KR20170102477A - Thermoelectric conversion device and electricity storage system - Google Patents

Abstract

A thermoelectric conversion device having optical transparency and capable of regenerating electric energy from thermal energy, the thermoelectric conversion device comprising a thermoelectric conversion layer formed of a thermoelectric material and an electrode layer connected to the thermoelectric conversion layer, Wherein at least the thermoelectric conversion layer among the thermoelectric conversion layer and the electrode layer has optical transparency.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a thermoelectric conversion device,

The present invention relates to a thermoelectric conversion device and a power storage system in which at least a substrate and a thermoelectric conversion layer among a substrate, a thermoelectric conversion layer and an electrode layer have light transmittance.

The thermoelectric material has a characteristic in which a potential difference is generated by imparting a temperature difference to both ends of the material. On the contrary, by imparting a potential difference to the thermoelectric material, a temperature difference is generated to cause release or absorption of heat energy, and the characteristic has a property of raising or lowering the ambient temperature. As an example utilizing this characteristic of the thermoelectric material, there is disclosed a technique of functioning as a cooling device by energizing a thermoelectric conversion device using a thermoelectric material having transparency in a state of being adhered to a window glass or the like (see Patent Document 1).

In recent years, by taking advantage of the above-mentioned characteristics of the thermoelectric material from the consideration of the environment and the interest in energy saving, it is possible to utilize the characteristics of the thermoelectric material contrary to the technology of the above-mentioned Patent Document 1, A technique of regenerating electrical energy from thermal energy by disposing a thermoelectric conversion device at a place where a temperature difference occurs is being studied.

International Publication No. 2012/140800

A further object of the present invention is to provide a thermoelectric conversion device and a power storage system which have optical transparency and can regenerate electric energy from thermal energy as a further application of the thermoelectric conversion device.

The present invention provides the following (1) to (9).

(1) A thermoelectric conversion device comprising a thermoelectric conversion layer formed of a thermoelectric material and an electrode layer connected to the thermoelectric conversion layer, wherein at least the thermoelectric conversion layer of the thermoelectric conversion layer and the electrode layer has light transmittance.

(2) In the above (1), in which at least the thermoelectric conversion layer of the thermoelectric conversion layer and the electrode layer cross the plane of the thermoelectric conversion layer and the visible light transmittance at 550 nm measured using a spectrophotometer is 60% A thermoelectric conversion device as set forth in claim 1.

(3) The thermoelectric conversion device according to the above (1) or (2), wherein the thermoelectric conversion layer and the electrode layer have a base material on the surface and the base material is an inorganic material having light transmission property or an organic material having light transmission property.

(4) The thermoelectric conversion device according to any one of (1) to (3), wherein the thermoelectric material is an n-type thermoelectric material.

(5) The thermoelectric conversion device according to any one of (1) to (3), wherein the thermoelectric material is a p-type thermoelectric material.

(6) The thermoelectric conversion element according to any one of (6) to (7), wherein the thermoelectric conversion layer has an n-type thermoelectric conversion layer formed of an n-type thermoelectric material and a p-type thermoelectric conversion layer formed of a p- The thermoelectric conversion device according to any one of (1) to (5), wherein the thermoelectric conversion device is connected to the thermoelectric conversion device.

(7) The thermoelectric conversion element according to any one of (1) to (6) above, wherein the ratio of the area of the area excluding the region where the electrode layer is formed to the flat area of the thermoelectric conversion device is not less than 1% and not more than 99% Conversion device.

(8) The thermoelectric conversion device according to any one of (1) to (7), wherein the electrode layer has light transmittance.

(9) A thermoelectric conversion device as described in any one of (1) to (8) above, and a power storage device for storing electricity, wherein the electrode layer of the thermoelectric conversion device is electrically connected to the power storage device The power storage system.

According to the present invention, it is possible to provide a thermoelectric conversion device and a power storage system that have optical transparency and can regenerate electric energy from thermal energy.

1 is a plan view of a thermoelectric conversion device 1 according to an embodiment of the present invention, viewed from a direction perpendicular to a main surface thereof.
Fig. 2 is a cross-sectional view taken along line F1-F1 shown in Fig.
3 is a plan view of the thermoelectric conversion device 2 according to the embodiment of the present invention, viewed from the vertical direction.
4 is a cross-sectional view taken along the line F3-F3 shown in Fig.
5 is a schematic view for explaining an example of the microstructure of the electrode layer of the thermoelectric conversion device according to the present embodiment.
6 is a schematic view for explaining an example of the microstructure of the electrode layer of the thermoelectric conversion device according to the present embodiment.

[Thermoelectric conversion device]

A thermoelectric conversion device according to an embodiment of the present invention is a thermoelectric conversion device comprising a thermoelectric conversion layer formed of a thermoelectric material and an electrode layer connected to the thermoelectric conversion layer, wherein at least the thermoelectric conversion layer And has light transmittance.

[Configuration of thermoelectric conversion device]

The thermoelectric conversion devices 1 and 2 according to the embodiment of the present invention will be described in detail with reference to the drawings. Fig. 1 is a plan view of a thermoelectric conversion device 1 formed in a sheet shape as viewed from a vertical direction, and Fig. 2 is a cross-sectional view taken along line F1-F1 shown in Fig.

The thermoelectric conversion device 1 includes a substrate 11 and a thermoelectric conversion layer 12 (p-type semiconductor layer) and a thermoelectric conversion layer 13 (n Type thermoelectric conversion layer) and an electrode layer 14 connected to the thermoelectric conversion layers 12 and 13, respectively. In the thermoelectric conversion device 1, at least the base material 11 and the thermoelectric conversion layers 12 and 13 among the base material 11, the thermoelectric conversion layers 12 and 13 and the electrode layer 14 have light transmittance. Each constituent requirement will be described later in detail.

The thermoelectric conversion device 2 shown in Figs. 3 and 4 differs from the thermoelectric conversion device 1 in the configuration of the thermoelectric conversion layer. called single-leg type structure using one type of thermoelectric conversion layer selected from a p-type thermoelectric conversion layer and an n-type thermoelectric conversion layer. Fig. 3 is a plan view of the thermoelectric conversion device 2 formed in a sheet shape as viewed from a vertical direction, and Fig. 4 is a cross-sectional view taken along line F3-F3 shown in Fig.

The thermoelectric conversion device 2 includes a substrate 21, a thermoelectric conversion layer 22, and an electrode layer 23 connected to the thermoelectric conversion layer 22. In the thermoelectric conversion device 2, at least the base material 21 and the thermoelectric conversion layer 22 among the base material 21, the thermoelectric conversion layer 22 and the electrode layer 23 have optical transparency. Each constituent requirement will be described later in detail.

It is preferable that at least the thermoelectric conversion layer among the thermoelectric conversion layers and the electrode layers in both of the thermoelectric conversion devices 1 and 2 has a visible light transmittance of 550 nm or more, which is measured using a spectrophotometer in a direction crossing the plane of the substrate, .

In the thermoelectric conversion devices 1 and 2, the substrates 11 and 21 may be omitted. That is, the thermoelectric conversion layer and the electrode layer may be formed directly on a display surface of an electronic device such as an information processing terminal, a window glass of a building, a glass for a car, or the like.

From the viewpoint of light transmittance, the thickness of the thermoelectric conversion devices 1 and 2 is preferably 0.2 m or more and 6000 m or less.

The thermoelectric conversion device 1 can be made into a sheet having a desired area by connecting a plurality of units by electrodes. The same applies to the thermoelectric conversion device 2.

Although not shown in Figs. 1 to 4, an electrode layer for taking out a thermoelectric power is connected to the electrode layer 14 of the thermoelectric conversion device 1, and the thermoelectric power from the thermoelectric conversion device 1 is taken out , A storage device or the like, or can be used as a power source of a device.

<Description>

The thermoelectric conversion layer 22 and the electrode layer 23 are disposed on the surfaces of the base materials 11 and 21 according to the present embodiment. The substrates 11 and 21 are not particularly limited as long as they are light-transmissive inorganic materials or light-permeable organic materials and have sufficient strength.

Examples of the material of the substrate include glass materials such as soda lime glass, borosilicate glass, quartz glass, borosilicate glass, alkali-free glass, cheeseclass glass, white plate glass, aluminosilicate glass and calcium fluoride glass, polyimide, polyamide, , Polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cycloolefin polymer, aromatic Based polymer, a polyurethane-based polymer, and the like.

Among them, a polyester, a polyamide or a cycloolefin-based polymer is preferable, and a polyester or a cycloolefin-based polymer is more preferable because of excellent transparency and versatility.

Examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyarylate.

Examples of polyamides include all aromatic polyamides, nylon 6, nylon 66, and nylon copolymers.

Examples of the cycloolefin-based polymer include a norbornene polymer, a monocyclic cycloolefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and hydrides thereof. Specific examples thereof include Arpel (registered trademark, ethylene-cycloolefin copolymer of Mitsui Chemical), Aton (registered trademark, norbornene polymer of JSR Corporation), Zeonoa (registered trademark, norbornene polymer of Nippon Zeon Co., ) And the like.

Of these, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and polyarylate are preferable from the viewpoint of versatility and cost, and polyethylene terephthalate is more preferable.

The substrate may contain various additives such as an antioxidant, a flame retardant, a lubricant and the like in addition to these components as long as the transparency and the like are not impaired.

The thickness of the substrate is preferably from 0.1 탆 to 5000 탆. When the thickness of the base material is within this range, a thermoelectric conversion device having excellent transparency can be easily obtained.

The total light transmittance of the substrate (measured in accordance with JIS K7361-1) is preferably 70% or more, more preferably 70 to 100%, and still more preferably 80 to 95%. The haze value of the substrate is preferably 10% or less, and more preferably 1 to 10%. By making the total light transmittance or haze value of the substrate fall within these ranges, it is possible to easily obtain a thermoelectric conversion device having excellent transparency.

Particularly, the visible light transmittance (transmittance at 550 nm) of the substrate is preferably 60% or more, more preferably 80% or more, still more preferably 85% or more and 99% or less, Or less. The refractive index of the base material differs depending on the material and the presence or absence of stretching, but is usually in the range of 1.45 to 1.75, preferably 1.6 to 1.75 from the viewpoint of transparency.

&Lt; Thermoelectric conversion layer &

In the present embodiment, the thermoelectric conversion layers 12, 13, and 22 are formed of a thermoelectric material having a high defoaming effect and also having light transmittance.

The thermoelectric material includes an inorganic material and an organic material. Examples of the inorganic material include a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, and the like. Specifically, tin oxide, tin oxide doped with antimony (ATO); Fluorine-doped tin oxide (FTO), zinc oxide, gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), indium oxide, indium tin oxide (ITO), zinc oxide indium Conductive metal oxides; Metals such as gold, silver, chromium, and nickel; Mixtures of these metals with conductive metal oxides; Inorganic conductive substances such as copper iodide and copper sulfide; Organic conductive materials such as polyaniline, polythiophene, and polypyrrole; And the like.

Among these, conductive metal oxides are preferable from the viewpoint of conductivity. In order to suppress the use of rare metal and to design the product in consideration of the environment, zinc oxide, gallium-doped zinc oxide (GZO) Zinc oxide (AZO), zinc oxide indium (IZO), and the like are more preferable, and zinc oxide (GZO) doped with gallium is more preferable in consideration of durability and material cost, , And zinc oxide in which the amount of gallium trioxide is added in the range of 1 to 10% is particularly preferable. The thermoelectric conversion layers 12, 13, and 22 may be formed by stacking a plurality of layers including the above-described materials.

On the other hand, examples of the organic material that can be used for forming the thermoelectric conversion layer include those having a Seebeck effect and having optical transparency. Examples of such organic polymer compounds include polyanilines, polypyrroles, or polythiophenes and their derivatives, which are conductive polymers having conductivity by the π electron conjugation, in view of their excellent dispersibility, easy formation of a coating film, and high transparency. Is preferably used.

The polyaniline is a high molecular weight compound of a compound obtained by substituting an alkyl group, an alkoxy group, an aryl group, or a sulfonic acid group having 1 to 18 carbon atoms for the 2-position or 3-position or the N-position of aniline, Methylaniline, poly-2-ethoxyaniline, poly-3-ethoxyaniline, poly-N-methylaniline, , Poly N-propylaniline, poly N-phenyl-1-naphthylaniline, poly 8-anilino-1-naphthalenesulfonic acid, Sulfonic acid and the like.

The polypyrrole is a high molecular weight compound of a compound obtained by substituting the 1-position or 3-position of pyrrole with an alkyl group or an alkoxy group having 1 to 18 carbon atoms at the 4-position, and examples thereof include poly-1-methyl pyrrole, 1-ethylpyrrole, poly-3-ethylpyrrole, poly-1-methoxypyrrole, 3-methoxypyrrole, poly-1-ethoxypyrrole and poly-3-ethoxypyrrole.

The polythiophenes are high molecular weight compounds of compounds in which the 3-position or 4-position of thiophene is substituted with an alkyl or alkoxy group having 1 to 18 carbon atoms, and examples thereof include poly-3-methylthiophene, , Poly-3-methoxythiophene, poly-3-ethoxythiophene, and poly 3,4-ethylenedioxythiophene (PEDOT).

Examples of derivatives of polyanilines, polypyrroles or polythiophenes include dopants thereof.

Examples of the dopant include halide ions such as chloride ion, bromide ion and iodide ion; Perchlorate ion; Tetrafluoroboric acid ion; Hexafluorosulfate ion; Sulfate ion; Nitrate ion; Thiocyanate ions; Hexafluorosilicate ion; Phosphate ions such as phosphate ions, phenylphosphate ions, and hexafluorophosphate ions; Trifluoroacetic acid ion; Alkylbenzenesulfonic acid ions such as tosylate ion, ethylbenzenesulfonate ion and dodecylbenzenesulfonate ion; Alkylsulfonic acid ions such as methylsulfonic acid ion and ethylsulfonic acid ion; Or polymer ions such as polyacrylate ion, polyvinyl sulfonate ion, polystyrenesulfonate ion (PSS), and poly (2-acrylamide-2-methylpropanesulfonate) ion. May be used.

Among them, a polyacrylate ion, a polyvinyl sulfonate ion, a polystyrenesulfonate ion (PSS) ion, and the like are preferable from the point of view of having a hydrophilic skeleton which can easily adjust high conductivity and which is useful for easy dispersion in an aqueous solution. , Poly (2-acrylamido-2-methylpropanesulfonic acid) ion and the like are preferable, and polystyrenesulfonic acid ion (PSS) which is water-soluble and strongly acidic polymer is more preferable.

As the derivatives of the polyanilines, polypyrroles or polythiophenes, derivatives of polythiophenes are preferable. Among them, a mixture of poly (3,4-ethyleneoxy dithiophene) and polystyrene sulfonate ion as a dopant Hereinafter sometimes referred to as &quot; PEDOT: PSS &quot;).

Among the thermoelectric conversion layers obtained using the above-described materials, a single-leg type thermoelectric conversion layer containing only n-type GZO can be used as the thermoelectric conversion layer including the n-type thermoelectric material. Further, a single-leg type thermoelectric conversion layer containing only PEDOT: PSS can be used as the thermoelectric conversion layer including the p-type thermoelectric material.

In the embodiment of the present invention, the thermoelectric conversion layer has an n-type thermoelectric conversion layer formed of an n-type thermoelectric material and a p-type thermoelectric conversion layer formed of a p-type thermoelectric material, A pn junction type in which the conversion layer is connected by an electrode layer is preferable. Among them, a pn junction type in which PEDOT: PSS and GZO are combined is preferable.

The thermoelectric conversion layer may be a single layer containing the above-described materials, or may be a structure in which two or more layers of the above-mentioned materials each containing a different kind of material are laminated.

The total thickness of the thermoelectric conversion layer and the electrode layer to be described later is preferably not less than 0.1 mu m and not more than 1,000 mu m, more preferably not less than 0.1 mu m and not more than 10 mu m. Within this range, the total light transmittance is high and good transparency is obtained.

The total light transmittance of the thermoelectric conversion layer alone is preferably 50% or more, more preferably 60% or more and 90% or less, and still more preferably 70% or more and 90% or less.

The haze value of the thermoelectric conversion layer alone is preferably 10% or less, more preferably 1% or more and 5% or less. By making the total light transmittance and the haze value of the thermoelectric conversion layer fall within these ranges, it is possible to easily obtain the thermoelectric conversion layer having excellent transparency.

In particular, the visible light transmittance (transmittance at 550 nm) of the thermoelectric conversion layer alone is preferably 60% or more, more preferably 65% or more and 90% or less, and still more preferably 70% or more and 90% or less.

The electrical conductivity of the thermoelectric conversion layer is preferably 100 S / cm or more and 1500 S / cm or less, more preferably 400 S / cm or less, from the viewpoint of raising the output voltage regardless of whether the thermoelectric conversion layer is n- cm or more and 1300 S / cm or less.

The thermal conductivity of the thermoelectric conversion layer is preferably from 0.1 to 100, more preferably from 0.1 W / m · K to 50 W / m · K from the viewpoint of increasing the output voltage without regard to whether the thermoelectric conversion layer is n-type or p- More preferably 0.1 W / m · K or more and 10 W / m · K or less.

&Lt; Electrode layer &

In consideration of the light transmittance of the thermoelectric conversion device 1 in the thermoelectric conversion device 1 according to the present embodiment, the electrode layer 14 has an area of a region excluding a region where the electrode layer is formed, Is preferably 1% or more and 99% or less. From the viewpoint of improving the light transmittance of the thermoelectric conversion device 1, it is more preferable that the electrode layer 14 is formed of a material having optical transparency. Since the electrode layer 23 in the thermoelectric conversion device 2 can be similarly defined, the electrode layer 14 used in the thermoelectric conversion device 1 will be described below.

The electrode layer 14 has a microstructure such as a metal grid pattern used as an electromagnetic wave shielding film of a plasma display, for example, the shape seen from the vertical direction on the main surface of the thermoelectric conversion device 1. [

When the electrode layer 14 is formed of a material having no light transmittance, it is preferable that a number of openings are formed in the electrode layer 14 so as not to interfere with the light transmittance of the thermoelectric conversion device 1 .

As the shape of the opening of the electrode layer 14 viewed from the vertical direction on the main surface of the thermoelectric transducer 1, there may be used a stripe shape, a linear shape, a curved shape, a wavy line shape such as a sine curve, Shape, a circular mesh shape, an elliptical mesh shape, or an amorphous shape.

(B) a hexagonal opening, (c) a triangular opening, (d) a circular opening, and (c) a triangular opening as shown in Figures 5 (a) (E) a net shape in which a plurality of openings of a square shape (lattice shape) are arranged, and (f) a wavy line shape (sinusoidal line, etc.).

Further, as shown in Fig. 6 (a), it is preferable that a part of the outer frame is cut, as shown in Figs. 6 (b) and 6 (c)

The thickness of the electrode layer 14 is preferably 0.1 mu m or more and 1000 mu m or less, more preferably 1 mu m or more and 500 mu m or less, and still more preferably 5 mu m or more and 100 mu m or less.

The opening ratio of the electrode layer 14 is preferably 1% or more and 99% or less, more preferably 90% or more and 99% or less, and still more preferably 95% or more and 99% or less, from the viewpoint of light transmittance of the thermoelectric conversion device 1. [ % Or less. The aperture ratio is the ratio of the area of the area excluding the area where the electrode layer 14 is formed to the flat area of the thermoelectric conversion device 1.

The line width of the electrode layer 14 is preferably 10 nm to 1000 mu m, more preferably 10 to 500 mu m. If the line width is within the above range, good light transmittance can be obtained without deteriorating the conductivity. The aperture ratio is obtained as follows.

Opening percentage (%) = [area of opening / (area of line portion of electrode layer + area of opening)] x 100

In the present embodiment, the material for forming the electrode layer 14 is an alloy including at least one kind selected from gold, silver, copper, and platinum, or an alloy thereof. Among these metals, these materials are suitable because they have a low ionization tendency and therefore have high corrosion resistance.

The alloy is not particularly limited as long as it is an alloy mainly containing at least one kind selected from gold, silver, copper and platinum or one of them. Examples of these alloys include bronze, phosphor bronze, brass, white copper, monel, and the like, and can be appropriately selected. In particular, an alloy mainly composed of copper is preferably used since it has excellent conductivity and good processability.

The electrode layer 14 may be a single layer or a multilayer structure. It is preferable that the electrode layer has a multilayer structure in that corrosion resistance can be improved while maintaining conductivity.

The multi-layer structure may be a multi-layer structure in which layers containing the same kind of material are stacked, or a multi-layer structure in which layers including at least two types of materials are stacked.

Layer structure in which layers including at least two kinds of materials are laminated is preferable in that corrosion resistance can be improved. As the multilayer structure, a pattern layer containing an alloy material containing at least one kind selected from gold, silver, copper, and platinum, or an alloy material thereof is formed on a base material 11, It is preferable to laminate a pattern layer containing a material having higher corrosion resistance than the formed material.

As the multilayer structure, it is more preferable to have a two-layer structure in which layers including different kinds of materials are laminated. As such a multi-layer structure, for example, when a silver pattern layer is formed first and a pattern layer of copper having higher corrosion resistance than silver is formed thereon, the corrosion resistance is improved while maintaining high conductivity of silver.

[Manufacturing method of thermoelectric conversion device]

Next, a manufacturing method of the thermoelectric conversion device will be described.

On the surface of the substrate 11, the electrode layer 14 is formed using the above-described thermoelectric material. After the electrode layer 14 is formed, the thermoelectric conversion layers 12 and 13 are formed. Again, the electrode layer 14 is formed.

Examples of the method for forming the thermoelectric conversion layer using an inorganic material include a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, and a plasma CVD method. Of these, in the present invention, a sputtering method is preferable in that a conductor layer can be easily formed.

In the sputtering method, a discharge gas (argon or the like) is introduced into a vacuum chamber, a high-frequency voltage or a direct-current voltage is applied between the target and the substrate to make the discharge gas plasma, and the target material is blown by colliding the plasma with the target, 11) to obtain a thin film. As the target, a material including the material for forming the thermoelectric conversion layer is used.

Examples of the method for forming the thermoelectric conversion layer using an organic material include wet coating such as various coating methods such as dip coating, spin coating, spray coating, gravure coating, die coating and doctor blade, and electrochemical deposition. Is selected.

Among them, the aqueous dispersion or solution (coating liquid) of the organic polymer compound is applied onto the surface of the substrate 11 by various coating methods such as dip coating, spin coating, spray coating, gravure coating, die coating, 14). &Lt; / RTI &gt;

Examples of the method of providing the electrode layer 14 on the substrate 11 include a method of attaching the electrode layer 14 using an adhesive agent or a conductive paste or the like or a method of forming a pattern on the substrate 11 A method in which an electrode layer having no openings (without openings) is formed and then processed into a fine structure by various known mechanical treatments or chemical treatments; a method in which a conductive metal pattern is directly formed on a substrate 11 by an inkjet method, And the like.

Examples of the method for forming the electrode layer include dry processes such as 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) , A wet process such as various coating methods such as spin coating, spray coating, gravure coating, die coating, and doctor blade, and electrochemical deposition, and silver salt method, and is appropriately selected depending on the material of the conductive metal layer.

Further, the electrode layer 14 formed on the base material 11 by various methods described above is subjected to photolithography; A method of printing an etching resist pattern by an ink-jet method, a screen printing method, or the like, and performing etching processing; Various known mechanical treatments or chemical treatments such as an imprint method can be applied. Of these methods, the method is suitably selected according to the material and the putter of the microstructure.

In order to improve the adhesion between the electrode layer 14 and the substrate 11, a primer layer such as conventionally known acrylic resin or polyurethane resin having light transmittance may be interposed.

[Form of power storage system]

A configuration of a power storage system according to an embodiment of the present invention will be described. The power storage system includes, in addition to the thermoelectric conversion device, a power storage device for storing electricity. And a control circuit for controlling a charging operation of electric energy obtained from the thermoelectric conversion device.

The power storage device comprises a secondary battery, a capacitor, and the like. The secondary battery can be any type of battery that can be charged. Examples of the secondary battery include a lithium battery, a lithium polymer battery, a lithium ion battery, a nickel hydride battery, a nickel-cadmium battery, an organic radical battery, a lead acid battery, an air secondary battery, a nickel zinc battery, . Examples of the capacitor include an electric double layer capacitor and a lithium ion capacitor.

Example

Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[Assessment Methods]

The thermoelectric performance of the thermoelectric conversion device described later was evaluated by the following method.

&Lt; Electrical conductivity and Seebeck coefficient >

The electrical conductivity and the Seebeck coefficient of the thermoelectric conversion layer were measured using a thermoelectric property evaluation device ("ZEM-3" manufactured by ULVACO CO., LTD.).

<Thermal Conductivity>

The thermal conductivity of the thermoelectric conversion layer was measured by the 3? Method.

<Output voltage>

A cooling device comprising a combination of a chiller (LTCi-150H manufactured by Asuzen Co., Ltd., and a water-cooled cooler (P-200S, manufactured by Takagi Seisakusho K.K.) and a hot plate (manufactured by Asuzen Kabushiki Kaisha, A hot plate heated to 50 DEG C was brought into close contact with the substrate side of the thermoelectric conversion device and a temperature gradient was set at 0 DEG C on the opposite side of the substrate of the thermoelectric conversion device In this state, the temperature of the base material in contact with the hot plate and the temperature of the upper surface of the electrode layer in contact with the chiller were measured with a K-type thermocouple and a data logger The output voltage of the thermoelectric conversion device was measured with a digital multimeter (&quot; DT4282 &quot;, manufactured by Hioki DENKI KABUSHIKI KAISHA) Respectively.

&Lt; Optical transmittance (% T ₅₅₀ ) >

Visible light transmittance (transmittance at 550 nm) of the thermoelectric conversion device was measured using a spectrophotometer ("UV3601" manufactured by Shimadzu Corporation) according to JIS K7361-1.

[Example]

A thermoelectric conversion device was produced as follows.

&Lt; Example 1 >

A silver paste was printed on a surface of a glass substrate ("Eagle XG", thickness: 0.7 mm, manufactured by CORNING CORPORATION) in a striped pattern using a screen printing method and in a predetermined pattern, And dried to form a light-transmitting electrode layer in a predetermined pattern.

Subsequently, an organic-based p-type thermoelectric material PEDOT: PSS ("S-305" manufactured by Agromaterials Co., Ltd., thermal conductivity of 0.3 W / mK) was applied to an inkjet printing apparatus (manufactured by MicroJet Co., NanoPrinter-300 &quot;), a p-type thermoelectric conversion layer was formed. After formation, it was dried at 150 ° C in the atmosphere. Subsequently, a transparent n-type thermoelectric conversion layer was formed by sputtering using gallium-doped zinc oxide (GZO) which is an n-type thermoelectric material.

After both thermoelectric conversion layers were formed, silver paste was printed in a predetermined pattern and dried at 150 캜 for 30 minutes in the same manner as the above method to form a light-transmitting electrode layer of a predetermined pattern, A thermoelectric conversion device a of the type shown in Fig.

The dimensions of the thermoelectric conversion layer and the electrode layer in the thermoelectric conversion device a are as shown below. That is, D11 = 8 mm, D12 = 2 mm, D13 = 2 mm, d1 = 0.5 mm, and d2 = 0.5 mm were set in the respective portions shown in Fig. 1 or Fig. The thickness h12 of the p-type thermoelectric conversion layer 12 and the thickness h13 of the n-type thermoelectric conversion layer were set to 0.2 mu m and the thickness h14 of the electrode layer was set to 0.1 mu m.

Heat was applied to the specimen by the above-described method to measure the temperature difference generated in the thermoelectric transducer a. Further, the obtained potential difference and the light transmittance of the thermoelectric conversion device were measured. The results are shown in Table 1 together with the electrical conductivity and the thermal conductivity of the p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer, respectively.

&Lt; Example 2 >

The silver paste was printed on the surface of a glass substrate ("Eagle XG", thickness: 0.7 mm, manufactured by CORNING CORPORATION) using a screen printing method in a predetermined pattern, and then dried at 150 ° C. for 30 minutes, Transmitting electrode was formed.

Subsequently, an organic-based p-type thermoelectric material PEDOT: PSS ("S-305" manufactured by Agromaterials Co., Ltd., thermal conductivity of 0.3 W / mK) was applied to an inkjet printing apparatus (manufactured by MicroJet Co., NanoPrinter-300 &quot;), a p-type thermoelectric conversion layer was formed. After formation, it was dried at 150 ° C in the atmosphere.

Subsequently, the silver paste was printed in a predetermined pattern and dried at 150 DEG C for 30 minutes in the same manner as the above method to form a light-transmitting electrode of a predetermined pattern, Conversion apparatus b was prepared.

The dimensions of the thermoelectric conversion layer and the electrode layer in the thermoelectric conversion device b are as shown below. That is, D21 = 8 mm and D22 = 2 mm were set for the respective portions shown in Figs. 3 and 4. The thickness h22 of the thermoelectric conversion layer was set to 0.2 mu m, and the thickness h23 of the electrode layer was set to 0.1 mu m.

Heat was applied to the specimen by the above-described method to measure the temperature difference generated in the thermoelectric conversion device b. Further, the obtained potential difference and the light transmittance of the thermoelectric conversion device were measured. The results are shown in Table 1 together with the electrical conductivity and the thermal conductivity of the p-type thermoelectric conversion layer used.

&Lt; Example 3 >

A transparent n-type thermoelectric conversion layer was formed by the sputtering method using gallium-doped zinc oxide (GZO) after the light-transmitting electrode layer was formed on the glass substrate in the same manner as in Example 1. [ After the formation of the thermoelectric conversion layer, a light-transmitting electrode layer of a predetermined pattern was formed in the same manner as in the method of Example 1 to manufacture a thermoelectric conversion device c of the type shown in Figs. 3 and 4. The dimensions of the thermoelectric conversion layer and the electrode layer in the thermoelectric conversion device c were the same as those of the thermoelectric conversion device b.

Heat was applied to the specimen by the above-described method to measure the temperature difference generated in the thermoelectric conversion device c. Further, the obtained potential difference and the light transmittance of the thermoelectric conversion device were measured. The results are shown in Table 1 together with the electrical conductivity and the thermal conductivity of the n-type thermoelectric conversion layer used.

<Example 4>

A transparent n-type thermoelectric conversion layer was formed by sputtering using indium tin oxide (ITO) after a light-transmitting electrode layer having a mesh structure was formed on a glass substrate in the same manner as in Example 1. After the formation of the thermoelectric conversion layer, a light-transmitting electrode layer of a predetermined pattern was formed in the same manner as in the method of Example 1 to produce the thermoelectric conversion device d of the type shown in Figs. 3 and 4. The dimensions of the thermoelectric conversion layer and the electrode layer in the thermoelectric conversion device d were the same as those of the thermoelectric conversion device b.

Heat was applied to the specimen by the above-described method to measure the temperature difference generated in the thermoelectric conversion device d. Further, the obtained potential difference and the light transmittance of the thermoelectric conversion device were measured. The results are shown in Table 1 together with the electrical conductivity and the thermal conductivity of the n-type thermoelectric conversion layer used.

[Evaluation results]

It can be seen that the specimens of Examples 1 to 4 have optical transparency and can regenerate electrical energy from thermal energy.

Since the thermoelectric conversion device of the present invention has light transmittance and can regenerate a part of heat energy into electric energy, it is preferable that the display surface of an electronic device such as an information processing terminal requiring energy saving, A window glass, a car glass, or the like.

1, 2 thermoelectric conversion device, 11, 21 substrate, 12, 13, 22 thermoelectric conversion layer, 14, 23 electrode layer

Claims (9)

A thermoelectric conversion device comprising a thermoelectric conversion layer formed of a thermoelectric material and an electrode layer connected to the thermoelectric conversion layer,
Wherein at least the thermoelectric conversion layer of the thermoelectric conversion layer and the electrode layer has optical transparency. The thermoelectric conversion device according to claim 1, wherein at least the thermoelectric conversion layer of the thermoelectric conversion layer and the electrode layer intersects a plane of the thermoelectric conversion layer, and the visible light transmittance of 550 nm, which is measured using a spectrophotometer, Conversion device. The thermoelectric conversion device according to claim 1 or 2, wherein the thermoelectric conversion layer and the electrode layer have a base material on the surface, and the base material is an inorganic material having light transmission property or an organic material having light transmission property. The thermoelectric conversion device according to any one of claims 1 to 3, wherein the thermoelectric material is an n-type thermoelectric material. The thermoelectric conversion device according to any one of claims 1 to 3, wherein the thermoelectric material is a p-type thermoelectric material. The thermoelectric conversion device according to any one of claims 1 to 5, wherein the thermoelectric conversion layer has an n-type thermoelectric conversion layer formed of an n-type thermoelectric material and a p-type thermoelectric conversion layer formed of a p-type thermoelectric material, Layer and the p-type thermoelectric conversion layer are connected by the electrode layer. The thermoelectric conversion device according to any one of claims 1 to 6, wherein a ratio of an area of a region excluding a region where the electrode layer is formed to a plane area (plane area) of the thermoelectric conversion device is 1% or more and 99% . The thermoelectric conversion device according to any one of claims 1 to 7, wherein the electrode layer has optical transparency. 9. A thermoelectric conversion device comprising the thermoelectric conversion device according to any one of claims 1 to 8 and a power storage device for storing electricity,
And the electrode layer in the thermoelectric conversion device is electrically connected to the power storage device.

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