WO2020203612A1 - Couche de matériau thermoélectrique et son procédé de production - Google Patents

Couche de matériau thermoélectrique et son procédé de production Download PDF

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WO2020203612A1
WO2020203612A1 PCT/JP2020/013552 JP2020013552W WO2020203612A1 WO 2020203612 A1 WO2020203612 A1 WO 2020203612A1 JP 2020013552 W JP2020013552 W JP 2020013552W WO 2020203612 A1 WO2020203612 A1 WO 2020203612A1
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Prior art keywords
material layer
conversion material
thermoelectric conversion
thermoelectric
thermoelectric semiconductor
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PCT/JP2020/013552
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English (en)
Japanese (ja)
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佑太 関
昌也 戸▲高▼
邦久 加藤
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リンテック株式会社
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Priority to CN202080024639.7A priority Critical patent/CN113632252A/zh
Priority to JP2021511900A priority patent/JPWO2020203612A1/ja
Publication of WO2020203612A1 publication Critical patent/WO2020203612A1/fr

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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
    • 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
    • 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
    • H10N10/856—Thermoelectric active materials comprising organic compositions
    • 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
    • H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material

Definitions

  • the present invention relates to a thermoelectric conversion material layer and a method for producing the same.
  • thermoelectric conversion module having a thermoelectric effect such as the Seebeck effect and the Peltier effect.
  • thermoelectric conversion module the use of a so-called ⁇ -type thermoelectric conversion element is known.
  • a pair of electrodes separated from each other are provided on the substrate, for example, a P-type thermoelectric element is provided on the-one electrode and an N-type thermoelectric element is provided on the other electrode, also separated from each other.
  • It is configured by connecting the top surfaces of both thermoelectric materials to the electrodes of the opposing substrates.
  • in-plane type thermoelectric conversion element is known.
  • thermoelectric elements and N-type thermoelectric elements are alternately provided in the in-plane direction of the substrate.
  • the lower part of the joint between the two thermoelectric elements is connected in series via electrodes.
  • a resin substrate such as polyimide is used from the viewpoint of heat resistance and flexibility.
  • thermoelectric semiconductor material As the N-type thermoelectric semiconductor material and the P-type thermoelectric semiconductor material, a bismasterlide-based material is used from the viewpoint of thermoelectric performance, and for example, a resin and a thermoelectric semiconductor material are included from the viewpoint of flexibility and thinning.
  • the thermoelectric semiconductor composition is formed in the form of a coating film by using a screen printing method or the like. (Patent Document 1 etc.).
  • thermoelectric semiconductor material used for the thermoelectric conversion module is formed as a thermoelectric conversion material layer in the form of a coating film from a thermoelectric semiconductor composition containing a resin, a thermoelectric semiconductor material, etc.
  • the obtained thermoelectric conversion material layer is not available. , High electrical conductivity could not be obtained sufficiently, and thermoelectric performance was not sufficient.
  • the present invention provides a thermoelectric conversion material layer having high thermoelectric performance and a method for producing the same, in which the electric conductivity of the thermoelectric conversion material in the thermoelectric conversion material layer composed of a coating film of a thermoelectric semiconductor composition is improved. That is the issue.
  • thermoelectric conversion material layer composed of a coating film of a thermoelectric semiconductor composition, wherein the thermoelectric conversion material layer has voids, and the thermoelectric semiconductor composition in a vertical cross-sectional area including a central portion of the thermoelectric conversion material layer.
  • thermoelectric conversion material layer having a filling rate of 0.800 or more and less than 1.000, where the filling rate is taken as a proportion of the area of an object.
  • the thermoelectric semiconductor composition contains a thermoelectric semiconductor material, and the thermoelectric semiconductor material is a bismuth-tellu-based thermoelectric semiconductor material, a telluride-based thermoelectric semiconductor material, an antimony-tellu-based thermoelectric semiconductor material, or a bismuth selenide-based thermoelectric semiconductor material.
  • thermoelectric conversion material layer according to (1) or (2) above, wherein the thermoelectric semiconductor composition further contains a heat-resistant resin.
  • the thermoelectric semiconductor composition further contains an ionic liquid and / or an inorganic ionic compound.
  • the filling rate is 0.850 to 0.999.
  • thermoelectric conversion material layer composed of a coating film of a thermoelectric semiconductor composition, wherein (A) a step of forming a thermoelectric conversion material layer, and (B) the step obtained in the step (A). The step of drying the thermoelectric conversion material layer, (C) the step of pressurizing the thermoelectric conversion material layer after drying obtained in the step (B), and (D) the addition obtained in the step (C).
  • a method for producing a thermoelectric conversion material layer which comprises a step of annealing a compressed thermoelectric conversion material layer. (9) The method for producing a thermoelectric conversion material layer according to (8) above, wherein the annealing treatment is performed at a temperature of 250 to 600 ° C. (10) The method for producing a thermoelectric conversion material layer according to (8) or (9) above, wherein the pressurization is performed at 1.0 to 60 MPa.
  • thermoelectric conversion material layer having high thermoelectric performance and a method for producing the same, in which the electric conductivity of the thermoelectric conversion material in the thermoelectric conversion material layer composed of a coating film of a thermoelectric semiconductor composition is improved. it can.
  • thermoelectric conversion material layer of this invention It is a figure for demonstrating the definition of the longitudinal section of the thermoelectric conversion material layer of this invention. It is sectional drawing for demonstrating the vertical cross section of the thermoelectric conversion element layer obtained in the Example or the comparative example of this invention. It is explanatory drawing which shows an example of the manufacturing method of the thermoelectric conversion material layer of this invention in process order.
  • thermoelectric conversion material layer of the present invention is a thermoelectric conversion material layer made of a coating film of a thermoelectric semiconductor composition, and the thermoelectric conversion material layer has voids and has a vertical cross section including a central portion of the thermoelectric conversion material layer.
  • the filling rate is 0.800 or more and less than 1.000.
  • FIG. 1 is a diagram for explaining the definition of a vertical cross section of the thermoelectric conversion material layer of the present invention
  • FIG. 1A is a plan view of the thermoelectric conversion material layer 2
  • the thermoelectric conversion material layer 2 is in the width direction.
  • thermoelectric conversion material layer 2 has a length X and a length Y in the depth direction
  • (b) is a vertical cross section of the thermoelectric conversion material layer 2 including the voids 3 formed on the substrate 1a, and the vertical cross section is the above-mentioned ( It includes the central portion C of a), and is composed of a length X and a thickness D obtained when cutting between A and A'in the width direction (rectangular in the figure).
  • FIG. 2 is a schematic cross-sectional view for explaining a vertical cross section of the thermoelectric conversion material layer of the example or comparative example of the present invention, and FIG. 2A is formed on the alumina substrate 1b obtained in Comparative Example 1. It is a vertical cross section of the thermoelectric conversion material layer 2s, and the thermoelectric conversion material layer 2s has a vertical cross section consisting of a curve having a length X in the width direction and Dmin and Dmax values in the thickness direction. The upper part of the is provided with a concave portion and a convex portion, and a gap portion 3b exists in the vertical cross section.
  • (b) is a vertical cross section of the thermoelectric conversion material layer 2t formed on the alumina substrate 1b obtained in Example 1, and the vertical cross section of the thermoelectric conversion material layer 2t has a length X in the width direction.
  • the thickness in the thickness direction is D [when the values of Dmin and Dmax in (a) of FIG. 2 are small], the upper part of the vertical cross section is substantially linear, and there are voids in the vertical cross section. There are voids 4b in which the number and volume are suppressed.
  • Dmin means the minimum value of the thickness in the thickness direction of the vertical cross section
  • Dmax means the maximum value of the thickness in the thickness direction of the vertical cross section.
  • thermoelectric semiconductor composition in the thermoelectric conversion material layer is defined by the ratio of the area of the thermoelectric semiconductor composition to the area of the longitudinal section including the central portion of the thermoelectric conversion material layer.
  • the filling rate of is 0.800 or more and less than 1.000, and there are few voids in the thermoelectric conversion material layer.
  • the filling rate of the thermoelectric semiconductor composition in the thermoelectric conversion material layer is less than 0.800, the number of voids in the thermoelectric conversion material layer increases, it becomes difficult to obtain excellent electric conductivity, and high thermoelectric performance can be obtained. I can't.
  • the filling rate is preferably 0.810 to 0.999, more preferably 0.850 to 0.999, still more preferably 0.900 to 0.999, and particularly preferably 0.950 to 0.999. When the rate is in this range, excellent electrical conductivity is obtained, and the thermoelectric conversion material layer has high thermoelectric performance.
  • thermoelectric conversion material layer of the present invention (hereinafter, may be referred to as “thin film composed of a thermoelectric conversion material layer”) is made of a coating film of a thermoelectric semiconductor composition.
  • the thermoelectric semiconductor composition preferably contains a thermoelectric semiconductor material and a heat-resistant resin from the viewpoint of shape stability of the thermoelectric conversion material layer, and from the viewpoint of thermoelectric performance, the thermoelectric semiconductor material, the heat-resistant resin, and an ionic liquid and / Or more preferably it consists of a thermoelectric semiconductor composition containing an inorganic ionic compound.
  • the thermoelectric semiconductor material is preferably used as thermoelectric semiconductor particles (hereinafter, the thermoelectric semiconductor material may be referred to as "thermoelectric semiconductor particles").
  • the thickness of the thermoelectric conversion material layer is not particularly limited, but is preferably 1 nm to 1000 ⁇ m, more preferably 3 to 600 ⁇ m, and further preferably 5 to 400 ⁇ m from the viewpoint of flexibility, thermoelectric performance, and film strength.
  • thermoelectric semiconductor material used in the present invention is not particularly limited as long as it is a material capable of generating thermoelectromotive force by applying a temperature difference.
  • bismuth such as P-type bismasterlide and N-type bismasterlide.
  • Tellur-based thermoelectric semiconductor material Telluride-based thermoelectric semiconductor material such as GeTe, PbTe; Antimon-Teruru-based thermoelectric semiconductor material; Zinc-antimon-based thermoelectric semiconductor material such as ZnSb, Zn 3 Sb 2, Zn 4 Sb 3 ; Silicon such as SiGe -Germanium-based thermoelectric semiconductor material; Bismus selenide-based thermoelectric semiconductor material such as Bi 2 Se 3 ; VDD-based thermoelectric semiconductor material such as ⁇ -FeSi 2 , CrSi 2 , MnSi 1.73 , Mg 2 Si; Oxide-based thermoelectric semiconductor Materials: Whistler materials such as FeVAl, FeVALSi, and FeVTiAl, sulfide-based thermoelectric semiconductor materials such as TiS 2 , and the like are used. Among these, bismuth-tellu-based thermoelectric semiconductor materials, telluride-based thermoelectric semiconductor materials, antimony-tellu-based thermoelectric semiconductor materials, or bismuth selenide-based thermoelectric
  • a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuthellide or N-type bismuthellide is more preferable.
  • P-type bismuth telluride those having holes as carriers and a positive Seebeck coefficient, for example, represented by Bi X Te 3 Sb 2-X , are preferably used.
  • X is preferably 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • the Seebeck coefficient and the electric conductivity become large, and the characteristics as a P-type thermoelectric element are maintained, which is preferable.
  • N-type bismuth telluride one having an electron carrier and a negative Seebeck coefficient, for example, represented by Bi 2 Te 3-Y Se Y is preferably used.
  • the Seebeck coefficient and the electric conductivity become large, and the characteristics as an N-type thermoelectric element are maintained, which is preferable.
  • thermoelectric semiconductor particles used in the thermoelectric semiconductor composition are obtained by pulverizing the above-mentioned thermoelectric semiconductor material to a predetermined size by a fine pulverizer or the like.
  • the blending amount of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. It is more preferably 50 to 96% by mass, and even more preferably 70 to 95% by mass.
  • the Seebeck coefficient absolute value of the Peltier coefficient
  • the decrease in the electric conductivity is suppressed, and only the thermal conductivity is decreased, so that high thermoelectric performance is exhibited.
  • a film having sufficient film strength and flexibility can be obtained, which is preferable.
  • the average particle size of the thermoelectric semiconductor particles is preferably 10 nm to 200 ⁇ m, more preferably 10 nm to 30 ⁇ m, still more preferably 50 nm to 10 ⁇ m, and particularly preferably 1 to 6 ⁇ m. Within the above range, uniform dispersion can be facilitated and the electric conductivity can be increased.
  • the method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor particles is not particularly limited, and it may be pulverized to a predetermined size by a known pulverizer such as a jet mill, a ball mill, a bead mill, a colloid mill, a roller mill or the like. ..
  • the average particle size of the thermoelectric semiconductor particles was obtained by measuring with a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern), and was used as the median value of the particle size distribution.
  • thermoelectric semiconductor particles are preferably heat-treated in advance (the "heat treatment” referred to here is the “annealing treatment” performed in the annealing treatment step in the method for producing a thermoelectric conversion material layer of the present invention described later. Is different).
  • the heat treatment is not particularly limited, but before preparing the thermoelectric semiconductor composition, the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles under an atmosphere of an inert gas such as nitrogen or argon.
  • thermoelectric semiconductor particles It is preferably performed in a reducing gas atmosphere such as hydrogen or under vacuum conditions, and more preferably in a mixed gas atmosphere of an inert gas and a reducing gas.
  • a reducing gas atmosphere such as hydrogen or under vacuum conditions
  • a mixed gas atmosphere of an inert gas and a reducing gas The specific temperature condition depends on the thermoelectric semiconductor particles used, but it is usually preferable to carry out the temperature at a temperature equal to or lower than the melting point of the particles and at 100 to 1500 ° C. for several minutes to several tens of hours.
  • thermoelectric semiconductor composition used in the present invention a heat-resistant resin is preferably used from the viewpoint of annealing the thermoelectric semiconductor material at a high temperature. It acts as a binder between thermoelectric semiconductor materials (thermoelectric semiconductor particles), can increase the flexibility of the thermoelectric conversion module, and facilitates the formation of a thin film by coating or the like.
  • the heat-resistant resin is not particularly limited, but when a thin film made of a thermoelectric semiconductor composition is subjected to crystal growth of thermoelectric semiconductor particles by annealing or the like, various factors such as mechanical strength and thermal conductivity as the resin are obtained. A heat-resistant resin that maintains its physical properties without being impaired is preferable.
  • the heat-resistant resin is preferably a polyamide resin, a polyamideimide resin, a polyimide resin, or an epoxy resin, and has excellent flexibility, because it has higher heat resistance and does not adversely affect the crystal growth of thermoelectric semiconductor particles in the thin film. From this point of view, polyamide resin, polyamideimide resin and polyimide resin are more preferable.
  • the polyimide resin is a general term for polyimide and its precursor.
  • the heat-resistant resin preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the flexibility can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the heat-resistant resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and further preferably 1% or less at 300 ° C. by thermogravimetric analysis (TG). ..
  • TG thermogravimetric analysis
  • the blending amount of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15. It is mass%.
  • the blending amount of the heat-resistant resin is within the above range, it functions as a binder for the thermoelectric semiconductor material, facilitates the formation of a thin film, and provides a film having both high thermoelectric performance and film strength.
  • the ionic liquid used in the present invention is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist as a liquid in any temperature range of ⁇ 50 to 400 ° C.
  • the ionic liquid is an ionic compound having a melting point in the range of ⁇ 50 ° C. or higher and lower than 400 ° C.
  • the melting point of the ionic liquid is preferably ⁇ 25 ° C. or higher and 200 ° C. or lower, and more preferably 0 ° C. or higher and 150 ° C. or lower.
  • Ionic liquids have features such as extremely low vapor pressure, non-volatility, excellent thermostability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive auxiliary agent, it is possible to effectively suppress the reduction of the electric conductivity between the thermoelectric semiconductor particles. Further, since the ionic liquid exhibits high polarity based on the aprotic ionic structure and has excellent compatibility with the heat-resistant resin, the electric conductivity of the thermoelectric conversion material layer can be made uniform.
  • ionic liquid known or commercially available ones can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; amine-based cations of tetraalkylammonium and their derivatives; phosphine such as phosphonium, trialkylsulfonium, tetraalkylphosphonium. systems cations and their derivatives; and cationic components, such as lithium cations and derivatives thereof, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc.
  • the cation component of the ionic liquid is a pyridinium cation and its derivatives from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor particles and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor particle gaps.
  • At least one selected from imidazolium cations and derivatives thereof is preferably contained.
  • Anionic component of the ionic liquid preferably contains a halide anion, Cl -, Br - and I - is more preferably contains at least one selected from.
  • an ionic liquid in which the cation component contains a pyridinium cation and a derivative thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 3-methyl-hexylpyridinium.
  • Chloride 4-methyl-octylpyridinium chloride, 3-methyl-octylpyridinium chloride, 3,4-dimethyl-butylpyridinium chloride, 3,5-dimethyl-butylpyridinium chloride, 4-methyl-butylpyridinium tetrafluoroborate, 4- Methyl-butylpyridinium hexafluorophosphate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium iodide and the like. Be done.
  • 1-butylpyridinium bromide 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, and 1-butyl-4-methylpyridinium iodide are preferable.
  • the ionic liquid in which the cation component contains an imidazolium cation and a derivative thereof [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [1-butyl-3- (2) -Hydroxyethyl) imidazolium tetrafluoroborate], 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3 -Methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-Tetradecyl-3-methylimidazolium chloride, 1-ethyl-3- (2-hydroxyeth
  • the above-mentioned ionic liquid preferably has an electric conductivity of 10-7 S / cm or more, and more preferably 10-6 S / cm or more.
  • the electric conductivity is in the above range, the reduction of the electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductivity auxiliary agent.
  • the above-mentioned ionic liquid preferably has a decomposition temperature of 300 ° C. or higher. As long as the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the above-mentioned ionic liquid preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and further preferably 1% or less at 300 ° C. by thermogravimetric analysis (TG). ..
  • TG thermogravimetric analysis
  • the blending amount of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 20% by mass.
  • the blending amount of the ionic liquid is within the above range, the decrease in electrical conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
  • the inorganic ionic compound used in the present invention is a compound composed of at least cations and anions.
  • the inorganic ionic compound is solid at room temperature, has a melting point in any temperature in the temperature range of 400 to 900 ° C., and has characteristics such as high ionic conductivity. Therefore, it can be used as a conductive auxiliary agent. It is possible to suppress a decrease in electrical conductivity between thermoelectric semiconductor particles.
  • a metal cation is used as the cation.
  • the metal cation include alkali metal cations, alkaline earth metal cations, typical metal cations and transition metal cations, and alkali metal cations or alkaline earth metal cations are more preferable.
  • the alkali metal cation include Li + , Na + , K + , Rb + , Cs +, Fr + and the like.
  • Examples of the alkaline earth metal cation include Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
  • the anion such as, F -, Cl -, Br -, I -, OH -, CN -, NO 3 -, NO 2 -, ClO -, ClO 2 -, ClO 3 -, ClO 4 -, CrO 4 2 -, HSO 4 -, SCN - , BF 4 -, PF 6 - , and the like.
  • a cation component such as potassium cation, sodium cation, or lithium cations, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc. of bromide ion, I -, etc. iodide ion, BF 4 -, PF 6 - fluoride ions, F (HF) n, such as - such as halide anions of, NO 3 -, OH -, CN - and the ones mentioned consists the anion component of such Be done.
  • a cation component such as potassium cation, sodium cation, or lithium cations
  • the cationic component of the inorganic ionic compound is potassium from the viewpoints of high temperature stability, compatibility with thermoelectric semiconductor particles and resins, and suppression of decrease in electrical conductivity between thermoelectric semiconductor particle gaps.
  • Sodium, and lithium are preferably included.
  • the anion component of the inorganic ionic compound preferably contains a halide anion, and more preferably contains at least one selected from Cl ⁇ , Br ⁇ , and I ⁇ .
  • Cationic component is, as a specific example of the inorganic ionic compound containing a potassium cation, KBr, KI, KCl, KF , KOH, K 2 CO 3 and the like. Of these, KBr and KI are preferable.
  • Specific examples of the inorganic ionic compound whose cation component contains a sodium cation include NaBr, NaI, NaOH, NaF, Na 2 CO 3 and the like. Of these, NaBr and NaI are preferable.
  • Specific examples of the inorganic ionic compound whose cation component contains a lithium cation include LiF, LiOH, and LiNO 3 . Of these, LiF and LiOH are preferable.
  • the above-mentioned inorganic ionic compound preferably has an electric conductivity of 10-7 S / cm or more, and more preferably 10-6 S / cm or more.
  • the electric conductivity is within the above range, the reduction of the electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductivity auxiliary agent.
  • the decomposition temperature of the above-mentioned inorganic ionic compound is preferably 400 ° C. or higher. As long as the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the above-mentioned inorganic ionic compound preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and preferably 1% or less at 400 ° C. by thermogravimetric analysis (TG). More preferred. As long as the mass reduction rate is within the above range, the effect as a conductive auxiliary agent can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • TG thermogravimetric analysis
  • the blending amount of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 10% by mass. ..
  • the blending amount of the inorganic ionic compound is within the above range, the decrease in electrical conductivity can be effectively suppressed, and as a result, a film having improved thermoelectric performance can be obtained.
  • the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass. It is preferably 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
  • thermoelectric semiconductor composition used in the present invention further contains, if necessary, a dispersant, a film-forming aid, a light stabilizer, an antioxidant, a tackifier, a plasticizer, a colorant, and the like. It may contain other additives such as resin stabilizers, fillers, pigments, conductive fillers, conductive polymers and hardeners. These additives can be used alone or in combination of two or more.
  • thermoelectric conversion material layer of the present invention has improved electrical conductivity, and by applying it as a thermoelectric conversion material layer of a thermoelectric conversion module, a thermoelectric conversion module having high thermoelectric performance can be obtained.
  • the method for producing a thermoelectric conversion material layer of the present invention is a method for producing a thermoelectric conversion material layer composed of a coating film of a thermoelectric semiconductor composition, wherein (A) a step of forming a thermoelectric conversion material layer, (B) the above-mentioned (). A step of drying the thermoelectric conversion material layer obtained in the step A, (C) a step of pressurizing the dried thermoelectric conversion material layer obtained in the step (B), and (D) the step (D). It is characterized by including a step of annealing the pressurized thermoelectric conversion material layer obtained in the step of C).
  • thermoelectric conversion material layer of the present invention After forming the thermoelectric conversion material layer, it is dried at a predetermined temperature, and then the upper surface of the thermoelectric conversion material layer is pressed with a predetermined pressure to form the thermoelectric conversion material layer. By reducing the volume of the voids and then annealing, a thermoelectric conversion material layer with improved electrical conductivity can be obtained.
  • FIG. 3 is an explanatory view showing an example of a method for manufacturing a thermoelectric conversion material layer of the present invention in order of steps
  • FIG. 3A is a cross-sectional view showing an embodiment in which a thermoelectric conversion material layer 2s is formed on a substrate 1a.
  • a thermoelectric conversion material layer 2s is formed on 1a as a coating film (including a gap 3a) and dried at a predetermined temperature
  • (B) is a cross-sectional view showing an aspect after the press pressurizing portion 5 is opposed to the upper surface of the thermoelectric conversion material layer 2s, and the dried thermoelectric conversion material layer 2s obtained in (a) is cooled to room temperature.
  • thermoelectric conversion material layer 2s and the press pressurizing section 5 face each other;
  • (C) is a cross-sectional view showing an aspect after pressurizing the upper surface of the thermoelectric conversion material layer 2s by the press pressurizing section 5 and then releasing the press pressurizing section 5 from the thermoelectric conversion material layer 2s. Then, by performing an annealing treatment, the thermoelectric conversion material layer 2t of the present invention (including the void portion 4a in which the number of voids and the volume are reduced) can be obtained.
  • the thermoelectric conversion material layer may be formed on a substrate in the form of a solid film, and then individualized into a desired chip size. Further, as another preferred embodiment, a coating film may be formed on the substrate in the size of the chip of the thermoelectric conversion material described above. Further, from the viewpoint of shape controllability of the thermoelectric conversion material layer, as a more preferable embodiment, a grid-like pattern frame member including a separated opening having a chip shape of the thermoelectric conversion material may be used.
  • the chip size is, for example, about 0.1 to 20 mm on the short side and 0.2 to 25 mm on the long side.
  • thermoelectric conversion material layer when the grid-like pattern frame member including the separated openings having the chip shape of the thermoelectric conversion material is used is as follows, for example.
  • P A grid-like pattern frame member including a separated opening having a chip shape of a thermoelectric conversion material is placed on the substrate;
  • Q A coating film of a thermoelectric conversion material layer is formed in the opening of the pattern frame member and dried at a predetermined temperature;
  • R After cooling the dried thermoelectric conversion material layer obtained in (q) to room temperature, the thermoelectric conversion material layer and the press pressurizing section (corresponding to the press pressurizing section 5 in FIG.
  • thermoelectric conversion material layer of the present invention is obtained by subjecting the thermoelectric conversion material layer reflecting the shape of the opening of the pattern frame member obtained on the substrate to an annealing treatment.
  • the opening is not particularly limited, but may be rectangular, square, or circular as long as it has a shape that is reflected in the shape of the chip of the thermoelectric conversion material after the pattern frame member is released. Is preferable, and it is more preferable that the shape is rectangular or square.
  • the pattern frame member stainless steel, copper or the like can be used from the viewpoint of ease of formation.
  • thermoelectric conversion material layer forming step is a step of forming a thermoelectric conversion material layer on a substrate.
  • a thermoelectric semiconductor composition is formed on a substrate 1a. This is a step of coating and forming a thermoelectric conversion material layer 2s.
  • the substrate is not particularly limited, and examples thereof include glass, silicon, ceramic, metal, and plastic. Glass, silicon, ceramic and metal are preferable from the viewpoint of performing the annealing treatment at a high temperature, and glass, silicon and ceramic are more preferable from the viewpoint of dimensional stability after heat treatment. From the viewpoint of process and dimensional stability, the thickness of the substrate can be 100 to 10000 ⁇ m.
  • thermoelectric semiconductor composition As the thermoelectric semiconductor composition used in the present invention, the same thermoelectric semiconductor composition as described above can be used. The same applies to preferable materials, blending amounts, etc. for thermoelectric semiconductor materials, heat-resistant resins, ionic liquids, inorganic ionic compounds, and the like.
  • thermoelectric semiconductor composition used in the present invention is not particularly limited, and the thermoelectric semiconductor particles and the heat-resistant resin are prepared by a known method such as an ultrasonic homogenizer, a spiral mixer, a planetary mixer, a disperser, and a hybrid mixer. , One or both of the ionic liquid and the inorganic ionic compound, and if necessary, the other additive and a solvent may be added and mixed and dispersed to prepare the thermoelectric semiconductor composition.
  • the solvent examples include solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve.
  • solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve.
  • solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve.
  • One of these solvents may be used alone, or two or more of these solvents may be mixed and used.
  • the solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.
  • the thin film made of the thermoelectric semiconductor composition can be formed, for example, by applying the thermoelectric semiconductor composition on the substrate and drying it.
  • thermoelectric semiconductor composition As a method of applying the thermoelectric semiconductor composition on a substrate, a screen printing method, a flexographic printing method, a gravure printing method, a spin coating method, a dip coating method, a die coating method, a spray coating method, a bar coating method, a doctor blade method, etc.
  • Known methods such as the applicator method can be mentioned and are not particularly limited.
  • the coating film is formed into a pattern, screen printing, stencil printing, slot die coating, etc., which can easily form a pattern using a screen plate having a desired pattern, are preferably used.
  • thermoelectric conversion material layer drying step is a step of drying the thermoelectric conversion material layer obtained in the step (A). For example, in FIG. 3A, on the substrate 1a. This is a step of drying the thermoelectric conversion material layer 2s.
  • drying method conventionally known drying methods such as a hot air drying method, a hot roll drying method, and an infrared irradiation method can be adopted.
  • the heating temperature is usually 80 to 170 ° C., preferably 100 to 150 ° C., more preferably 110 to 145 ° C., still more preferably 120 to 140 ° C.
  • the heating time varies depending on the heating method, but is usually 30 seconds to 5 hours, preferably 1 minute to 3 hours, more preferably 5 minutes to 2 hours, and further preferably 10 minutes to 50 minutes.
  • the heating temperature and the heating time are within this range, it is easy to improve the electric conductivity of the thermoelectric conversion material layer after pressurization and annealing treatment.
  • the heating temperature may be in a temperature range in which the solvent used can be dried or in a temperature range lower than that.
  • thermoelectric conversion material layer pressurizing step is a step of pressurizing the dried thermoelectric conversion material layer obtained in the step (B), for example, in FIG. 3 (b). Is a step of pressurizing the upper surface of the thermoelectric conversion material layer 2s with the press pressurizing section 5.
  • the pressurization is preferably performed in an atmospheric pressure atmosphere after the dried thermoelectric conversion material layer obtained in the step (B) is cooled to room temperature. Further, as another embodiment, the pressurization is performed by maintaining the drying temperature without cooling the thermoelectric conversion material layer after drying obtained in the step (B) to room temperature, and an annealing treatment step described later, which is a next step. It is preferable to put it in.
  • the pressurizing method include a method using a physical pressurizing means such as a hydraulic press, a vacuum press, and a weight.
  • the amount of pressurization varies depending on the viscosity of the thermoelectric conversion material layer, the amount of voids, etc., but is usually 0.1 to 80 MPa, preferably 1.0 to 60 MPa, more preferably 5 to 50 MPa, still more preferable. Is 10 to 42 MPa.
  • the pressurization may be performed by increasing the pressurization amount to a predetermined amount at once, but the shape stability of the thermoelectric conversion material layer is maintained and the voids in the thermoelectric conversion material layer are further reduced to reduce the filling rate of the thermoelectric conversion material.
  • the pressure is adjusted as appropriate from the viewpoint of improving the above pressure, but is usually 0.1 to 50 MPa / min, preferably 0.5 to 30 MPa / min, and more preferably 1.0 to 10 MPa / min to a predetermined pressurization amount.
  • the pressurization time varies depending on the pressurization method, but is usually 5 seconds to 5 hours, preferably 30 seconds to 3 hours, more preferably 5 minutes to 2 hours, and further preferably 10 minutes to 1 hour. When the pressurization amount and the pressurization time are within this range, the filling rate increases, and the electric conductivity of the thermoelectric conversion material layer after the annealing treatment tends to improve.
  • the annealing treatment step is a step of annealing the pressurized thermoelectric conversion material layer obtained in the step (C) above. For example, in FIG. 3C, after pressurization. This is a step of annealing the thermoelectric conversion material layer 2s of No. 2 at the temperature of the annealing treatment (after the annealing treatment, the thermoelectric conversion material layer 2t is obtained).
  • the thermoelectric conversion material layer is formed as a thin film, dried, and then annealed to stabilize the thermoelectric performance, and the thermoelectric semiconductor particles in the thin film can be crystal-grown to further improve the thermoelectric performance. it can.
  • the annealing treatment is performed with or without pressurizing the thermoelectric conversion material layer.
  • the amount of pressurization in the case of pressurization is usually 0.1 to 80 MPa, preferably 1.0 to 60 MPa, more preferably 5 to 50 MPa, still more preferably 10 to 42 MPa.
  • a thermoelectric semiconductor material used in a thermoelectric semiconductor composition which is usually carried out under an inert gas atmosphere such as nitrogen or argon, a reducing gas atmosphere, or under vacuum conditions in which the gas flow rate is controlled.
  • the temperature of the annealing treatment is usually 100 to 600 ° C. for several minutes to several tens of hours, preferably 250 to 450 ° C. for several minutes to several tens of hours. Do time.
  • the thickness of the thermoelectric conversion material layer is not particularly limited as long as the shape stability and thermoelectric performance are not impaired by pressurization, and are as described above.
  • thermoelectric conversion material layer of the present invention According to the method for producing a thermoelectric conversion material layer of the present invention, a thermoelectric conversion material layer having improved electrical conductivity can be produced by a simple method.
  • thermoelectric conversion material layer produced in Examples and Comparative Examples The evaluation of the filling rate and the electric conductivity of the thermoelectric semiconductor composition in the thermoelectric conversion material layer produced in Examples and Comparative Examples was carried out by the following methods.
  • (A) Evaluation of filling rate A vertical cross section of the thermoelectric conversion material layer produced in Examples and Comparative Examples including the central portion of the thermoelectric conversion material layer by a polishing device (manufactured by Refine Tech, model name: Refine Polisher HV). After taking out, the vertical cross section was observed using FE-SEM / EDX (FE-SEM: manufactured by Hitachi High-Technologies Corporation, model name: S-4700), and then Image J (image processing software, ver.1.
  • the filling rate defined by the ratio of the area of the thermoelectric semiconductor composition to the area of the longitudinal section of the thermoelectric conversion material layer was calculated.
  • an SEM image longitudinal cross section
  • the measurement range is surrounded by 1280 pixels in the width direction and 220 pixels in the thickness direction with reference to the boundary between the thermoelectric conversion material layer and the alumina substrate. It was taken as a range and cut out as an image.
  • the cut-out image is binarized from "Brightness / Contrast" with the maximum contrast value, and the dark part and the bright part in the binarization process are regarded as the thermoelectric semiconductor composition, and the thermoelectric semiconductor is used in "Throld".
  • the filling rate of the composition was calculated.
  • the filling rate was calculated for three SEM images and used as the average value thereof.
  • the image to be cut out is selected within the region portion of the vertical cross section.
  • the void portion (air layer portion) around the thermoelectric conversion material layer is not captured.
  • a region not exceeding X in the width direction and Dmin in the thickness direction of the vertical cross section was selected.
  • (B) Evaluation of Electrical Conductivity The thermoelectric conversion material layers produced in Examples and Comparative Examples were subjected to an environment of 25 ° C. and 60% RH using a low resistance measuring device (manufactured by Hioki Co., Ltd., model name: RM3545). The surface resistance value was measured by the four-terminal method, and the electric conductivity was calculated.
  • thermoelectric conversion material layer ⁇ Preparation of thermoelectric conversion material layer> (1) Preparation of thermoelectric semiconductor composition (production of thermoelectric semiconductor particles) P-type bismuth tellurium Bi 0.4 Te 3 Sb 1.6 (manufactured by High Purity Chemical Laboratory, particle size: 180 ⁇ m), which is a bismuth-tellurium thermoelectric semiconductor material, is used in a planetary ball mill (manufactured by Fritsch Japan, Premium line P). Thermoelectric semiconductor particles having an average particle size of 2.0 ⁇ m were produced by pulverizing in a nitrogen gas atmosphere using -7). The thermoelectric semiconductor particles obtained by pulverization were subjected to particle size distribution measurement with a laser diffraction type particle size analyzer (Mastersizer 3000 manufactured by Malvern).
  • thermoelectric semiconductor composition P-type bismuthellide Bi 0.4 Te 3 Sb 1.6 particles 82.5% by mass obtained above, polyamic acid which is a polyimide precursor as a heat-resistant resin (manufactured by Ube Kosan Co., Ltd., U-Wanis A, solvent: A coating liquid consisting of a thermoelectric semiconductor composition in which N-methylpyrrolidone, solid content concentration: 18% by mass) 3.2% by mass (solid content), and 1-butylpyridinium bromide 14.3% by mass as an ionic liquid are mixed and dispersed. Was prepared.
  • thermoelectric conversion material layer On an alumina substrate (manufactured by Kyocera Corporation, trade name: alumina substrate A0476T, 100 mm ⁇ 100 mm, thickness: 1 mm), the coating liquid prepared in (1) above is applied.
  • the film was printed as a solid film using an applicator and dried at a temperature of 140 ° C. for 40 minutes in an argon atmosphere to form a thin film (thermoelectric conversion material layer before annealing treatment) having a thickness of 37 ⁇ m.
  • the dried thermoelectric conversion material layer was cooled to room temperature, and the alumina substrate on which the thermoelectric conversion material layer was printed was cut out to a size of 5 mm ⁇ 15 mm.
  • thermoelectric conversion material layer was uniformly applied at 40.0 MPa.
  • thermoelectric conversion material layer was prepared in the same manner as in Example 1 except that the entire upper surface of the thermoelectric conversion material layer was uniformly pressurized at 30.0 MPa in Example 1. The obtained thermoelectric conversion material layer was evaluated for filling rate and electric conductivity. The results are shown in Table 1.
  • thermoelectric conversion material layer was prepared in the same manner as in Example 1 except that the pressure treatment was not performed, and the obtained thermoelectric conversion material layer was evaluated for filling rate and electric conductivity. .. The results are shown in Table 1.
  • thermoelectric conversion material layer of the present invention in which the filling rate of the thermoelectric conversion material in the thermoelectric conversion material layer composed of the coating film of the thermoelectric semiconductor composition satisfies the specification of the present invention
  • Comparative Example 1 in which the filling rate is outside the range of the specification of the present invention. It can be seen that the electrical conductivity is increased by 50 to 118%. Therefore, by applying the thermoelectric conversion material layer of the present invention and the manufacturing method thereof to the thermoelectric conversion module, the thermoelectric performance of the thermoelectric conversion module can be improved.
  • thermoelectric conversion material layer composed of the coating film of the thermoelectric semiconductor composition of the present invention and the method for producing the same, the electric conductivity of the thermoelectric conversion material layer is increased. Therefore, the thermoelectric conversion material layer of the present invention is incorporated into the thermoelectric conversion module. This can be expected to improve thermoelectric performance.
  • the obtained thermoelectric conversion module has the possibility of being more flexible and thinner (smaller and lighter) than the thermoelectric conversion module using a sintered body of a conventional thermoelectric semiconductor material.
  • the thermoelectric conversion module using the above thermoelectric conversion material layer converts exhaust heat from various combustion furnaces such as factories, waste combustion furnaces, cement combustion furnaces, automobile combustion gas exhaust heat, and electronic equipment exhaust heat into electricity. It is conceivable to apply it to power generation applications.
  • As a cooling application in the field of electronic equipment, for example, it can be considered to be applied to temperature control of various sensors such as CCD (Charge Coupled Device), MEMS (Micro Electro Mechanical Systems), and light receiving element, which are semiconductor elements. ..
  • Substrate 1b Alumina substrate 2,2s, 2t: Thermoelectric conversion material layer 3: Void portion 3a, 4a: Void portion 3b: Void portion (Comparative Example 1) 4b: Void portion (Example 1) 5: Press pressurizing part X: Length (width direction) Y: Length (depth direction) D: Thickness (thickness direction) Dmax: Maximum value of thickness in the thickness direction (longitudinal section) Dmin: Minimum value of thickness in the thickness direction (longitudinal section) C: Central part of thermoelectric conversion material layer

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Abstract

L'invention concerne : une couche de matériau thermoélectrique haute performance comprenant un film de revêtement d'une composition semi-conductrice thermoélectrique et étant configurée de telle sorte que la conductivité électrique du matériau thermoélectrique dans la couche de matériau thermoélectrique est améliorée ; et un procédé de production de la couche de matériau thermoélectrique. La couche de matériau thermoélectrique comprend un film de revêtement d'une composition semi-conductrice thermoélectrique, la couche de matériau thermoélectrique ayant des parties vides, et la vitesse de remplissage est égale ou supérieure à 0,800 et inférieure à 1,000 lorsque la vitesse de remplissage est définie comme étant le ratio de la surface de la composition semi-conductrice thermoélectrique par rapport à la surface d'une section transversale longitudinale comprenant la partie centrale de la couche de matériau thermoélectrique.
PCT/JP2020/013552 2019-03-29 2020-03-26 Couche de matériau thermoélectrique et son procédé de production WO2020203612A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023013590A1 (fr) * 2021-08-02 2023-02-09 リンテック株式会社 Couche de matériau de conversion thermoélectrique et module de conversion thermoélectrique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002223013A (ja) * 2001-01-29 2002-08-09 Kyocera Corp 熱電変換素子及びその製造方法
JP2014029932A (ja) * 2012-07-31 2014-02-13 Nippon Valqua Ind Ltd 熱電変換材料、熱電変換シートおよびその製造方法ならびに熱電変換モジュール
WO2017122627A1 (fr) * 2016-01-13 2017-07-20 積水化学工業株式会社 Matériau de conversion thermoélectrique et dispositif de conversion thermoélectrique
WO2018159291A1 (fr) * 2017-02-28 2018-09-07 リンテック株式会社 Module de conversion thermoélectrique et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002223013A (ja) * 2001-01-29 2002-08-09 Kyocera Corp 熱電変換素子及びその製造方法
JP2014029932A (ja) * 2012-07-31 2014-02-13 Nippon Valqua Ind Ltd 熱電変換材料、熱電変換シートおよびその製造方法ならびに熱電変換モジュール
WO2017122627A1 (fr) * 2016-01-13 2017-07-20 積水化学工業株式会社 Matériau de conversion thermoélectrique et dispositif de conversion thermoélectrique
WO2018159291A1 (fr) * 2017-02-28 2018-09-07 リンテック株式会社 Module 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
WO2023013590A1 (fr) * 2021-08-02 2023-02-09 リンテック株式会社 Couche de matériau de conversion thermoélectrique et module de conversion thermoélectrique

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