電素子用の材料の製造方法
CN104465980A (zh) * 2014-11-17 2015-03-25 陕西师范大学 基于铝/纳晶硅/铜薄膜的热电材料及其制备方法
CN104505457A (zh) * 2014-12-08 2015-04-08 陕西师范大学 基于Al/CuO薄膜的热电材料及其制备方法
CN104505457B (zh) * 2014-12-08 2017-07-11 陕西师范大学 基于Al/CuO薄膜的热电材料及其制备方法
US11637230B2 (en) 2018-06-28 2023-04-25 Nihon Parkerizing Co., Ltd. Thermoelectric conversion element and thermoelectric conversion module having same
US11165007B2 (en) 2019-01-25 2021-11-02 King Abdulaziz University Thermoelectric module composed of SnO and SnO2 nanostructures
US11309475B2 (en) 2019-01-25 2022-04-19 King Abdulaziz University Tin oxide-based thermoelectric device

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