WO2023013590A1

WO2023013590A1 - Thermoelectric conversion material layer and thermoelectric conversion module

Info

Publication number: WO2023013590A1
Application number: PCT/JP2022/029511
Authority: WO
Inventors: 俊弥山▲崎▼; 邦久加藤; 佑太関
Original assignee: リンテック株式会社
Priority date: 2021-08-02
Filing date: 2022-08-01
Publication date: 2023-02-09
Also published as: JP2023021733A

Abstract

The present invention provides a thermoelectric conversion material layer which exhibits high thermoelectric performance, wherein the electrical conductivity of a thermoelectric conversion material in the thermoelectric conversion material layer is further improved. This thermoelectric conversion material layer contains a thermoelectric conversion material that is composed of a thermoelectric semiconductor composition which contains thermoelectric semiconductor particles, a binder resin and an ionic liquid; and the average particle diameter of the thermoelectric semiconductor particles is not less than 8.0 µm but less than 50.0 µm.

Description

[Title of invention determined by ISA based on Rule 37.2] Thermoelectric conversion material layer and thermoelectric conversion module

The present invention relates to a thermoelectric conversion material layer.

In recent years, thermoelectric power generation technology, which has a simple system and can be downsized, has been attracting attention as a recovery power generation technology for unused waste heat energy generated from fossil fuel resources used in buildings, factories, etc. However, thermoelectric power generation generally has poor power generation efficiency, and various companies and research institutes are actively conducting research and development to improve power generation efficiency. In order to improve the efficiency of power generation, it is essential to improve the efficiency of thermoelectric conversion materials. It is rare.

The thermoelectric conversion characteristics of a thermoelectric conversion material can be evaluated by a thermoelectric figure of merit Z (Z=σS ² /λ). Here, S is the Seebeck coefficient, σ is electrical conductivity, and λ is thermal conductivity.
If the value of the thermoelectric figure of merit Z is increased, the power generation efficiency is improved. Therefore, in order to improve the efficiency of power generation, a thermoelectric conversion material with a large Seebeck coefficient S and a large electrical conductivity σ and a small thermal conductivity λ is found. This is very important.
As mentioned above, it is necessary to study how to improve power generation efficiency. It was essential to reduce manufacturing costs for further spread to applications with large areas. In addition, thermoelectric conversion elements that are currently manufactured are inferior in flexibility, so thermoelectric conversion elements that have excellent flexibility are desired.
Under such circumstances, Patent Literature 1 discusses a thermoelectric conversion material having a thin film made of a thermoelectric semiconductor composition containing thermoelectric semiconductor fine particles, a heat-resistant resin, and an ionic liquid.

WO2015/019871

In Patent Document 1, an ionic liquid is used as a conductive auxiliary agent in order to have flexibility and effectively suppress a decrease in electrical conductivity between thermoelectric semiconductor particles, thereby improving the total thermoelectric performance. However, further improvement in thermoelectric performance is required in order to realize smaller size, lighter weight, and higher integration.

In view of the above, it is an object of the present invention to provide a thermoelectric conversion material layer with high thermoelectric performance in which the electrical conductivity of the thermoelectric conversion material in the thermoelectric conversion material layer is further improved.

The present inventors have made intensive studies to solve the above problems, and as a result, the thermoelectric conversion material layer is composed of thermoelectric semiconductor particles having a specific average particle size that contribute to a decrease in thermal conductivity and an increase in electrical conductivity. A thin film made of a thermoelectric semiconductor composition containing a binder resin that suppresses the remaining voids in the thermoelectric conversion material layer and an ionic liquid that suppresses a decrease in electrical conductivity in the voids between particles. The inventors have found that the thermoelectric performance of the conversion material layer is more improved than that of the conventional thermoelectric conversion materials, and completed the present invention.
That is, the present invention provides the following [1] to [9].
[1] A thermoelectric conversion material layer containing a thermoelectric conversion material made of a thermoelectric semiconductor composition containing thermoelectric semiconductor particles, a binder resin and an ionic liquid, wherein the thermoelectric semiconductor particles have an average particle size of 8.0 μm or more and less than 50.0 μm A thermoelectric conversion material layer.
[2] When the thermoelectric conversion material layer has the thermoelectric conversion material and voids, and the ratio of the area occupied by the thermoelectric conversion material in the area of the longitudinal section including the central portion of the thermoelectric conversion material layer is defined as the filling rate. The thermoelectric conversion material layer according to [1] above, wherein the filling rate is 0.900 or more and less than 1.000.
[3] The thermoelectric conversion material layer according to the above [1] or [2], wherein the thermoelectric conversion material layer is made of a fired body of a coating film of a thermoelectric semiconductor composition.
[4] The thermoelectric conversion material layer according to [1] above, wherein the binder resin decomposes by 90% by mass or more at the firing temperature of the fired body.
[5] The thermoelectric conversion material layer according to [1] or [4] above, wherein the binder resin contains at least one selected from polycarbonates, cellulose derivatives and polyvinyl polymers.
[6] The thermoelectric conversion material layer according to any one of [1], [4] and [5] above, wherein the binder resin decomposes at 400° C. by 90% by mass or more.
[7] The thermoelectric according to [1] above, wherein the thermoelectric semiconductor particles are composed of a bismuth-tellurium-based thermoelectric semiconductor material, a telluride-based thermoelectric semiconductor material, an antimony-tellurium-based thermoelectric semiconductor material, or a bismuth-selenide-based thermoelectric semiconductor material. conversion material layer.
[8] The thermoelectric conversion material layer according to [1] or [7] above, wherein the thermoelectric semiconductor particles have an average particle size of 8.0 μm or more and less than 40.0 μm.
[9] A thermoelectric conversion module including the thermoelectric conversion material layer according to any one of [1] to [8] above.

According to the present invention, it is possible to provide a thermoelectric conversion material layer with high thermoelectric performance in which the electrical conductivity of the thermoelectric conversion material in the thermoelectric conversion material layer is further improved.

It is a figure for demonstrating the definition of the vertical cross section of the thermoelectric conversion material layer of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram for demonstrating the vertical cross section of the thermoelectric conversion material layer of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing explaining an example of the manufacturing method of the thermoelectric conversion material layer of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing explaining an example of the method of manufacturing the thermoelectric conversion module containing the thermoelectric conversion material layer of this invention.

[Thermoelectric conversion material layer]
The thermoelectric conversion material layer of the present invention is a thermoelectric conversion material layer containing a thermoelectric conversion material composed of a thermoelectric semiconductor composition containing thermoelectric semiconductor particles, a binder resin and an ionic liquid, wherein the thermoelectric semiconductor particles have an average particle diameter of 8.5. It is characterized by being 0 μm or more and less than 50.0 μm.
By using a particulate thermoelectric semiconductor material having a specific average particle size as the thermoelectric semiconductor particles constituting the thermoelectric conversion material layer of the present invention, the interfacial resistance between the thermoelectric semiconductor particles is reduced, and the rate of increase in thermal conductivity is reduced. It is possible to further increase the rate of increase in electrical conductivity compared to , and the total thermoelectric performance of the thermoelectric conversion material layer can be improved. Furthermore, in addition to the thermoelectric semiconductor particles, the thermoelectric conversion material layer is composed of a binder resin that suppresses the remaining voids in the thermoelectric conversion material layer, and ions that suppress a decrease in electrical conductivity in the voids between the thermoelectric semiconductor particles. By forming a thin film made of a thermoelectric semiconductor composition containing a liquid, a thermoelectric conversion material layer having higher thermoelectric performance than conventional thermoelectric conversion material layers can be obtained.
In this specification, the “thermoelectric conversion material layer” is a layer containing a thermoelectric conversion material and, if there are gaps around the thermoelectric conversion material, those gaps.
In the present specification, the term "thermoelectric conversion material" means a product obtained by baking a thermoelectric semiconductor composition (for example, a baked body of a coating film of a thermoelectric semiconductor composition). Even if the thermoelectric semiconductor composition contains a binder resin, which will be described later, if the binder resin is completely decomposed by firing, the thermoelectric conversion material does not contain the binder resin.
Furthermore, the thermoelectric conversion material layer after baking (annealing) may be referred to as a "thermoelectric conversion material layer chip" or a "thermoelectric conversion material chip".

The thermoelectric conversion material layer of the present invention contains a thermoelectric conversion material comprising a thermoelectric semiconductor composition containing thermoelectric semiconductor particles, a binder resin and an ionic liquid.
The thermoelectric conversion material layer of the present invention is preferably made of a sintered body of a coating film of a thermoelectric semiconductor composition. A sintered body is obtained by sintering a coating film of a thermoelectric semiconductor composition at a sintering temperature. The firing temperature is usually determined according to the type of thermoelectric semiconductor particles contained in the thermoelectric semiconductor composition, and is usually 260 to 500°C, preferably 400 to 460°C, more preferably 410 to 450°C, particularly preferably It is 420-450°C. Incidentally, in the examples, the firing temperature is 430°C.

<Thermoelectric semiconductor particles>
The thermoelectric semiconductor composition includes thermoelectric semiconductor particles.
The thermoelectric semiconductor particles used in the present invention are obtained by pulverizing a thermoelectric semiconductor material, which will be described later, to a predetermined size using a pulverizer or the like.
The method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor particles is not particularly limited, and may be pulverized to a predetermined size by a known pulverizing device such as a jet mill, ball mill, bead mill, colloid mill, roller mill, or the like. .
The average particle size of the thermoelectric semiconductor particles is obtained by measurement using, for example, a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern), and is the median value of the particle size distribution.

The thermoelectric semiconductor particles are preferably heat-treated in advance. By performing the heat treatment, the crystallinity of the thermoelectric semiconductor particles is improved, and the surface oxide film of the thermoelectric semiconductor particles is removed. It can be improved further. The heat treatment is not particularly limited, but before preparing the thermoelectric semiconductor composition, in an inert gas atmosphere such as nitrogen, argon, etc., in which the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles. It is preferably carried out under a reducing gas atmosphere such as hydrogen or under vacuum conditions, more preferably under a mixed gas atmosphere of an inert gas and a reducing gas. Although the specific temperature conditions depend on the thermoelectric semiconductor particles used, it is generally preferred that the temperature be below the melting point of the particles and be 100 to 1500° C. for several minutes to several tens of hours.

The thermoelectric semiconductor material is not particularly limited as long as it can generate a thermoelectromotive force by applying a temperature difference. Thermoelectric semiconductor materials; telluride-based thermoelectric semiconductor materials such as GeTe and PbTe; antimony-tellurium-based thermoelectric semiconductor materials; zinc-antimony-based thermoelectric semiconductor materials such as ZnSb, Zn ₃ Sb _{2 and} Zn ₄ Sb ₃ ; silicon-germanium such as SiGe Bismuth selenide-based thermoelectric semiconductor materials such as Bi ₂ Se ₃ ; Silicide-based thermoelectric semiconductor materials such as β-FeSi ₂ , CrSi ₂ , MnSi _1.73 and Mg ₂ Si; Oxide-based thermoelectric semiconductor materials; Heusler materials such as FeVAl, FeVAlSi and FeVTiAl; sulfide thermoelectric semiconductor materials such as _TiS2 ; and the like are used. These may be used individually by 1 type, and may use 2 or more types together.

Among these, bismuth-tellurium-based thermoelectric semiconductor materials, telluride-based thermoelectric semiconductor materials, antimony-tellurium-based thermoelectric semiconductor materials, and bismuth-selenide-based thermoelectric semiconductor materials are preferable. Bismuth-tellurium based thermoelectric semiconductor materials such as type bismuth telluride are more preferred.

P-type bismuth telluride has holes as carriers and a positive Seebeck coefficient, and is preferably represented by, for example, Bi _X Te ₃ Sb _2-X . In this case, X preferably satisfies 0<X≦0.8, more preferably 0.4≦X≦0.6. When X is greater than 0 and 0.8 or less, the Seebeck coefficient and electrical conductivity are increased, and the properties of the P-type thermoelectric element are maintained, which is preferable.
N-type bismuth telluride has electrons as carriers and a negative Seebeck coefficient, and is represented by Bi ₂ Te _3-Y Se _Y , for example. In this case, Y preferably satisfies 0≦Y≦3 (when Y=0: Bi ₂ Te ₃ ), more preferably 0<Y≦2.7. When Y is 0 or more and 3 or less, the Seebeck coefficient and electrical conductivity are increased, and the properties of the N-type thermoelectric element are maintained, which is preferable.

The average particle size of the thermoelectric semiconductor particles is 8.0 μm or more and less than 50.0 μm. When the average particle size is less than 8.0 μm, the interfacial resistance between the thermoelectric semiconductor particles tends to increase, which tends to lead to a decrease in electrical conductivity. When the average particle size is 50.0 μm or more, the interfacial resistance between the thermoelectric semiconductor particles tends to decrease, which tends to lead to an increase in electrical conductivity, but the increase in thermal conductivity tends to become more pronounced. The increase in thermoelectric performance at is suppressed. The average particle diameter of the thermoelectric semiconductor particles is preferably 8.0 μm or more and less than 45.0 μm, more preferably 8.0 μm or more and less than 42.0 μm, still more preferably 10.0 μm or more and less than 40.0 μm, Particularly preferably, it is 15.0 μm or more and less than 35.0 μm. If the average particle size of the thermoelectric semiconductor particles is within the above range, the interfacial resistance between the thermoelectric semiconductor particles is reduced, making it possible to increase the rate of increase in electrical conductivity more than the rate of increase in thermal conductivity. The total thermoelectric performance can be improved.

The content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30-99% by mass, more preferably 50-96% by mass, and particularly preferably 70-95% by mass. If the content of the thermoelectric semiconductor particles is within the above range, the Seebeck coefficient (absolute value of the Peltier coefficient) is large, and the decrease in electrical conductivity is suppressed, and only the thermal conductivity tends to decrease. It is preferable because a film having sufficient film strength and flexibility can be obtained while exhibiting performance.

<Binder resin>
The thermoelectric semiconductor composition contains a binder resin.
The binder resin facilitates the separation of the thermoelectric conversion material layer after the firing (annealing) treatment from the substrate described later used in the production of the chip, and also acts as a binder between the thermoelectric semiconductor particles to improve the flexibility of the thermoelectric conversion module described later. can be increased, and the formation of a thin film by coating or the like can be facilitated.

The binder resin is preferably a resin that decomposes at a firing (annealing) temperature of 90% by mass or more, more preferably a resin that decomposes at 95% by mass or more, and a resin that decomposes at 99% by mass or more. It is particularly preferred to have
In addition, a resin that maintains various physical properties such as mechanical strength and thermal conductivity without impairing when crystal growth of thermoelectric semiconductor particles is performed by baking (annealing) a coating film (thin film) made of a thermoelectric semiconductor composition. more preferred.
As the binder resin, if a resin that decomposes at a firing (annealing) temperature of 90% by mass or more, that is, a resin that decomposes at a lower temperature than conventionally used heat-resistant resins, the binder resin will decompose upon firing. The content of the binder resin, which is an insulating component contained in the fired body, is reduced, and the crystal growth of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is promoted. rate can be improved.
As one aspect, it is preferable that 90% by mass or more of the binder resin decompose at a firing (annealing) temperature of 400°C.
Whether or not the resin decomposes at a predetermined value (e.g., 90% by mass) or more at the firing (annealing) temperature is determined by thermogravimetry (TG) at the mass reduction rate (mass before decomposition) at the firing (annealing) temperature. The value obtained by dividing the mass after decomposition by ).

A thermoplastic resin or a curable resin can be used as such a binder resin. Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polymethylpentene; polycarbonates; thermoplastic polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polystyrene, acrylonitrile-styrene copolymers, and polyacetic acid. Polyvinyl polymers such as vinyl, ethylene-vinyl acetate copolymer, vinyl chloride, polyvinylpyridine, polyvinyl alcohol and polyvinylpyrrolidone; polyurethanes; cellulose derivatives such as ethyl cellulose; Examples of curable resins include thermosetting resins and photocurable resins. Examples of thermosetting resins include epoxy resins and phenol resins. Examples of photocurable resins include photocurable acrylic resins, photocurable urethane resins, and photocurable epoxy resins. These may be used individually by 1 type, and may use 2 or more types together.
Among these, from the viewpoint of the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer, thermoplastic resins are preferred, cellulose derivatives such as polycarbonate and ethyl cellulose are more preferred, and polycarbonate is particularly preferred.

The binder resin is appropriately selected according to the temperature of the baking (annealing) treatment for the thermoelectric semiconductor material in the baking (annealing) treatment step (B), which will be described later. From the viewpoint of the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer, it is preferable to perform the baking (annealing) treatment at a temperature higher than the final decomposition temperature of the binder resin.
As used herein, the term “final decomposition temperature” refers to the temperature at which the mass reduction rate at the firing (annealing) temperature by thermogravimetry (TG) is 100% (the mass after decomposition is 0% of the mass before decomposition). say.

The final decomposition temperature of the binder resin is generally 150-600°C, preferably 200-560°C, more preferably 220-460°C, and particularly preferably 240-360°C. If a binder resin having a final decomposition temperature within this range is used, it functions as a binder for the thermoelectric semiconductor material and facilitates the formation of a thin film during printing.
The binder resin is preferably decomposed and vaporized during heat pressing and/or firing, which will be described later.

The content of the binder resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5% by mass. % by mass. When the content of the binder resin is within the above range, the electric resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer can be reduced.

<Ionic liquid>
Thermoelectric semiconductor compositions include ionic liquids.
An ionic liquid 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 from -50°C to less than 400°C. In other words, an 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, more preferably 0° C. or higher and 150° C. or lower. Ionic liquids have characteristics such as extremely low vapor pressure and non-volatility, excellent thermal and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, it can effectively suppress the decrease in electrical conductivity between thermoelectric semiconductor materials as a conductive auxiliary agent. In addition, the ionic liquid exhibits high polarity based on an aprotic ionic structure and is excellent in compatibility with the binder resin, so that the electrical conductivity of the thermoelectric conversion material can be made uniform.

Known or commercially available ionic liquids can be used. For example, nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; tetraalkylammonium-based amine-based cations and their derivatives; Phosphine-based cations and derivatives thereof; cation components such as lithium cations and derivatives thereof, Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (FSO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , F(HF) _n ⁻ , (CN) ₂ N ⁻ , C ₄ F ₉ SO ₃ ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N ⁻ , C ₃ F ₇ COO ⁻ , (CF ₃ SO ₂ )(CF ₃ CO)N ⁻ and other anion components. These may be used individually by 1 type, and may use 2 or more types together.

Among the above ionic liquids, the cation component of the ionic liquid is pyridinium cation and its It preferably contains at least one selected from derivatives, imidazolium cations and derivatives thereof. The anion component of the ionic liquid preferably contains a halide anion, more preferably at least one selected from Cl ⁻ , Br ⁻ and I ⁻ .

Specific examples of ionic liquids in which the cationic component contains pyridinium cations and derivatives thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 3-methyl-hexylpyridinium chloride. 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. These may be used individually by 1 type, and may use 2 or more types together.
Among these, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, and 1-butyl-4-methylpyridinium iodide are preferred.

Specific examples of ionic liquids containing imidazolium cations and derivatives thereof as cationic components include [1-butyl-3-(2-hydroxyethyl)imidazolium bromide], [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-methylimidazolium tetrafluorooroborate, 1-butyl-3-methylimidazolium tetrafluorooroborate, 1-hexyl-3-methylimidazolium tetrafluoro Oroborate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-butylimidazolium methylsulfate, 1,3-dibutylimidazolium methyl Sulfate and the like can be mentioned. These may be used individually by 1 type, and may use 2 or more types together.
Among these, [1-butyl-3-(2-hydroxyethyl)imidazolium bromide] and [1-butyl-3-(2-hydroxyethyl)imidazolium tetrafluoroborate] are preferred.

The electrical conductivity of the ionic liquid is preferably 10 ⁻⁷ S/cm or higher, more preferably 10 ⁻⁶ S/cm or higher. If the electrical conductivity is within the above range, it can effectively suppress the decrease in the electrical conductivity between the thermoelectric semiconductor particles as a conductive auxiliary agent.

Further, the above ionic liquid preferably has a decomposition temperature of 300° C. or higher. If the decomposition temperature is within the above range, the effect as a conductive auxiliary agent can be maintained even when a coating film (thin film) made of the thermoelectric semiconductor composition is subjected to baking (annealing) treatment, as described later.
As used herein, the term "decomposition temperature" refers to the temperature at which the mass reduction rate at the firing (annealing) temperature by thermogravimetry (TG) is 10%.

In addition, in the above ionic liquid, the mass reduction rate at 300°C by thermogravimetry (TG) is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. If the mass reduction rate is within the above range, as described later, even when a coating film (thin film) made of the thermoelectric semiconductor composition is subjected to baking (annealing) treatment, the effect as a conductive auxiliary agent can be maintained.

The content of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01-50% by mass, more preferably 0.5-30% by mass, and particularly preferably 1.0-20% by mass. If the content 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.

<Inorganic ionic compound>
The thermoelectric semiconductor composition may further contain an inorganic ionic compound.
An inorganic ionic compound is a compound composed of at least a cation and an anion. Inorganic ionic compounds are solid at room temperature, have a melting point in a temperature range of 400 to 900° C., and have high ionic conductivity. Reduction in electrical conductivity between thermoelectric semiconductor particles can be suppressed.

The content 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, particularly preferably when the thermoelectric semiconductor composition contains the inorganic ionic compound. is 1.0 to 10% by mass. If the content 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 with improved thermoelectric performance can be obtained.
When the inorganic ionic compound and the ionic liquid are used together, 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, more preferably is 0.5 to 30% by weight, particularly preferably 1.0 to 10% by weight.

<Other additives>
In addition to the above, if necessary, the thermoelectric semiconductor composition may further contain a dispersant, a film forming aid, a light stabilizer, an antioxidant, a tackifier, a plasticizer, a colorant, a resin stabilizer, a filler, Other additives such as pigments, conductive fillers, conductive polymers, and curing agents may be included. These may be used individually by 1 type, and may use 2 or more types together.

The thickness of the thermoelectric conversion material layer (the thickness of the coating film (thin film) made of the thermoelectric semiconductor composition) is determined because the average particle size of the thermoelectric semiconductor fine particles used in the present invention is 8.0 μm or more and less than 50.0 μm. , preferably 6 times or more, more preferably 20 times or more, at least the average particle diameter. When the thickness of the thermoelectric conversion material layer is within the above range with respect to the average particle size of the thermoelectric semiconductor particles, the decrease in electrical conductivity due to the surface roughness of the thermoelectric conversion material layer is suppressed, so the thermoelectric performance is maintained at a high level. can.
The thickness of the thermoelectric conversion material layer is preferably 1000 μm or less, more preferably 600 μm or less, and even more preferably 400 μm or less from the viewpoints of thermoelectric performance, flexibility and film strength while satisfying the above requirements.

<Longitudinal section of thermoelectric conversion material layer>
The thermoelectric conversion material layer of the present invention has a thermoelectric conversion material and voids. The ratio is preferably 0.900 or more and less than 1.000.

The definition of "longitudinal section including the central portion of the thermoelectric conversion material layer" in this specification will be explained with reference to the drawings.
FIG. 1 is a view for explaining the definition of the longitudinal section of the thermoelectric conversion material layer of the present invention, FIG. 1(a) is a plan view of the thermoelectric conversion material layer 20, the thermoelectric conversion material layer 20 It has a length X in the width direction and a length Y in the depth direction. FIG. 1(b) is a longitudinal section of the thermoelectric conversion material layer 20 formed on the substrate 1a. ), and has a length X and a thickness D obtained by cutting across AA' in the width direction (the figure is a rectangle). Note that the thermoelectric conversion material layer 20 includes voids 30 .

A longitudinal section of the thermoelectric conversion material layer of the present invention will be described with reference to the drawings.
FIG. 2 is a schematic cross-sectional view for explaining the longitudinal section of the thermoelectric conversion material layer of the present invention, and FIG. 2(a) is an example of the longitudinal section of the thermoelectric conversion material layer 20s formed on the substrate 1a. , the thermoelectric conversion material layer 20s has a longitudinal section formed by a curve having a length X in the width direction and Dmin and Dmax in the thickness direction. A void 30b exists in the plane. FIG. 2(b) is an example of a longitudinal section of the thermoelectric conversion material layer 20t formed on the substrate 1a. The height is D [when the values of Dmin and Dmax in (a) of FIG. A suppressed void 40b exists. Dmin means the minimum thickness in the thickness direction of the longitudinal section, and Dmax means the maximum thickness in the thickness direction of the longitudinal section.

In the thermoelectric conversion material layer of the present invention, the filling rate of the thermoelectric conversion material in the thermoelectric conversion material layer, which is defined as the ratio of the area of the thermoelectric conversion material to the area of the longitudinal section including the central portion of the thermoelectric conversion material layer, is It is more than 0.900 and less than 1.000, and there are few voids in the thermoelectric conversion material layer.
If the filling rate of the thermoelectric conversion material in the thermoelectric conversion material layer is 0.900 or less, the number of voids in the thermoelectric conversion material layer increases, and the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer is difficult to decrease (excellent It becomes difficult to obtain a high electrical conductivity), and high thermoelectric performance cannot be obtained. The filling rate is preferably more than 0.900 and 0.999 or less, more preferably 0.920 or more and 0.999 or less, still more preferably 0.950 or more and 0.999 or less, particularly preferably 0.970 or more and 0.999 or less. is. When the filling rate is within this range, the electrical resistivity of the thermoelectric conversion material in the thermoelectric conversion material layer is reduced (excellent electrical conductivity is obtained), and high thermoelectric performance is obtained.

A method for measuring the filling rate of the thermoelectric conversion material in the thermoelectric conversion material layer will be described using test pieces (chips) made of the thermoelectric conversion material layers produced in Examples and Comparative Examples to be described later as examples.
For each test piece (chip) composed of the thermoelectric conversion material layer obtained in each example and comparative example, the center part of the thermoelectric conversion material layer is included with a polishing apparatus (manufactured by Refinetech, model name: Refine Polisher HV). A longitudinal section is taken out, a scanning electron microscope (SEM) (manufactured by Keyence Corporation) is used to observe the longitudinal section, and then image processing software (National Institutes of Health, ImageJ ver.1.44P) is used to perform thermoelectric A filling rate defined as a ratio of the area of the thermoelectric conversion material to the area of the longitudinal section of the conversion material layer was calculated.
In the measurement of the filling rate, an SEM image (longitudinal section) with a magnification of 500 times is used, and the measurement range is a range surrounded by 1280 pixels in the width direction and 220 pixels in the thickness direction with respect to an arbitrary position of the thermoelectric conversion material layer. , cropped as an image. The clipped image is subjected to binarization processing with the contrast set to the maximum value from "Brightness/Contrast". was calculated. The filling rate was calculated for three SEM images and taken as their average value.

[Thermoelectric conversion module]
The thermoelectric conversion material layer of the present invention is preferably applied to a thermoelectric conversion module having a structure such as a π-type thermoelectric conversion element (FIG. 4(f) described later) or an in-plane type thermoelectric conversion element.

<Method for manufacturing thermoelectric conversion module>
A method of manufacturing a thermoelectric conversion module including a thermoelectric conversion material layer of the present invention includes the following steps (i) to (vii).
(i): a step of forming a coating film of a thermoelectric semiconductor composition on a substrate;
(ii): a step of baking (annealing) the coating film of the thermoelectric semiconductor composition obtained in step (i) to obtain a thermoelectric conversion material layer (chip) made of the thermoelectric conversion material;
(iii): preparing a first layer having a first resin film and a first electrode in this order;
(iv): preparing a layer 2A having a second resin film and a second electrode in this order, or a layer 2B having a second resin film and no electrode;
(v): One surface of the thermoelectric conversion material layer (chip) obtained in the step (ii) above and the electrodes of the first layer prepared in the step (iii) above are bonded together to form a first bonding material layer. intervening bonding;
(vi): a step of peeling the other surface of the thermoelectric conversion material layer (chip) from the substrate after the step of (v); and (vii): the thermoelectric conversion material obtained by peeling in the step of (vi). A step of bonding the other surface of the layer (chip) and the electrode of the 2A layer prepared in the step (iv) above with a second bonding material layer interposed therebetween, or prepared in the step (iv) a step of bonding the second B layer through the third bonding material layer;

<Method for producing thermoelectric conversion material layer (chip)>
The method for manufacturing the thermoelectric conversion material layer (chip) is, for example,
(A) forming a coating film of a thermoelectric semiconductor composition on a substrate;
(B) a step of drying the coating film of the thermoelectric semiconductor composition obtained in step (A);
(C) a step of peeling off the coating film of the thermoelectric semiconductor composition after drying obtained in (B) above from the substrate;
(D) A step of subjecting the coating film of the thermoelectric semiconductor composition obtained in (C) above to heat press treatment (heat and pressure treatment);
(E) A step of firing (annealing) the thermoelectric semiconductor composition coating film after pressing obtained in step (D) above.

FIG. 3 is an explanatory diagram illustrating an example of the method for producing the thermoelectric conversion material layer (chip) of the present invention. A coating film 12 of a thermoelectric semiconductor composition is formed on the substrate 1, and then dried, peeled off from the substrate 1, heat-pressed (heated and pressurized), and fired (annealed) to obtain thermoelectricity. A thermoelectric conversion material layer (chip) made of a conversion material can be obtained as a self-supporting film.
In the method for producing the thermoelectric conversion material layer (chip), the case where the thermoelectric conversion material layer (chip) is obtained as a self-supporting film is described. The layer (chip) is formed on the substrate instead of being a self-supporting film, and the thermoelectric conversion material layer (chip) is separated from the substrate in step (vi) to form a self-supporting film.

((A) Step of forming coating film of thermoelectric semiconductor composition)
The step of forming a coating film of a thermoelectric semiconductor composition is a step of forming a coating film of a thermoelectric semiconductor composition on a substrate. For example, in FIG. That is, it is a step of applying a coating film 12a made of a thermoelectric semiconductor composition containing a P-type thermoelectric semiconductor material and a coating film 12b made of a thermoelectric semiconductor composition containing an N-type thermoelectric semiconductor material. The arrangement of the coating film 12a and the coating film 12b is not particularly limited, but from the viewpoint of thermoelectric performance, they should be configured to be used in a π-type or in-plane type thermoelectric conversion module, and should be connected by electrodes. preferably formed.
Here, when configuring a π-type thermoelectric conversion module, for example, a pair of electrodes (electrodes 5 in FIG. 4 described later) that are spaced apart from each other are provided on a substrate (resin film 4 in FIG. 4 described later). A fired body (P-type chip) of the coating film 12a made of a thermoelectric semiconductor composition containing a P-type thermoelectric semiconductor material is placed on the other electrode, and a thermoelectric semiconductor containing an N-type thermoelectric semiconductor material is placed on the other electrode. Firing bodies (N-type chips) of the coating film 12b made of the composition are similarly provided separately from each other, and the upper surfaces of both chips are electrically connected in series to electrodes on the facing substrate. From the viewpoint of efficiently obtaining high thermoelectric performance, a plurality of pairs of P-type chips and N-type chips with electrodes on opposing substrates interposed therebetween are electrically connected in series and used (see FIG. 4(f), which will be described later). is preferred.
Similarly, when configuring an in-plane type thermoelectric conversion module, for example, one electrode is provided on a substrate, a P-type chip is placed on the surface of the electrode, and an N-type chip is placed on the surface of the electrode. The two chips are provided so that the side surfaces of both chips (for example, the surfaces perpendicular to the substrate) are in contact with each other or separated from each other, and are electrically connected in series via electrodes in the in-plane direction of the substrate. From the viewpoint of efficiently obtaining high thermoelectric performance, it is preferable that the same number of P-type chips and N-type chips are alternately connected in series in the in-plane direction of the substrate with electrodes interposed. .

-substrate-
Materials used for the substrate are not particularly limited, and include glass, silicon, ceramics, metals, plastics, and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, glass, silicon, ceramic, and metal are preferable from the viewpoint of firing (annealing) treatment, and glass, silicon, and ceramic are preferable from the viewpoint of adhesion with thermoelectric conversion materials, material cost, and dimensional stability after heat treatment. is more preferred.
A substrate thickness of 100 to 10000 μm can be used from the viewpoint of process and dimensional stability.

-Method for preparing thermoelectric semiconductor composition-
The method for preparing the thermoelectric semiconductor composition is not particularly limited, and thermoelectric semiconductor particles, a binder resin, an ionic liquid, and optionally An inorganic ionic compound, other additives, and a solvent may be added and mixed and dispersed to prepare the thermoelectric semiconductor composition.
The thermoelectric semiconductor particles, binder resin, ionic liquid, inorganic ionic compound, and other additives are as described above.
Examples of solvents include toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, N-methylpyrrolidone, ethyl cellosolve, and the like. These may be used individually by 1 type, and may use 2 or more types together. The solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.

A coating film (thin film) made of a thermoelectric semiconductor composition can be formed by coating a thermoelectric semiconductor composition on a substrate and drying it.

The method of applying the thermoelectric semiconductor composition onto the substrate is not particularly limited, and may be screen printing, flexographic printing, gravure printing, spin coating, dip coating, die coating, spray coating, bar coating. , a known method such as a doctor blade method. When the coating film is formed in a pattern, screen printing, stencil printing, slot die coating, or the like, which enables easy pattern formation using a screen plate having a desired pattern, is preferably used.

((B) Drying process)
The drying treatment step is a step of forming a coating film (thin film) of a thermoelectric semiconductor composition on a substrate and then drying the coating film of the thermoelectric semiconductor composition at a predetermined temperature while holding the substrate.
A coating film (thin film) is formed by drying the obtained coating film, and as a drying method, a conventionally known drying method such as a hot air drying method, a hot roll drying method, an infrared irradiation method, or the like can be employed. The heating temperature is usually 80 to 150° C., and the heating time is usually several seconds to several tens of minutes, depending on the heating method.
Moreover, when a solvent is used in the preparation of the thermoelectric semiconductor composition, the heating temperature is not particularly limited as long as it is within a temperature range where the solvent used can be dried.
The thickness of the coating film (thin film) made of the thermoelectric semiconductor composition is as described above.

((C) Coating film stripping step)
The coating film stripping step is a step of stripping the coating film (thin film) made of the thermoelectric semiconductor composition from the substrate after the drying treatment.
The method for peeling off the coating film is not particularly limited as long as it is a method that allows the coating film (thin film) to be peeled off from the substrate after the drying process. It may be peeled off in the form of a piece, or may be peeled off collectively in the form of a plurality of coating films (thin films).

((D) Heat press (heat pressurization) treatment step)
The hot pressing (heating and pressurizing) treatment step is a step of performing a hot pressing (heating and pressurizing) treatment after peeling off the coating film (thin film) of the thermoelectric semiconductor composition from the substrate.
This heat pressing (heating and pressurizing) treatment is performed by applying a predetermined pressure to the entire upper surface of the coating film (thin film) for a predetermined time at a predetermined temperature in an atmospheric atmosphere using a device such as a hydraulic press. This is a process of applying pressure.
The temperature of the heat press (heat pressurization) treatment is not particularly limited, but is usually 100 to 300°C, preferably 200 to 300°C.
The pressure of the heat press (heat pressurization) treatment is not particularly limited, but is usually 20 to 200 MPa, preferably 50 to 150 MPa.
The duration of the heat pressing (heating and pressurizing) treatment is not particularly limited, but is usually several seconds to several tens of minutes, preferably several tens of seconds to ten and several minutes.

((E) Firing (annealing) treatment step)
The baking (annealing) treatment step is a step of heat-pressing (heating and pressurizing) a coating film (thin film) of a thermoelectric semiconductor composition, and then heat-treating the coating film of the thermoelectric semiconductor composition at a predetermined temperature.
By performing the baking (annealing) treatment, the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thermoelectric semiconductor composition in the coating film (thin film) can be crystal-grown, and the thermoelectric performance of the thermoelectric conversion material layer can be further improved. can be improved.

The firing (annealing) treatment is not particularly limited, but is usually performed under an atmosphere of an inert gas such as nitrogen or argon with a controlled gas flow rate, under a reducing gas atmosphere, or under vacuum conditions.
The temperature of the baking (annealing) treatment depends on the thermoelectric semiconductor particles, the binder resin, the ionic liquid, the inorganic ionic compound, etc. used in the thermoelectric semiconductor composition, and is adjusted appropriately. °C.
The firing (annealing) time is not particularly limited, but is usually several minutes to several tens of hours, preferably several minutes to several hours.

According to the method for manufacturing the thermoelectric conversion module, the thermoelectric conversion material layer (chip) can be manufactured by a simple method. In addition, since the coating film (thin film) of the thermoelectric semiconductor composition and the electrode are not subjected to firing (annealing) treatment in the form of bonding, the electrical resistance value between the thermoelectric conversion material layer (chip) and the electrode increases. There is no problem such as deterioration of thermoelectric performance.

In the method for manufacturing the thermoelectric conversion module, the thermoelectric conversion module is manufactured using the thermoelectric conversion material layers (chips) obtained through the steps (i) and (ii) above. Here, the above step (i) corresponds to (A) the step of forming a coating film of the thermoelectric semiconductor composition in the method for producing the thermoelectric conversion material layer (chip), and the above step (ii) is the thermoelectric conversion material This corresponds to the (E) firing (annealing) step in the layer (chip) manufacturing method. In addition, the substrate to be used, the coating film (thin film) of the thermoelectric semiconductor composition, and the preferable material, thickness, formation method, and the like constituting them are all the same as those described above.

In the method for manufacturing the thermoelectric conversion module, from the viewpoint of thermoelectric performance, the step (iv) is a step of preparing the second A layer having the second resin film and the second electrode in this order. In the step (vii), the other surface of the chip of the thermoelectric conversion material obtained by peeling in the step (vi) above and the second electrode of the 2A layer prepared in the step (iv) above. It is preferable that it is a step of bonding with the second bonding material layer interposed therebetween.
The thermoelectric conversion module obtained by the above steps corresponds to the π-type thermoelectric conversion module described above.

Further, as another example of the method for manufacturing the thermoelectric conversion module, from the viewpoint of thermoelectric performance, the step (iv) prepares the second B layer having the second resin film and having no electrodes. step, wherein the step (vii) separates the other surface of the thermoelectric conversion material chip obtained by peeling in the step (vi) from the second B layer prepared in the step (iv). It is preferable that it is a step of bonding with the third bonding material layer interposed therebetween.
The thermoelectric conversion module obtained by the above steps corresponds to the in-plane type thermoelectric conversion module described above.

A method for manufacturing the thermoelectric conversion module will be described below with reference to the drawings.
FIG. 4 is an explanatory diagram illustrating an example of a method of manufacturing a thermoelectric conversion module including a thermoelectric conversion material layer of the present invention (method of manufacturing a π-type thermoelectric conversion module), FIG. FIG. 4B is a cross-sectional view after forming a solder-receiving layer, which will be described later, on one surface (upper surface) of the (chip), and FIG. 4B is a cross-sectional view after forming an electrode and a solder material layer on the resin film. , FIG. 4(c) shows the electrode on the resin film obtained in FIG. 4(c′) is a cross-sectional view after bonding the solder material layer by heating and cooling, and FIG. 4(d) is a cross-sectional view after bonding the solder material layer (upper surface) to the substrate. ) is a cross-sectional view after the other surface (lower surface) is peeled off, and FIG. 4(e) is the other surface (chip) of the thermoelectric conversion material layer (chip) on the resin film obtained in FIG. 4(f) is a cross-sectional view after forming a solder-receiving layer on the bottom surface), and FIG. 4(f) is a solder material layer and the solder-receiving layer of FIG. 2 is a cross-sectional view after lamination and bonding with the other surface (lower surface) of the thermoelectric conversion material layer (chip) with the .

<<Electrode formation process>>
In the step of forming an electrode, in the step of preparing the first layer having the first resin film and the first electrode in this order of (iii) in the method for manufacturing the thermoelectric conversion module, This is the step of forming the first electrode. Alternatively, in the step (iv) of preparing the layer 2A having the second resin film and the second electrode in this order, the step of forming the second electrode on the second resin film. In FIG. 4B, for example, a metal layer is formed on the resin film 4 and processed into a predetermined pattern to form the electrode 5 .

(resin film)
The first resin film and the second resin film may be resin films of the same material or resin films of different materials. It has excellent flexibility, and even when a coating film (thin film) made of a thermoelectric semiconductor composition is baked (annealed), the performance of the thermoelectric element can be maintained without thermal deformation of the resin film. A polyimide film, a polyamide film, a polyetherimide film, a polyaramid film, and a polyamideimide film are preferable from the viewpoint of high stability, and a polyimide film is particularly preferable from the viewpoint of high versatility.

The thicknesses of the first resin film and the second resin film are each independently preferably 1 to 1000 μm, more preferably 5 to 500 μm, particularly preferably 10 μm, from the viewpoint of flexibility, heat resistance and dimensional stability. ~100 μm.
The 5% mass loss temperature measured by thermogravimetric analysis (TG) of the first resin film and the second resin film is preferably 300° C. or higher, more preferably 400° C. or higher. The heat dimensional change rate measured at 200° C. in accordance with JIS K7133 (1999) is preferably 0.5% or less, more preferably 0.3% or less. The coefficient of linear expansion in the plane direction measured according to JIS K7197 (2012) is preferably 0.1 to 50 ppm·°C ^-1 , more preferably 0.1 to 30 ppm·°C ^-1 .

(electrode)
As metal materials for the first electrode and the second electrode of the thermoelectric conversion module, copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, or any of these metals are independently used. and alloys containing. These may be used individually by 1 type, and may use 2 or more types together.
The thickness of the electrode (metal material) layer is preferably 10 nm to 200 μm, more preferably 30 nm to 150 μm, particularly preferably 50 nm to 120 μm. If the thickness of the electrode (metal material) layer is within the above range, the electrical conductivity is high, the resistance is low, and sufficient strength as an electrode is obtained.

The electrodes are formed using the metal material described above.
As a method for forming the electrodes, after providing an electrode having no pattern formed on a resin film, a known physical treatment or chemical treatment mainly based on a photolithography method, or a combination thereof, etc., is performed to obtain a predetermined pattern. or a method of directly forming an electrode pattern by a screen printing method, an inkjet method, or the like.
Methods for forming electrodes without a pattern include PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion plating, or CVD (chemical vapor deposition) such as thermal CVD and atomic layer deposition (ALD). dry processes such as vapor phase epitaxy); various coatings such as dip coating, spin coating, spray coating, gravure coating, die coating, doctor blade, and wet processes such as electrodeposition; silver salt method; Electroplating; electroless plating; lamination of metal foil;
From the viewpoint of maintaining the thermoelectric performance, the electrodes are required to have high electrical conductivity and high thermal conductivity. Therefore, it is preferable to use electrodes formed by a plating method or a vacuum film forming method. A vacuum deposition method such as a vacuum deposition method and a sputtering method; an electroplating method; an electroless plating method; Depending on the size of the formed pattern and the required dimensional accuracy, the pattern can be easily formed by interposing a hard mask such as a metal mask.

<<First electrode bonding step>>
The first electrode bonding step is the above step (v) of the method for manufacturing a thermoelectric conversion module, and one surface of the thermoelectric conversion material layer (chip) obtained in the above step (ii) and the above (iii) ) is a step of bonding the first electrode of the first layer prepared in the step of ) with the first bonding material layer interposed therebetween.
In the first electrode bonding step, for example, in FIG. 4(c), a solder material layer 6 on the electrode 5 of the resin film 4 and a thermoelectric conversion material layer (P-type chip) 2a made of a P-type thermoelectric conversion material. , a solder receiving layer 3 formed on one surface of each thermoelectric conversion material layer (N-type chip) 2b made of an N-type thermoelectric conversion material. The P-type chip 2a and the N-type chip 2b are bonded to the electrode 5 by heating the solder material layer 6 to a predetermined temperature, holding it for a predetermined time, and then returning it to room temperature. The heating temperature, holding time, etc. are as described later. FIG. 4(c') shows the state after the solder material layer 6 is returned to room temperature (the solder material layer 6' is solidified by heating and cooling and the thickness is reduced).

(First bonding material layer forming step)
The first electrode bonding step includes a first bonding material layer forming step.
The first bonding material layer forming step is a step of forming the first bonding material layer on the first electrode obtained in the step (iii) in the step (v) of the method for manufacturing a thermoelectric conversion module. be.
The first bonding material layer forming step is, for example, a step of forming a solder material layer 6 on the electrode 5 in FIG. 4B.
The bonding material constituting the first bonding material layer includes a solder material, a conductive adhesive, a sintered bonding agent, etc., and the solder material layer, the conductive adhesive layer, the sintered bonding agent layer, respectively is preferably formed on the electrode. In this specification, the term “conductivity” refers to an electrical resistivity of less than 1×10 ⁶ Ω·m.

The solder material constituting the solder material layer may be appropriately selected in consideration of electrical conductivity and thermal conductivity. Examples include Sn, Sn/Pb alloy, Sn/Ag alloy, Sn/Cu alloy, Sn/Sb. alloy, Sn/In alloy, Sn/Zn alloy, Sn/In/Bi alloy, Sn/In/Bi/Zn alloy, Sn/Bi/Pb/Cd alloy, Sn/Bi/Pb alloy, Sn/Bi/Cd alloy , Bi/Pb alloy, Sn/Bi/Zn alloy, Sn/Bi alloy, Sn/Bi/Pb alloy, Sn/Pb/Cd alloy, Sn/Cd alloy. These may be used individually by 1 type, and may use 2 or more types together.
Among these, 43Sn/57Bi alloy, 42Sn/58Bi alloy, 40Sn/56Bi/4Zn alloy, 48Sn/52In alloy, 39.8Sn/ Alloys such as 52In/7Bi/1.2Zn alloys are preferred.
Commercially available solder materials include the following. For example, 42Sn/58Bi alloy (manufactured by Tamura Corporation, product name: SAM10-401-27), 41Sn/58Bi/Ag alloy (manufactured by Nihon Handa Co., Ltd., product name: PF141-LT7HO), 96.5Sn3Ag0.5Cu alloy (Nihon Handa Co., Ltd. product name: PF305-207BTO), etc. can be used.

The thickness of the solder material layer (after heating and cooling) is preferably 10-200 μm, more preferably 20-150 μm, still more preferably 30-130 μm, and particularly preferably 40-120 μm. When the thickness of the solder material layer is within this range, it becomes easier to obtain adhesion between the thermoelectric conversion material chip and the electrode.

Known methods such as stencil printing, screen printing, and dispensing can be used as methods for applying the solder material onto the substrate. The heating conditions vary depending on the solder material, resin film, etc. used, but are usually carried out at 150 to 280° C. for 3 to 20 minutes.

In addition, when using a solder material layer, it is preferable to interpose a solder-receiving layer, which will be described later, in order to improve the adhesion of the thermoelectric conversion material to the chip.

The conductive adhesive constituting the conductive adhesive layer is not particularly limited, and examples thereof include conductive pastes and binders. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the conductive paste include copper paste, silver paste, nickel paste, and the like. These may be used individually by 1 type, and may use 2 or more types together.
Examples of binders include epoxy resins, acrylic resins, and urethane resins. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the method of applying the conductive adhesive onto the resin film include known methods such as screen printing and dispensing. These may be used individually by 1 type, and may use 2 or more types together.

The thickness of the conductive adhesive layer is preferably 10-200 μm, more preferably 20-150 μm, still more preferably 30-130 μm, and particularly preferably 40-120 μm.

The sintering bonding agent forming the sintering bonding agent layer is not particularly limited, and examples thereof include sintering paste.
Sintering paste consists of, for example, micron-sized metal powder and nano-sized metal particles. Unlike conductive adhesives, sintering paste directly joins metals by sintering. Epoxy resin, acrylic resin, urethane resin, etc. of resin may be included.
Examples of the sintering paste include silver sintering paste and copper sintering paste. These may be used individually by 1 type, and may use 2 or more types together.
Methods for applying the sintered bonding agent layer onto the resin film include known methods such as screen printing, stencil printing, and dispensing. These may be used individually by 1 type, and may use 2 or more types together.
The sintering conditions are usually 100 to 300° C. for 30 to 120 minutes, although they differ depending on the metal material used.
Examples of commercially available sintering bonding agents include silver sintering pastes such as sintering paste (manufactured by Kyocera Corporation, product name: CT2700R7S), sintering type metal bonding materials (manufactured by Nihon Handa Co., Ltd., product name: MAX102), and the like. Available.

The thickness of the sintered adhesive layer is preferably 10-200 μm, more preferably 20-150 μm, still more preferably 30-130 μm, and particularly preferably 40-120 μm.

<<Solder Receiving Layer Forming Process>>
In the method for manufacturing a thermoelectric conversion module, for example, when manufacturing a π-type thermoelectric conversion module or an in-plane type thermoelectric conversion module, the thermoelectric conversion after the firing (annealing) treatment obtained in the above step (ii) Preferably, the step of forming a solder receptive layer on one side of the chip of material is included.

The solder-receiving layer forming step is a step of forming a solder-receiving layer on a thermoelectric conversion material layer (chip) made of a thermoelectric conversion material. In this step, a solder receiving layer 3 is formed on one surface of a thermoelectric conversion material layer (P-type chip) 2a and a thermoelectric conversion material layer (N-type chip) 2b made of an N-type thermoelectric conversion material.

Preferably, the solder-receiving layer comprises a metallic material. The metal material is preferably at least one selected from gold, silver, aluminum, rhodium, platinum, chromium, palladium, tin, and alloys containing any of these metal materials. Among these, a two-layer structure of gold, silver, aluminum, or tin and gold is preferable, and from the viewpoint of material cost, high thermal conductivity, and bonding stability, silver and aluminum are more preferable.
Furthermore, the solder receiving layer may be formed using a paste material containing a solvent or a resin component in addition to the metal material. When a paste material is used, it is preferable to remove the solvent and resin components by firing or the like as described later. Silver paste and aluminum paste are preferable as the paste material.

The thickness of the solder-receiving layer is preferably 10 nm to 50 μm, more preferably 50 nm to 16 μm, even more preferably 200 nm to 4 μm, particularly preferably 500 nm to 3 μm. When the thickness of the solder receiving layer is within this range, the adhesion to the surface of the thermoelectric conversion material layer (chip) made of the thermoelectric conversion material and the adhesion to the surface of the solder material layer on the electrode side are excellent, resulting in high reliability. high bonding is obtained. In addition, since high thermal conductivity can be maintained as well as electrical conductivity, the thermoelectric performance of the thermoelectric conversion module is maintained without deteriorating.
The solder-receiving layer may be formed by forming a metal material as it is and used as a single layer, or may be used as a multilayer by laminating two or more metal materials. Alternatively, the film may be formed as a composition containing a metal material in a solvent, resin, or the like. However, in this case, from the viewpoint of maintaining high electrical conductivity and high thermal conductivity (maintaining thermoelectric performance), it is recommended to remove the resin components, including the solvent, etc., by baking, etc., as the final form of the solder-receiving layer. preferable.

Formation of the solder-receiving layer is preferably carried out using the aforementioned metal material.
As a method for forming the solder-receiving layer, after providing a solder-receiving layer having no pattern formed on the thermoelectric conversion material layer (chip), a known physical treatment or chemical treatment mainly based on a photolithographic method, Alternatively, a method of forming a predetermined pattern shape by using them in combination, or a method of directly forming a pattern of the solder receiving layer by a screen printing method, a stencil printing method, an inkjet method, or the like can be mentioned.
Methods for forming a solder-receiving layer having no pattern include PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion plating; CVD such as thermal CVD and atomic layer deposition (ALD); chemical vapor deposition method); various coating methods such as dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method; wet process such as electrodeposition method; salt method; electrolytic plating method; electroless plating method; metal foil lamination;
From the viewpoint of maintaining thermoelectric performance, the solder-receiving layer is required to have high electrical conductivity and high thermal conductivity. It is preferred to use a deposited solder-receiving layer.

<<Chip Batch Peeling Process>>
The chip batch peeling step is the step (vi) of the method for manufacturing a thermoelectric conversion module, and is a step of peeling the other surface of the thermoelectric conversion material layer (chip) after the step (v) from the substrate.
For example, in (d) of FIG. 4, the chip batch peeling process is performed by separating a thermoelectric conversion material layer (P-type chip) 2a made of a P-type thermoelectric conversion material from the substrate 1 and a thermoelectric conversion material layer (P-type chip) 2a made of an N-type thermoelectric conversion material ( In this step, the other surface of the N-type chip 2b is collectively peeled off.
The method for peeling off the thermoelectric conversion material layer is not particularly limited as long as it is a method capable of removing all the thermoelectric conversion material layers (chips) from the substrate at once.

<<Second electrode bonding step>>
The second electrode bonding step is included in the above step (vii) of the method for manufacturing a thermoelectric conversion module, and the other side of the thermoelectric conversion material layer (chip) obtained by peeling in the above step (vi) This is a step of bonding the surface and the second electrode of the 2A layer prepared in the step (iv) with the second bonding material layer interposed therebetween.
In the second electrode bonding step, for example, in (f) of FIG. In this step, the other surface of the chip 2b is joined to the electrodes 5 on the resin film 4 with the solder receiving layer 3 and the solder material layer 6 interposed.
The materials for both the second electrode and the second resin film of the 2A layer can be the same as those described in the first electrode bonding step, and the bonding method is also the same.
It is preferable that the bonding with the electrode is performed through the solder material layer, the conductive adhesive layer, or the sintered bonding agent layer.

(Second bonding material layer forming step)
The second electrode bonding step includes a second bonding material layer forming step.
The second bonding material layer forming step includes forming a second bonding material layer on the second electrode of the 2A layer prepared in the step (iv) in the step (vii) of the method for manufacturing a thermoelectric conversion module. It is a process of forming.
The second bonding material layer can use the same material as the first bonding material layer described above, and the formation method, thickness, etc. are all the same.

Further, for example, when a solder material layer is used when manufacturing a π-type thermoelectric conversion module, a Preferably, the step of forming a solder receptive layer is included.
For example, in (e) of FIG. 4, the other surface of the thermoelectric conversion material layer (P-type chip) 2a made of the P-type thermoelectric conversion material and the thermoelectric conversion material layer (N-type chip) 2b made of the N-type thermoelectric conversion material This is the step of forming the solder receiving layer 3 on the substrate.

The combination of the bonding material layers used for the electrodes on the pair of resin films in the thermoelectric conversion module (except for the case where there is no electrode on either of the pair of resin films) is not particularly limited, but the thermoelectric conversion From the viewpoint of preventing mechanical deformation of the module and suppressing deterioration in thermoelectric performance, a combination of solder material layers, conductive adhesive layers, or sintered adhesive layers is preferable.

<<Resin film bonding process>>
The resin film bonding step is included in the above step (vii) of the method for manufacturing a thermoelectric conversion module, and the other surface of the thermoelectric conversion material layer (chip) obtained by peeling in the above step (vi). 2) is a step of bonding the 2B layer having the second resin film and having no electrodes prepared in the step (iv) with the third bonding material layer interposed therebetween. The second resin film is as described above. A third bonding material layer is used for bonding with the 2B layer having the second resin film and no electrode.

The bonding material forming the third bonding material layer is preferably a resin material, and is formed on the resin film as the resin material layer.
The resin material preferably contains a polyolefin resin, an epoxy resin, or an acrylic resin. Furthermore, it is preferable that the resin material has adhesiveness and low water vapor permeability. In the present specification, having tackiness means that the resin material has tackiness, adhesiveness, and pressure-sensitive tackiness that enables adhesion by pressure-sensitivity at the initial stage of application.
Formation of the resin material layer can be performed by a known method.

The thickness of the resin material layer is preferably 1-100 μm, more preferably 3-50 μm, and particularly preferably 5-30 μm.

(Another method for manufacturing a thermoelectric conversion module)
Another example of the method for manufacturing the thermoelectric conversion module is the following method.
Specifically, a plurality of chips are obtained by peeling off the plurality of chips one by one from the substrate described above, and the plurality of chips are arranged one by one on predetermined electrodes on a resin film. This is a method of forming a thermoelectric conversion module through processes.
As a method of arranging a plurality of chips on the electrode, a known method can be used, such as handling each chip one by one by a robot or the like, aligning the chips with a microscope or the like, and arranging them.

According to the manufacturing method of the thermoelectric conversion module, the chips can be formed by a simple method, and in the thermoelectric conversion module in which a plurality of chips are combined, the thermoelectric semiconductor composition in the conventional firing (annealing) treatment process It is possible to prevent deterioration of thermoelectric performance due to the formation of an alloy layer due to diffusion between and electrodes.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

For the thermoelectric performance evaluation of the test piece (chip) obtained by dicing the thermoelectric conversion material layer prepared in Examples and Comparative Examples, the electrical conductivity, Seebeck coefficient and thermal conductivity are calculated by the following method. It was done by
<Thermoelectric performance evaluation>
(a) Electrical conductivity For each test piece (chip) obtained by dicing the thermoelectric conversion material layers obtained in Examples and Comparative Examples, using a low resistance meter (manufactured by Hioki Electric Co., Ltd., RM3545), 4 The electrical resistance value (Ω) is measured by terminal measurement, and the thickness (cm) of the test piece and the area of the test piece (the plane perpendicular to the thickness direction of the test piece; cm ² ) are used to determine the electrical conductivity. The ratio σ (S/cm) was calculated from the following formula.
Electrical conductivity σ = (electric resistance value x thickness of test piece) / area of test piece (b) Seebeck coefficient The thermoelectromotive force of the test piece (chip) obtained by the above was measured, and the Seebeck coefficient S was calculated. The thermoelectromotive force is obtained by heating one end of the thermoelectric conversion material prepared, measuring the temperature difference generated between both ends of the thermoelectric conversion material using a chromel-alumel thermocouple, and measuring the potential between the electrodes adjacent to the thermocouple installation position. It was measured. Specifically, the distance between both ends of the sample for measuring the temperature difference and electromotive force was set to 25 mm, one end was kept at 20 ° C., and the other end was heated from 25 ° C. to 50 ° C. in 1 ° C. steps. The power was measured and the Seebeck coefficient S (μV/K) was calculated from the slope. The thermocouple and the electrode were installed at symmetrical positions with respect to the center line of the thin film, and the distance between the thermocouple and the electrode was 1 mm.
(c) Thermal conductivity Thermal conductivity λ (W/(m·K)) was calculated using the 3ω method for measuring thermal conductivity.
A thermoelectric figure of merit Z (Z=σS ² /λ) was obtained from the obtained electrical conductivity σ, Seebeck coefficient S and thermal conductivity λ, and a dimensionless thermoelectric figure of merit ZT (T=300K) was calculated.
However, the thermoelectric figure of merit Z was calculated using the electric conductivity σ (S/m) and the Seebeck coefficient S (V/K).

(Example 1)
<Preparation of test piece (chip) made of thermoelectric conversion material>
(1) Preparation of thermoelectric semiconductor particles As thermoelectric semiconductor particles, P-type bismuth telluride Bi _0.4 Te _3.0 Sb _1.6 (manufactured by Kojundo Chemical Laboratory, particle size: 16 .0 μm) was used. Further, the thermoelectric semiconductor particles were subjected to particle size distribution measurement using a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern).
(2) Preparation of thermoelectric semiconductor composition As shown in Example 1 of Table 1, P-type bismuth telluride Bi _0.4 Te _3.0 Sb _1.6 particles (average particle size 16.0 μm) 78.5 mass %, polyethylene carbonate solution containing polyethylene carbonate (final decomposition temperature: 250 ° C.) as a binder resin (manufactured by Empower Materials, QPAC25, solvent: N-methylpyrrolidone, solid content concentration: 25% by mass) 20.7% by mass ( Solid content 6.7% by mass) and 1-butylpyridinium bromide (manufactured by Koei Chemical Industry Co., Ltd., IL-P18B) 0.8% by mass as an ionic liquid are mixed and dispersed to prepare a coating liquid consisting of a thermoelectric semiconductor composition. bottom.
(3) Preparation of test piece (chip) composed of thermoelectric conversion material layer (formation of thermoelectric conversion material layer)
The coating liquid prepared in (2) is applied to a polyimide film (manufactured by Ube Industries, Ltd., trade name “Kapton 500H”, thickness 125 μm) using an applicator, and dried by heating at a temperature of 110 ° C. for 20 minutes. A thin film with a thickness of 600 μm was formed. Then, the obtained thin film was subjected to heat and pressure press at 250° C. and 50 MPa for 30 minutes to produce a wafer having a thermoelectric semiconductor material layer with a thickness of 250 μm on the polyimide film. Furthermore, the temperature of the fabricated wafer was raised at a heating rate of 5 K/min in a mixed gas atmosphere of hydrogen and argon (hydrogen: argon = 3% by volume: 97% by volume), and the firing (annealing) temperature was 430°C. After holding the wafer for 30 minutes, the wafer was diced to obtain a test piece (chip) of 1.0×1.0 mm square.

(Example 2)
A thermoelectric conversion material layer was produced in the same manner as in Example 1, except that the average particle size of the thermoelectric semiconductor particles was changed from 16.0 μm to 8.0 μm.
The thermoelectric semiconductor particles having an average particle size of 8.0 μm are P-type bismuth telluride Bi _0.4 Te _3.0 Sb _1.6 (manufactured by Kojundo Chemical Laboratory, particle size: 16.0 μm). It was prepared by grinding in a nitrogen gas atmosphere using a ball mill (Premium line P-7 manufactured by Fritsch Japan). Particle size distribution of the pulverized thermoelectric semiconductor particles was measured using a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern).

(Example 3)
A thermoelectric conversion material layer was produced in the same manner as in Example 1, except that the average particle diameter of the thermoelectric semiconductor particles was 35.0 μm (manufactured by Kojundo Chemical Laboratory Co., Ltd.).

(Comparative example 1)
A thermoelectric conversion material layer was produced in the same manner as in Example 1, except that the average particle size of the thermoelectric semiconductor particles was changed from 16.0 μm to 2.0 μm.
The thermoelectric semiconductor particles having an average particle size of 2.0 μm are P-type bismuth telluride Bi _0.4 Te _3.0 Sb _1.6 (manufactured by Kojundo Chemical Laboratory, particle size: 16.0 μm). It was prepared by grinding in a nitrogen gas atmosphere using a ball mill (Premium line P-7 manufactured by Fritsch Japan). Particle size distribution of the pulverized thermoelectric semiconductor particles was measured using a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern).

(Comparative example 2)
A thermoelectric conversion material layer was produced in the same manner as in Example 1, except that the average particle diameter of the thermoelectric semiconductor particles was 50.0 μm (manufactured by Kojundo Chemical Laboratory Co., Ltd.).

(Comparative Example 3)
A thermoelectric conversion material layer was produced in the same manner as in Example 1, except that the average particle size of the thermoelectric semiconductor particles was changed from 16.0 μm to 5.0 μm.
The thermoelectric semiconductor particles having an average particle size of 5.0 μm are P-type bismuth telluride Bi _0.4 Te _3.0 Sb _1.6 (manufactured by Kojundo Chemical Laboratory, particle size: 16.0 μm). It was prepared by grinding in a nitrogen gas atmosphere using a ball mill (Premium line P-7 manufactured by Fritsch Japan). Particle size distribution of the pulverized thermoelectric semiconductor particles was measured using a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern).

Table 2 shows the evaluation results of the thermoelectric performance of the test pieces (chips) of the thermoelectric conversion material layers obtained in Examples 1-3 and Comparative Examples 1-3.

The thermoelectric performance (dimensionless thermoelectric figure of merit ZT) of the thermoelectric conversion material layers of Examples 1 to 3, in which the range of the average particle diameter of the thermoelectric semiconductor particles satisfies the provisions of the present invention, was determined by the range of the average particle diameter of the thermoelectric semiconductor particles. It can be seen that the thermoelectric performance is better than the thermoelectric performance of the thermoelectric conversion material layers of Comparative Examples 1 to 3, which do not satisfy the provisions of the invention.

By using the thermoelectric conversion material layer of the present invention as a thermoelectric conversion element layer of a thermoelectric conversion module, for example, exhaust heat from various combustion furnaces such as factories, waste combustion furnaces, cement combustion furnaces, combustion gas exhaust from automobile It is conceivable to apply it to power generation applications that convert heat and waste heat from electronic equipment into electricity. For cooling applications, in the field of electronics equipment, for example, smartphones, CPUs (Central Processing Units) used in various computers, etc., image sensors such as CMOS (Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. , MEMS (Micro Electro Mechanical Systems), and temperature control of various sensors such as light receiving elements.

1, 1a: Substrate 2a: Thermoelectric conversion material layer (P-type chip) made of P-type thermoelectric conversion material
2b: Thermoelectric conversion material layer (N-type chip) made of N-type thermoelectric conversion material
3: Solder receiving layer 4: Resin film 5: Electrode 6: Solder material layer (when formed)
6': Solder material layer (after bonding)
12: Coating film 12a of thermoelectric semiconductor composition: Coating film 12b: Coating

films

20, 20s, 20t: Thermoelectric conversion material layer 30: Gap part 30b: Gap part 40b: Gap 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 thickness direction (longitudinal section)
C: Central part of the thermoelectric conversion material layer

Claims

A thermoelectric conversion material layer containing a thermoelectric conversion material made of a thermoelectric semiconductor composition containing thermoelectric semiconductor particles, a binder resin and an ionic liquid, wherein the thermoelectric semiconductor particles have an average particle size of 8.0 μm or more and less than 50.0 μm. Thermoelectric conversion material layer.
The thermoelectric conversion material layer has the thermoelectric conversion material and voids, and when the ratio of the area occupied by the thermoelectric conversion material in the area of the longitudinal section including the central portion of the thermoelectric conversion material layer is defined as the filling rate, the The thermoelectric conversion material layer according to claim 1, wherein the filling factor is 0.900 or more and less than 1.000.
The thermoelectric conversion material layer according to claim 1 or 2, wherein the thermoelectric conversion material layer is made of a sintered body of a coating film of a thermoelectric semiconductor composition.
The thermoelectric conversion material layer according to claim 1, wherein the binder resin decomposes by 90% by mass or more at the firing temperature of the fired body.
The thermoelectric conversion material layer according to claim 1 or 4, wherein the binder resin contains at least one selected from polycarbonates, cellulose derivatives and polyvinyl polymers.
The thermoelectric conversion material layer according to any one of claims 1, 4 and 5, wherein the binder resin decomposes at 400°C by 90% by mass or more.
The thermoelectric conversion material layer according to claim 1, wherein the thermoelectric semiconductor particles are composed of a bismuth-tellurium-based thermoelectric semiconductor material, a telluride-based thermoelectric semiconductor material, an antimony-tellurium-based thermoelectric semiconductor material, or a bismuth-selenide-based thermoelectric semiconductor material.
The thermoelectric conversion material layer according to claim 1 or 7, wherein the thermoelectric semiconductor particles have an average particle size of 8.0 µm or more and less than 40.0 µm.
A thermoelectric conversion module comprising the thermoelectric conversion material layer according to any one of claims 1 to 8.