JP2002118297A - Thermoelement module and manufacturing method thereof - Google Patents

Abstract

(57) [Summary] (Modified) [PROBLEMS] To provide a high-performance thermoelectric element module having excellent thermal efficiency and strength, high moisture resistance, and improved operation reliability, and a method for manufacturing the same. A plurality of n-type and p-type thermoelectric semiconductor elements are disposed adjacent to each other through a metal electrode bonded to the opposing surface of each of a plurality of opposing substrates. (A) to (d) on the surface other than the connection surface of each thermoelectric semiconductor element with the electrode.
A film selected from the film-forming components is applied, and adjacent thermoelectric elements are arranged apart from each other. (A) a composition comprising an organopolysiloxane as a main component and an organosiloxane having a functional side chain as a crosslinking agent and a curing catalyst, (b) a composition comprising ceramic particles and a high heat solvent, (c) ) A prepolymer prepared by reacting a low molecular weight glycidyl ether type epoxy resin with a catalyst in the presence of an organic solvent solution of perhydropolysilazane and (d) metal oxide powder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoelectric element module in which a large number of thermoelectric elements are arranged, and more particularly, to a thermoelectric module excellent in thermal efficiency and high in reliability, utilizing a Seebeck effect, or The present invention relates to a thermoelectric element module that can be used as a cooling or heating module using the Peltier effect.

[0002]

2. Description of the Related Art Conventionally, a plurality of substrates have been arranged to face each other, and a conductive metal electrode has been joined to an opposing surface of each of the plurality of opposing substrates, and a plurality of substrates have been connected via the metal electrodes. The thermoelectric element module in which the n-type and p-type thermoelectric semiconductor elements are disposed adjacent to each other is widely known, and is used in various fields. For example, as shown in FIG. 5, these thermoelectric element modules connect the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element in series with each other, and maintain the junction at a high temperature by using the junction as a high-temperature end. Then, each leg of the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element opposite to the high-temperature side end is kept at low temperature as a low-temperature side end, and the high-temperature side end and the low-temperature side end are kept at low temperature. By using the principle that an electromotive force is generated when a temperature difference is applied, the module is used as a thermoelectric element module for power generation, or as shown in FIG. 6, a so-called Peltier effect, that is, an n-type thermoelectric semiconductor element and a p-type thermoelectric element. Type thermoelectric semiconductor elements are connected in series, and a positive voltage is applied to the leg of the n-type thermoelectric semiconductor element opposite to the connection portion, and a negative voltage is applied to the leg of the p-type thermoelectric semiconductor element. P-type heat from semiconductor device When a current is applied to the semiconductor element, heat is absorbed at the junction between the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element, and heat is generated at each leg of the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element. Then, when a current flows from the p-type thermoelectric semiconductor element to the n-type thermoelectric semiconductor element, heat is generated at the junction between the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element, and each leg of the n-type semiconductor and the p-type semiconductor It is used as a thermoelectric element module for cooling or heating, utilizing the principle that heat is absorbed by the element.

[0003] These conventional thermoelectric element modules include 1
Although there is a stage module or a multi-stage module, the basic structure in the case of a single-stage module in which two substrates are arranged facing each other is a structure as schematically shown in FIG. That is, in the thermoelectric element module A, the metal electrodes 4 and 4 'are bonded to the opposing surfaces 2 and 2' of the substrates 1 and 1 'of the two opposing canes, respectively.
A plurality of n-type thermoelectric semiconductor elements 5 and p-type thermoelectric semiconductor elements 6 are connected alternately via 4 '. FIG.
Although not shown in the figure, generally, the metal electrodes 4, 4 '
Are bonded to the substrates 1 and 1 'by a bonding means such as an adhesive. The n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6 are connected to the metal electrodes 4 and 4' by, for example, a solder layer or the like. They are joined by joining means. Also, although not shown in FIG. 3, components or equipment such as heating means, cooling means, or an object to be cooled are generally joined to the outer surfaces 3, 3 'of the substrates 1, 1'. That is, the thermoelectric element module is used as a thermoelectric element module for power generation utilizing the Seebeck effect, and the opposing surface 2 side of the substrate 1 is provided with the legs of the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6. The low-temperature side end side, and the opposing surface 2 'side of the substrate 1' is n
If it is on the high-temperature end side of the junction between the p-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6, the low-temperature end of each of the legs, such as radiating fins, is provided on the outer surface 3 of the substrate 1. A cooling means for keeping the temperature low is joined, while a heating means for keeping the high-temperature end of the connection part such as a heat receiving fin at a high temperature is joined to the outer surface 3 'of the substrate 1'. Further, in the case where the thermoelectric element module is used as, for example, a thermoelectric element module for cooling utilizing the Peltier effect, a current flows from the p-type thermoelectric semiconductor element 6 to the n-type thermoelectric semiconductor element 5 and the thermoelectric element module faces the substrate 1. The surface 2 side is the heat absorbing side end of each leg of the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element 6, and the opposing surface 2 'side of the substrate 1' is the n-type thermoelectric semiconductor element 5 and the p-type thermoelectric semiconductor element. 6, the object to be cooled is joined to the outer surface 3 of the substrate 1 by the heat-absorbing ends of the legs, while the outer surface 3 of the substrate 1 'is connected to the outer surface 3 of the substrate 1. ′, A cooling means, such as a radiation fin, for radiating heat at the end on the heat generation side of the connection portion is joined.

In such a thermoelectric element module,
Generally, a ceramic plate is used as a substrate.
However, in the conventional thermoelectric element module using a ceramic plate as the substrate, there is a problem that the thermal efficiency and the cooling efficiency are poor because the ceramic plate has poor thermal conductivity. In other words, when used as a thermoelectric element module for power generation utilizing the Seebeck effect, both heating for maintaining the high-temperature side end at high temperature and cooling for maintaining the low-temperature side end at low temperature are performed through a ceramic substrate having poor thermal conductivity. The heat efficiency and the cooling efficiency are inevitably reduced. Also,
When used as a thermoelectric element module for cooling or heating using the Peltier effect, cooling of the object to be cooled by the heat-absorbing side end, and heating of the object to be heated by the heat-generating side end are performed through a ceramic substrate having poor thermal conductivity. In order to be
Inevitably, thermal efficiency and cooling efficiency decrease. In addition, since the upper and lower portions of the thermoelectric element are fixed by the ceramic plates, the structure of the thermoelectric element module becomes a rigid body structure, and there is a problem that the thermoelectric element is easily broken. Further, in the conventional thermoelectric element module, the p-type thermoelectric semiconductor element and the n-type thermoelectric semiconductor element used as the thermoelectric element are brittle materials, so that when the thermoelectric element module is subjected to impact or load, or when the thermoelectric element module is used. Occasionally, when thermal stress is applied to the thermoelectric element, the thermoelectric element may be broken, causing cracking or chipping. Further, these thermoelectric elements are inferior in moisture resistance, and the thermoelectric elements may corrode during repeated condensation and melting or in an atmosphere of high humidity, and the element performance may be deteriorated. For example, in the case of a lanthanoid sulfide-based thermoelectric element that has been announced to have an excellent Seebeck coefficient, it is possible that corrosive substances such as sulfuric acid may be produced as by-products due to the sulfur component, so that moisture resistance measures must be taken. Met.

[0005] In order to solve the problems and the like of the conventional thermoelectric element module, various types have been proposed so far. For example, Japanese Patent Application Laid-Open No. Hei 5-275754 discloses that a bonding material between a ceramic substrate and an electrode is heated. Japanese Patent Application Laid-Open No. H11-307825 discloses a curable resin in which the durability of a thermomodule is improved by absorbing thermal stress. Japanese Patent Application Laid-Open No. 2000-164942 discloses a method of improving the strength of the thermoelectric module by applying a coating made of an insulating material made of a polyimide vapor-deposited polymer film on a surface other than the surface of the thermoelectric element to be bonded to the electrode. Are improved in Japanese Patent Application Laid-Open Nos. 10-178216 and 2000-5893.
No. 0 discloses a thermoelectric element having a skeleton structure as shown in FIG. 4, wherein a thermoelectric element structure held by a partition plate prevents a decrease in cooling efficiency,
A device for extending the life of a thermoelectric element is disclosed. However, despite these proposals, the thermoelectric element module that solved the problems of the conventional thermoelectric element module, etc., was excellent in thermal efficiency and cooling efficiency, and improved reliability,
It was small and I was not satisfied enough.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of conventional thermoelectric element modules in view of the circumstances surrounding the above-mentioned thermoelectric element modules and to achieve excellent thermal efficiency.
An object of the present invention is to provide a high-performance thermoelectric element module that can improve the strength of a thermoelectric element module, has high moisture resistance, and has improved operation reliability, and a method for manufacturing the same.

[0007]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventor has found that when constructing a thermoelectric element module, the surfaces of n-type and p-type thermoelectric semiconductor elements used as thermoelectric elements are By coating a specific film, even when an impact or load is applied to the thermoelectric element module, the thermoelectric element is not broken, reliability and durability can be improved, and the object of the present invention can be achieved. Was. The present invention has been completed based on these findings.

That is, according to the first aspect of the present invention,
A plurality of substrates are arranged to face each other, a conductive metal electrode is bonded to an opposing surface of each of the plurality of opposing substrates, and a plurality of n-type and p-type thermoelectric devices are connected via the metal electrodes. In a thermoelectric element module in which semiconductor elements are arranged adjacent to each other, an insulation selected from the following film-forming components (a) to (d) is applied to a surface other than the connection surface of each thermoelectric semiconductor element with an electrode. The thermoelectric element module is characterized in that the thermoelectric element module is characterized in that a coating with a hydrophilic coating agent is applied in an arbitrary shape, and adjacent thermoelectric elements are spaced apart from each other. (A) A composition comprising an organopolysiloxane as a main component, an organosiloxane having a functional side chain as a crosslinking agent, and a curing catalyst (b) A composition comprising a ceramic particle and a high heat solvent (c) Hydropolysilazane organic solvent solution (d) Prepolymer prepared by reacting a low molecular weight glycidyl ether type epoxy resin with a catalyst in the presence of metal oxide powder

According to the second aspect of the present invention, a plurality of n-type and p-type thermoelectric semiconductor elements are disposed adjacent to each other, and the upper and lower surfaces of these thermoelectric elements are electrically conductive. In the thermoelectric element module in which the thermoelectric elements are connected by the electrodes and the central part of the thermoelectric elements is fixed to the partition plate, the above-mentioned (a) to (a) to
(D) A thermoelectric element module characterized in that a film of an insulating coating agent selected from the film-forming components is applied in an arbitrary shape, and adjacent thermoelectric elements are spaced apart from each other. Is done.

Further, according to a third aspect of the present invention, there is provided a thermoelectric element module according to the first aspect, wherein the plurality of substrates are formed of a carbonaceous substrate made of a carbonaceous material. Is done.

Further, according to a fourth aspect of the present invention, there is provided the thermoelectric element module according to the second aspect, wherein the partition plate is made of a heat-resistant resin having electrical insulation.

According to the fifth aspect of the present invention, on the other hand, a bonding step of bonding a conductive metal electrode to the opposing surface of the substrate, and a plurality of n-type and p-type thermoelectric semiconductor elements are mutually connected via the metal electrode. A thermoelectric semiconductor element arranging step of arranging the thermoelectric semiconductor elements adjacent to each other, and an insulating film forming step of applying an insulating film to a surface other than a connection surface of each thermoelectric semiconductor element with an electrode. According to a third aspect, there is provided a method for manufacturing a thermoelectric element module.

According to a sixth aspect of the present invention, there is provided a thermoelectric semiconductor device arranging step of arranging a plurality of n-type and p-type thermoelectric semiconductor devices adjacent to each other. A connecting step of connecting the thermoelectric elements with conductive electrodes, a thermoelectric element fixing step of fixing the central part of the thermoelectric element to a partition plate, and applying an insulating coating to surfaces other than the connection surfaces of the thermoelectric semiconductor elements with the electrodes. A method for manufacturing a thermoelectric element module according to the second or fourth aspect of the present invention, which includes an insulating film forming step, is provided.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Substrate A carbonaceous substrate is used as a substrate used in the thermoelectric element module according to the first aspect of the present invention. The carbonaceous substrate is generally made of carbon fiber reinforced with carbon fiber as a reinforcing material and carbon as a matrix. A plate made of a carbonaceous material such as a carbon composite material or an isotropic high-density carbon material is used. The thickness of the carbonaceous substrate can be appropriately set as necessary, but generally, 0.3 to 5 mm is appropriate from the viewpoint of strength and cost.

As the carbon fiber reinforced carbon composite material used for the carbonaceous substrate, various conventionally known carbon fiber reinforced carbon composite materials can be appropriately selected and used.
In general, carbon fiber reinforced carbon composite materials have various arrangements of carbon fibers. The carbon fibers are aligned in one direction and arranged in a primary orientation to form a bundle.
There are a secondary orientation made of a woven cloth such as satin weave, a tertiary orientation made by so-called three-dimensional weaving of carbon fibers, and an example using carbon fibers as felt or short fibers. In the present invention, various arrangements of carbon fibers can be appropriately selected and used. In addition, the carbon fiber reinforced carbon composite material generally includes a matrix material such as a thermosetting synthetic resin such as a phenolic resin, or a pitch such as a petroleum pitch, in a carbon fiber aggregate having the above various orientations. Impregnated to prepare a prepreg, laminating a plurality of such prepregs as needed, heating under pressure to cure the matrix material, further firing at high temperature in an inert atmosphere to carbonize the matrix material Manufactured. When the carbon fibers are short fibers, generally, short fibers of carbon fibers are mixed with a matrix material, the mixture is molded into a predetermined shape, and the molded material is heated under pressure to cure the matrix material, Further, the matrix material is carbonized by firing at a high temperature in an inert atmosphere to produce a carbon fiber reinforced carbon composite material. The carbon fiber reinforced carbon composite material used for the carbonaceous substrate may be a plate-like material having a predetermined thickness as the carbonaceous substrate, or a carbon fiber reinforced carbon composite material manufactured in a block shape. May be cut into a plate having a predetermined thickness as a carbonaceous substrate. Further, the carbon fibers and the carbon matrix constituting the various carbon fiber reinforced carbon composite materials may be graphitized.

Among the above various carbon fiber reinforced carbon composite materials, a block of a primary oriented carbon fiber reinforced carbon composite material in which carbon fibers are aligned in one direction is separated from the block in the direction in which the carbon fibers are arranged. A plate-like object in which carbon fibers are arranged in the thickness direction in a carbon matrix, such as cut and cut into a plate having a predetermined thickness in a perpendicular direction, is particularly excellent in heat conductivity in the thickness direction. Therefore, it is preferably used as a carbonaceous substrate. The cutting of the plate-like material from the block of the carbon fiber reinforced carbon composite material can be performed by a cutting means known per se such as a wire saw or a rotating diamond saw.

Also, as the isotropic high-density carbon material used for the carbonaceous substrate, various conventionally known isotropic high-density carbon materials can be appropriately selected and used. The isotropic high-density carbon material is generally obtained by firing fine particles of sinterable graphite precursor such as raw coke or mesocarbon microbeads at a high temperature while pressing, or by using graphite fine particles or carbon whisker powder. It is manufactured by mixing a body or the like with a binder comprising a carbon precursor such as a pitch or a synthetic resin, followed by pressure molding and baking. The isotropic high-density carbon material used for the carbonaceous substrate may be a plate-shaped one having a predetermined thickness as the carbonaceous substrate, or may be a block-shaped isotropic high-density carbon material. Alternatively, it may be cut and cut into a plate having a predetermined thickness as a carbonaceous substrate. The above various isotropic high-density carbon materials may be graphitized.

[0018] Either the carbon fiber reinforced carbon composite material or the isotropic high-density carbon material described above is generally porous and has fine pores derived from the production process. Then, by impregnating the fine pores of these materials with an inorganic coating agent or a metal to make the materials nonporous, the thermal conductivity of the materials is further improved. Therefore, in the present invention, each of the above-mentioned carbonaceous materials can be used as a carbonaceous substrate by impregnating the fine pores thereof with an inorganic coating agent or a metal, if necessary, thereby further improving the thermal conductivity of the substrate. From the viewpoint of this, it is preferable to do so.

The inorganic coating agent to be impregnated into each of the above carbonaceous materials is an inorganic material which is liquid and can be impregnated into fine pores of the carbonaceous material, and is cured after impregnation to make the carbonaceous material nonporous. Various inorganic coating agents that form a cured product can be appropriately selected and used. Examples thereof include an inorganic silicon-containing polymer in which a crosslinking reaction proceeds at room temperature or under heating to form a ceramic-like cured product,
Examples include cements such as alumina cement, and inorganic binders containing water glass and the like. These inorganic coating agents can be diluted with an organic solvent to enhance their impregnation. Still more specific examples of the inorganic coating agent include HEATLES GLASS GA forming a silicon-containing polymer.
Series (trade name: Homer Technology Co., Ltd.), Tonen polysilazane (trade name: Tonen Co., Ltd.), a polysilazane, Redproof MR-1 as an inorganic binder
00 series (trade name: manufactured by Neken Co., Ltd.).

As a method of impregnating the fine pores of the carbonaceous material with the inorganic coating agent, a method of applying the inorganic coating agent to the carbonaceous material by a brush or the like, a method of dipping the carbonaceous material in the inorganic coating agent, and a method of applying high pressure And a method of injecting the inorganic coating agent into the carbonaceous material under a high vacuum. The inorganic coating agent impregnated in the carbonaceous material,
Is cured. At this time, the curing conditions of the inorganic coating agent can be appropriately set according to the type of the inorganic coating agent used.
For ATLESS GLASS, generally about 13
Suitably heating at 0 ° C. for 60 minutes.

As the metal to be impregnated into each of the above carbonaceous materials, aluminum, copper, or both are generally preferred. As a method of impregnating a metal into the fine pores of the carbonaceous material, a method of impregnating a metal such as molten aluminum or copper under high temperature and high pressure can be used. As a carbonaceous material impregnated with aluminum, CC-M
A (trade name: C / C composite base manufactured by Advanced Materials Co., Ltd. in which carbon fibers are primarily arranged) and C-MA (trade name: isotropic high-density carbon material base manufactured by Advanced Materials Co., Ltd.), and the like, Further, as a carbonaceous material impregnated with copper, MB-
18 (trade name: Mobius A with primary arrangement of carbon fibers)
And C / C composite base manufactured by T Company).

2. Thermoelectric semiconductor element In the first and second inventions of the present invention, various types of conventionally known n-type thermoelectric semiconductor elements and p-type thermoelectric semiconductor elements are used as the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element used in the thermoelectric element module. A thermoelectric semiconductor element can be appropriately selected and used, and examples thereof include a Bi-Te-based element and a Si-Ge element.
P-type or n-type thermoelectric semiconductor elements such as a system.

3. Metal electrode In the thermoelectric element modules according to the first and second inventions of the present invention, copper, nickel, or the like is preferably used as a metal of a metal electrode for connecting an n-type thermoelectric semiconductor element and a p-type thermoelectric semiconductor element to be used. Can be

4. Coating agent The thermoelectric element module according to the first and second inventions of the present invention provides an insulating material selected from the following film-forming components (a) to (d) on a surface other than the surface of the thermoelectric semiconductor device connected to the electrode. The greatest feature is that a film is formed with a hydrophilic coating agent. As described above, in the conventional thermoelectric element module, the elements are firmly sandwiched between the substrates, that is, because of the rigid structure, the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element are brittle materials. Therefore, it is difficult to absorb heat distortion, external impact and load, which causes a failure of the thermoelectric element module, resulting in poor durability and reliability. Therefore, by reinforcing the periphery of the thermoelectric semiconductor element with a coating agent, mechanical strength against stress due to thermal strain, external impact, and the like can be improved, and durability and reliability of the thermoelectric element module can be improved. In order to improve such performance, a material that hardly expands in volume due to heat is desirable as a material for coating the thermoelectric element.

As one of the film-forming components of the coating agent used in the present invention, (a) an organopolysiloxane is a main component, and an organosiloxane having a functional side chain as a crosslinking agent and a curing catalyst are blended. A composition (hereinafter abbreviated as “organopolysiloxane composition”) is used. In this organopolysiloxane composition, the organopolysiloxane as a main component preferably has a methyl group or a phenyl group. As the crosslinking agent, an organosiloxane having a functional side chain such as an alkoxy group, an acyloxy group, and an oxime group is preferable. As the curing catalyst, an organic compound containing a metal such as Zn, Al, Co, and Sn and a halogen are preferable. The organopolysiloxane composition preferably contains a silicon component in an amount of 40% or more in terms of SiO ₂ , and does not contain a solvent, water or a hydroxyl group. Also,
The organopolysiloxane composition cures even when heated at low temperature or dried at room temperature to form a hard ceramic coating having excellent adhesion. Further, the curing mechanism is such that the functional group of the organopolysiloxane of the main agent is first hydrolyzed by moisture in the air to be changed to a hydroxyl group, and then the hydroxyl group of the organopolysiloxane is converted to the hydroxyl group of the crosslinking agent organosiloxane. It is considered that a functional group is attacked and a dealcoholization reaction is caused by the action of a curing catalyst to form a cured polysiloxane as a polymer compound having a three-dimensional structure. It becomes a metal alkoxy condensate by the so-called sol-gel method. Examples of such organopolysiloxane compositions include heatless glass (HEA) sold by Homer Technology Co., Ltd.
TLS GLASS) (trade name).
If necessary, the organopolysiloxane composition may be, for example, a silicone resin having an intermediate structure between inorganic and organic in which a siloxane bond has a three-dimensionally extended network structure and one methyl group bonded to a silicon atom. Other formulations, such as microparticles, can also be added. Examples of the silicone resin having an intermediate structure between inorganic and organic include Tospearl (trade name) sold by Toshiba Silicone Co., Ltd.

Further, as another one of the film-forming components,
(B) A composition in which a solvent for high heat is mixed with ceramic particles is used. Examples of the solvent for high heat in this composition include alcohol solvents such as butanol and isopropanol. Examples of the ceramic particles include ceramic particles such as alumina, aluminum, zirconia, fused silica, pearlite, and mullite, and the particle size can be appropriately selected as necessary. Ten μm is appropriate. As the solvent for high heat, a solvent which is blended so that the specific gravity of the entire film-forming component becomes about 2 to 3 is preferably used. As an example of a composition in which a solvent for high heat is blended with the ceramic particles, Red Proof (trade name) manufactured by Athen Co., Ltd. and the like can be mentioned.

As still another one of the film-forming components,
(C) An organic solvent solution of perhydropolysilazane is used. Perhydropolysilazane has a structural formula of [SiHa
NHb] n (where a is 1 to 3 and b is 0 or 1). This perhydropolysilazane can be synthesized, for example, by forming a complex of dichlorosilane and pyridine in a solvent (pyridine complex method) to obtain a relatively high molecular weight oligomer having a small number of low molecular weight cyclic substances. it can. The actual molecular structure is complex, but contains many irregular rings,
The oligomer has a number average molecular weight of several thousand. This perhydropolysilazane is converted into ceramics by being applied to the substrate surface and then baked, and when baked in air or an atmosphere similar thereto, silica glass (SiO ₂ )
Is converted to Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, among which xylene is preferably used. The concentration of perhydropolysilazane in the organic solvent solution can be appropriately selected as needed. However, if the concentration is high, it becomes syrupy and poor in workability, so that it is in a range having an appropriate viscosity. Examples of such perhydropolysilazane include Tonen polysilazane (trade name) manufactured by Tonen Corporation. In addition, in this organic solvent solution of perhydropolysilazane, if necessary,
Fillers such as magnesium oxide and silicon carbide can be blended.

Further, as another one of the film forming components, (d) a low molecular weight glycidyl ether type epoxy resin is reacted with a catalyst in the presence of a metal oxide powder using a catalyst to prepare a prepolymer. Used. This prepolymer is, for example, described in International Publication No. W090 / 08168.
In accordance with the description in Examples 1 to 5 of the publication, it can be obtained by the following production method. First, a low molecular weight glycidyl ether type epoxy resin and a catalyst are charged into a reaction vessel and reacted under heating. Next, the metal oxide powder is charged into the reaction vessel, heating is continued while stirring, and after a required time, the reaction is terminated to obtain a prepolymer. Examples of the low-molecular-weight glycidyl ether type epoxy resin used in the production of the prepolymer include diglycidyl ether of resorcinol, and diglycidyl ether of bisphenol A. Examples of the catalyst include 2-ethyl-4-methylimidazole, 2-methylimidazole, and 4-methylimidazole.
Further, the metal oxide powder is not particularly limited,
Silica powder, alumina powder, and magnesia powder are preferably used. Further, as an example of the prepolymer, Seraprotex (trade name) manufactured by Nikko Co., Ltd. can be mentioned.

The method for applying a coating with an insulating coating agent selected from the above-mentioned coating-forming components (a) to (d) on a surface other than the connection surface of the thermoelectric semiconductor element with the electrode is not particularly limited. Various coating methods are appropriately selected. For example, a method of assembling a pre-coated thermoelectric element on a substrate, or a method of pouring a coating agent into a thermoelectric element after assembling a thermoelectric element on a substrate, a method of immersing a thermoelectric element in a coating agent, and the like. . Among them, a method of coating the thermoelectric element in advance by a spray coating method, a method of dipping the thermoelectric element in a coating agent, and the like are preferable. By these methods,
A uniform coating having a desired thickness can be easily provided on the surface of the thermoelectric element. Preferably, the thickness of the coating is about 100 μm in order to improve the reliability of the thermoelectric element module. Further, on the surface other than the connection surface of the thermoelectric semiconductor element with the electrode, the location and shape of the coating are not particularly limited, for example, a coating is applied only to the side of the thermoelectric element, or the side of the thermoelectric element and The coating is applied including the substrate portion, and further, the space between the adjacent thermoelectric elements, that is, the space between the substrate and the thermoelectric element is completely filled with the coating agent (full filling). The substrate and the side surfaces of the thermoelectric element may be filled (semi-filled) with a coating agent.

5. Partition plate The thermoelectric element module according to the second invention or the like of the present invention includes:
A thermoelectric element module having a skeleton structure on both sides, wherein n
The central part of the type and p-type thermoelectric semiconductor elements is fixed while penetrating a partition plate (sometimes called a separator). In order for the partition plate and the thermoelectric semiconductor element to be in an electrically insulated state, the partition plate needs to have electrical insulation properties, and since one of the substrates is radiated or heated, heat resistance is reduced. It is necessary to have, for example, a thickness of 0.2 to 0.5 m
m glass epoxy plate, anodized aluminum plate, heat-resistant plastic (heat-resistant resin) plate,
Alternatively, there is a plate obtained by mixing an inorganic filler such as a shirasu balloon into heatless glass or the like and firing the mixture.

6. In the thermoelectric element module according to the second invention and the like of the present invention, the thermally conductive electric insulating thin film is usually provided on one side of the metal electrode, that is, on the lower surface in the case of the lower electrode and on the upper surface in the case of the upper electrode. To join. The thermally conductive electrically insulating thin film has a thickness of several tens to several hundreds μm, and preferably about 15 to 100 μm. Examples of the material include an epoxy resin to which a thermally conductive filler is added, and a fluororesin. A coat, a silicon-based heat conductive adhesive, or the like can be used.

7. Bonding (1) Substrate / electrode In the thermoelectric element module according to the first aspect of the present invention,
The bonding between the carbonaceous substrate made of carbonaceous material and the metal electrode is sufficiently thin and sufficiently insulating, as long as the carbonaceous substrate and the metal electrode can be bonded sufficiently firmly.
Various means can be appropriately selected and used. For this joining, (a) a joining means composed of a polyimide coating film provided on the carbonaceous substrate and an adhesive layer provided on the polyimide coating film, or (b) a bonding means provided on the carbonaceous substrate. (C) a primer layer provided on a carbonaceous substrate, and an elastomeric material provided on the primer layer, the bonding means comprising a metal plating layer formed on the metal plating layer and an adhesive layer provided on the metal plating layer. Is preferred because it has better adhesion between the carbonaceous substrate and the metal electrode. That is, in general, the carbonaceous material is relatively hard to be familiar with many adhesives, and is more preferably firmly applied when a base such as a polyimide coating or a metal plating layer or a primer layer is provided in advance. The carbonaceous material and the metal electrode can be adhered to the substrate. In general, the joining means is preferably thin so as not to hinder the thermal conductivity in the thickness direction of the thermoelectric element module.

In the bonding means (a), the polyimide coating film can be formed by applying various conventionally known polyimide coating materials to the carbonaceous substrate. In addition, as for the polyimide coating, both of a type in which polyamic acid is dissolved in a solvent and a type in which polyimide resin is dissolved in a solvent are applicable, but the latter does not require a step of dehydration and imidization by heating, It is preferable because a coating film having excellent insulating properties can be obtained at a relatively low temperature. As such an example, Rica Coat (trade name: manufactured by Shin Nippon Rika Co., Ltd.) may be mentioned. In addition, various additives can be added to the polyimide paint in order to improve insulation properties and stability of the coating film. Then, a metal electrode is further laminated on the polyimide coating via an adhesive layer, and then is bonded under pressure at a heating or normal temperature, and by a joining means composed of the polyimide coating and the adhesive layer. A metal electrode is bonded to the carbonaceous substrate. The processing conditions for the above-mentioned bonding can be appropriately set according to the type of the polyimide coating used and the like.

A preferred form of the polyimide coating in the bonding means (a) is a polyimide electrodeposition coating. The polyimide electrodeposition coating film can be formed from various kinds of polyimide electrodeposition coating materials in which a conventionally known resin component is polyimide and a medium is a cation solution. Various additives can be added to the polyimide electrodeposition paint in order to improve the insulating property and the stability of the coating film. The polyimide electrodeposition coating film can be obtained by electrodepositing the above-mentioned polyimide electrodeposition paint on a carbonaceous substrate. The electrodeposition method can be performed by appropriately selecting and employing a conventionally known method. Then, a metal electrode is further laminated on the above-mentioned polyimide electrodeposition coating film via an adhesive layer, and thereafter, is adhered by heating or pressurizing at room temperature, and a bonding comprising the polyimide coating film and the adhesive layer is performed. Bonded to the metal electrode or carbonaceous substrate by means. The conditions for the above-mentioned bonding can be appropriately set according to the type of the polyimide electrodeposition paint used.

In the bonding means (b), the metal plating layer can be formed by appropriately selecting and employing a conventionally known electroless plating method or electrolytic plating method. Examples of the metal to be plated include copper and nickel. Then, on the metal plating layer, a metal electrode is further laminated via an adhesive layer, and then bonded by heating or pressurizing at room temperature, and by a joining means composed of the metal plating layer and the adhesive layer. A metal electrode is bonded to the carbonaceous substrate.

As the adhesive used for the adhesive layer in the bonding means (a) or (b), an epoxy resin-based adhesive, a silicone-based adhesive and the like can be mentioned. For example, as the silicone adhesive, KE1800T (trade name: manufactured by Shin-Etsu Silicone Co., Ltd.), TES-3260 (trade name: manufactured by Toshiba Silicone Co., Ltd.) and the like are preferably used. In addition, the inorganic coating agent such as the above-mentioned heatless glass, which is mentioned as the material to be impregnated into the carbonaceous material, can also be used as the above-mentioned adhesive. These adhesives are applied on the above-mentioned polyimide coating film or metal plating layer (hereinafter referred to as “base” in this paragraph) to form an adhesive layer. It can be performed by appropriately selecting and adopting the various application methods thus obtained. In applying the adhesive, (a) first, the adhesive may be applied on a base provided on the carbonaceous substrate, and a metal electrode may be laminated on the coating film. An adhesive may be applied to one side, and the metal electrode may be laminated such that the coated surface of the adhesive contacts the substrate provided on the carbonaceous substrate, or (c) the substrate provided on the carbonaceous substrate. An adhesive may be applied to both the upper surface and one side of the metal electrode, and the adhesive may be laminated so that the coating surfaces of the respective adhesives are in contact with each other, or (d) a base material provided on the carbonaceous substrate. An adhesive and a metal electrode formed into a film in a semi-cured state may be sequentially laminated thereon. When laminating the metal electrodes, it is preferable to pressurize them with a roll, a flat plate press, or the like in order to eliminate the residual air and ensure the close contact. In bonding, the primer and the metal electrode may be subjected to a primer treatment by brushing various primers described later in advance. The processing conditions for drying or heating and curing the adhesive can be appropriately set according to the type of the adhesive used and the like. For example, the above-mentioned T
When ES-3260 (trade name: manufactured by Toshiba Silicone Co., Ltd.) is used, it may be formed by heating and pressing at 150 ° C. for 60 minutes.

In the bonding means (c), examples of primers used for the primer treatment of the carbonaceous substrate include primer A (trade name) and primer X (trade name) manufactured by Dow Corning Toray Silicone Co., Ltd. A mixture of the primer Y (trade name) and the like can be mentioned. Examples of the adhesive forming the adhesive layer provided on the primer layer include:
SOTEFA made by Toray Dow Corning Silicone
An elastomer adhesive such as -70 (trade name: silicone elastomer adhesive) is suitably used. In addition, this elastomer-based adhesive can also be used for the adhesive layer in the joining means (A) and (B). Also, if necessary, this elastomeric adhesive
An appropriate amount of a heat conductive filler in the form of fine particles such as SiN, SiC, and Al ₂ O ₃ can be added. In addition, the said heat conductive filler can also be added to the various adhesive layers in the joining means of said (a) and (b). Then, the elastomeric adhesive layer provided on the primer layer is dried or heat-cured, and the metal electrode is bonded to the carbonaceous substrate by the bonding means composed of the primer layer and the adhesive layer. The processing conditions for drying or heating and curing the above-mentioned elastomeric adhesive layer can be appropriately set according to the kind of the used elastomeric adhesive and the like.

In the bonding means (b) and (c), an appropriate amount of a fine particle-shaped filler having a spacer function can be added to each adhesive to be used, if necessary. Examples of the filler having the spacer function include silica, spherical alumina, and hollow balloon.

(2) Electrode / thermoelectric semiconductor device In the thermoelectric device module of the present invention, the metal electrode and the n-type thermoelectric semiconductor device and the p-type thermoelectric semiconductor device are joined together.
Various joining means, such as soldering or brazing, known as joining means between the metal electrode and the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element in the conventional thermoelectric element module can be appropriately selected and used.

8. Manufacture of thermoelectric element module The manufacture of the thermoelectric element module according to the first invention of the present invention, for example, when it is a one-stage module, is generally performed as follows. That is, first, on a carbonaceous substrate made of a carbonaceous material as described above, after impregnating an inorganic coating agent or a metal as described above in its fine pores as necessary, a metal electrode is joined and formed. .

One method for joining and forming the metal electrode on the carbonaceous substrate is as follows. First, a metal foil equivalent to the metal electrode is provided on the carbonaceous substrate with electrical insulation, and the metal foil is attached to the carbonaceous substrate. The metal-bonded laminated board is manufactured by bonding with a bonding means capable of bonding to the substrate, preferably with the bonding means (A), (B) or (C) described above. This metal-attached laminate may be a metal-attached laminate in which metal foil is laminated on only one side of the carbonaceous substrate, or may be a metal-attached laminate in which metal foil is laminated on both sides, as necessary. Can also. Then, on the metal foil surface of the obtained metal-laminated laminate, in the case of a metal-laminated laminate in which metal foils are laminated on both sides, on one side of the metal foil surface, a printed wiring board manufacturing technology has been established. Apply a photolithographic technique, that is, draw a desired pattern of a metal foil portion required for electrode formation using a photoresist, and perform etching or the like in accordance with the pattern to perform a metal foil portion unnecessary for electrode formation. The removal and the like can join and form the metal electrode on the carbonaceous substrate.

As another method for joining and forming the metal electrode on the carbonaceous substrate, a so-called lead frame formed by punching a metal plate into a desired pattern of the metal electrode on the carbonaceous substrate is used. Is bonded by a bonding means having an electrical insulation property and capable of bonding the lead frame to the carbonaceous substrate, preferably by the bonding means (a), (b) or (c) above, without performing etching or the like. It can also be done directly. In general, the method of applying the photolithography technique is suitable for fine processing, although the joining and forming steps of metal electrodes are relatively complicated.On the other hand, the method of using the lead frame is not suitable for fine processing. Although not suitable, the process of joining and forming metal electrodes is relatively simple, and by using a lead frame with a corresponding thickness to make the metal electrode to be joined and formed to have a corresponding thickness, the It is suitable for joining and forming a metal electrode capable of coping with a current and having a reduced resistance loss.

Next, the two carbonaceous substrates formed by bonding the metal electrodes obtained as described above are opposed to each other, and the n-type thermoelectric semiconductor element and By alternately connecting the p-type thermoelectric semiconductor elements, the thermoelectric element module of the present invention is manufactured. At this time, the metal electrode and the n-type thermoelectric semiconductor element and the p-type thermoelectric semiconductor element can be joined by a conventionally known joining means such as soldering. Further, the one-stage thermoelectric element module of the present invention uses a carbonaceous substrate as a substrate, and uses an electrically insulating bonding means for bonding a metal electrode to the carbonaceous substrate. Except for the two points that the joining means of (b) or (c) is used, its basic structure is the basic structure of a conventional one-stage thermoelectric element module whose cross section is schematically shown in FIG. Is the same as The basic structure of the multi-stage thermoelectric element module of the present invention is the same as the basic structure of the conventional multi-stage thermoelectric element module except for the above two points. In addition to the case where the carbonaceous substrate made of a carbonaceous material is used for all of the plurality of substrates (for example, the two substrates in the one-stage thermoelectric element module) as described above, one of the plurality of substrates is used. The present invention also includes a case where a carbonaceous substrate is used for the part. Therefore, for example, a carbonaceous substrate may be used only for the substrate on the heat receiving side, and the substrate on the heat radiating side may be a conventional ceramic substrate.

In the thermoelectric element module of the present invention, for example, when it is a one-stage module, the heating means, the cooling means, or the cooling target is formed on the outer surface of the carbonaceous substrate in the same manner as the conventional one-stage thermoelectric element module. Parts or equipment such as objects can be joined. In joining these parts or equipment to the outer surface of the carbonaceous substrate, the joining means does not need to be particularly electrically insulating, and any means capable of firmly joining these parts or equipment to the carbonaceous substrate. If necessary, any of the above-mentioned joining means (A), (B) and (C) is preferably used. In the thermoelectric element module of the present invention, for example, when it is a one-stage module, for example, heat receiving or heat radiating fins can be integrally formed on the outer surface of the carbonaceous substrate. As a specific example, there is a case where the carbonaceous substrate itself is processed into a fin shape by forming a slit in the carbonaceous substrate with a disk cutter or a saw blade.

The production of the thermoelectric element module according to the second aspect of the present invention is slightly different from the production of the thermoelectric element module according to the first aspect of the present invention. A thermoelectric element fixing step of fixing the thermoelectric element to the partition plate. Further, as described above, usually, a thermally conductive electrically insulating thin film bonding step of bonding a thermally conductive electrically insulating thin film to one surface of a metal electrode, that is, to a lower surface in the case of a lower electrode, and to an upper surface in the case of an upper electrode, is also included. Including. When using the thermoelectric element module of the second invention or the like,
A heat-dissipating or heat-absorbing metal member or the like can be provided via the thermally conductive electrically insulating thin film. In addition, a heat-resistant resin sheet may be provided on the thermally conductive electric insulating thin film,
In this case, since the metal electrode is fixed to the heat-resistant resin sheet via the heat-conductive electrically insulating thin film, more accurate positioning and the like can be performed. Further, a heat-dissipating or heat-absorbing metal member or the like can be provided via a heat-resistant resin sheet.

[0046]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments using drawings, but the present invention is not particularly limited to these embodiments.

Example 1 [Outline of Thermoelectric Element Module and Its Manufacturing Method (FIG. 1)] FIG. 1 is a sectional view showing a thermoelectric element module of Example 1. As the substrates 1 and 1 ′, CC (hereinafter, referred to as “C / C composite”) which is a plate-shaped carbon fiber reinforced carbon composite material (hereinafter, referred to as “C / C composite”) having a thickness of 1 mm in which carbon fibers are arranged in a thickness direction in a carbon matrix. (Trade name: manufactured by Advanced Materials Co., Ltd.). As the thermoelectric elements, an n-type thermoelectric semiconductor element 5 made of an n-type semiconductor and a p-type thermoelectric semiconductor element 6 made of a p-type semiconductor are used, and these thermoelectric semiconductor elements 5 and 6 are arranged on the same plane. Are arranged alternately at intervals,
Also, a large number of electrodes 4 are formed on the upper and lower surfaces of all the n-type thermoelectric semiconductor elements 5 and the p-type thermoelectric semiconductor elements 6 so that they are connected in series.
Are joined to the thermoelectric semiconductor elements so that the upper surfaces or the lower surfaces of the n-type and p-type thermoelectric semiconductor elements arranged adjacent to each other are alternately passed. A coating 7 made of an insulating coating agent was formed on the side peripheral surface of the thermoelectric semiconductor elements 5 and 6 produced in this manner other than the joint surface with the electrode 4. The method for forming the coating 7 is to assemble a thermoelectric element on a substrate, and then, as a coating agent, a composition containing an organopolysiloxane as a main component, an organosiloxane having a functional side chain as a crosslinking agent, and a curing catalyst. Used and immersed in this coating agent.

Example 2 [Outline of Thermoelectric Element Module with Skeleton Structure and Its Manufacturing Method (FIG. 2)] FIG. 2 is a cross-sectional view showing a thermoelectric element module of Example 2. As the partition plate 8, a heat-resistant resin made of glass epoxy resin was used. The central portion of the thermoelectric element was fixed to the partition plate 8 with the thermoelectric semiconductor elements 5 and 6 penetrating therethrough.
As in the first embodiment, an n-type thermoelectric semiconductor element 5 made of an n-type semiconductor and a p-type
Type thermoelectric semiconductor elements 6 are used. These thermoelectric semiconductor elements 5 and 6 are alternately arranged on the same plane with an interval, and all n-type thermoelectric semiconductor elements 5 and p
A large number of electrodes 4 are formed on both upper and lower surfaces of the thermoelectric semiconductor element 6 so that the thermoelectric semiconductor elements 6 are connected in series. The electrodes 4 are composed of n-type and p-type The thermoelectric semiconductor elements are joined to the thermoelectric elements such that the upper surfaces or the lower surfaces of the thermoelectric semiconductor devices are alternately passed. further,
On the upper surface of the upper electrode 4, an upper thermal conductive electrically insulating thin film 9 is provided.
Further, the lower thermal conductive electrical insulating thin film 9 ′ was joined to the lower surface of the lower electrode 4. The thermally conductive and electrically insulating thin films 9, 9 '
An epoxy resin to which a thermal conductive filler was added was used. Thermoelectric semiconductor elements 5, 6 produced in this way
A coating 7 made of an insulating coating agent was formed on the side peripheral surface other than the bonding surface with the electrode 4. The method of forming the coating 7 is the same as in Example 1, after assembling the thermoelectric element on the substrate, using an organopolysiloxane as a main agent as a coating agent, an organosiloxane having a functional side chain as a crosslinking agent, and a curing catalyst. Was used and immersed in this coating agent.

As shown in Examples 1 and 2, the surface of the n-type and p-type thermoelectric semiconductor elements used as thermoelectric elements are coated with a specific film, whereby the strength of the thermoelectric element is reinforced and the thermoelectric element module is Even when a shock or load was applied to the, the thermoelectric element was not broken, and the reliability and durability could be improved.

[0050]

According to the present invention, there is provided a high-performance thermoelectric element module which is excellent in thermal efficiency and which does not break even when an impact or a load is applied to the thermoelectric element module, and has high reliability. You. INDUSTRIAL APPLICABILITY The thermoelectric element module of the present invention has high thermal efficiency and high reliability, and can function as power generation using the Seebeck effect or as cooling or heating using the Peltier effect. It is useful in.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a section of a thermoelectric element module (Example 1) of the present invention.

FIG. 2 is a cross-sectional view showing a skeleton-structured thermoelectric element module (Example 2) of the present invention.

FIG. 3 is a sectional view showing an example of a conventional thermoelectric element module.

FIG. 4 is a sectional view showing an example of a thermoelectric element module having a skeleton structure.

FIG. 5 is a diagram illustrating the principle of the Seebeck effect.

FIG. 6 is a diagram illustrating the principle of the Peltier effect.

[Explanation of symbols]

 1: substrate 1 ': substrate 2: substrate facing surface 2': substrate facing surface 3: outer surface of substrate 4: metal electrode 5: n-type thermoelectric semiconductor element 6: p-type thermoelectric semiconductor element 7: coating 8: partition plate 9: Thermally conductive electrical insulating thin film 9 ': Thermally conductive electrical insulating thin film

Claims (6)

[Claims] A plurality of n-type substrates, wherein a plurality of substrates are arranged to face each other, a conductive metal electrode is bonded to an opposing surface of each of the plurality of substrates, and a plurality of n-type electrodes are provided via the metal electrodes. And a thermoelectric element module in which p-type thermoelectric semiconductor elements are arranged adjacent to each other, on the surface other than the connection surface of each thermoelectric semiconductor element with the electrode, the following film forming properties (a) to (d) A thermoelectric element module characterized in that a coating of an insulating coating agent selected from the components is applied in an arbitrary shape, and adjacent thermoelectric elements are spaced apart from each other. (A) A composition comprising an organopolysiloxane as a main component, an organosiloxane having a functional side chain as a crosslinking agent, and a curing catalyst (b) A composition comprising a ceramic particle and a high heat solvent (c) Hydropolysilazane organic solvent solution (d) Prepolymer prepared by reacting a low molecular weight glycidyl ether type epoxy resin with a catalyst in the presence of metal oxide powder 2. A plurality of n-type and p-type thermoelectric semiconductor elements are arranged adjacent to each other, the upper and lower surfaces of these thermoelectric elements are connected by conductive electrodes, and the center of the thermoelectric element is In a thermoelectric element module in which a part is fixed to a partition plate, an insulating coating agent selected from the following film-forming components (a) to (d) on a surface other than a connection surface of each thermoelectric semiconductor device with an electrode. A thermoelectric element module, characterized in that a coating of any desired shape is applied, and adjacent thermoelectric elements are spaced apart from each other. (A) A composition comprising an organopolysiloxane as a main component, an organosiloxane having a functional side chain as a crosslinking agent, and a curing catalyst (b) A composition comprising a ceramic particle and a high heat solvent (c) Hydropolysilazane organic solvent solution (d) Prepolymer prepared by reacting a low molecular weight glycidyl ether type epoxy resin with a catalyst in the presence of metal oxide powder 3. The thermoelectric element module according to claim 1, wherein the plurality of substrates are formed of a carbonaceous substrate made of a carbonaceous material. 4. The thermoelectric element module according to claim 2, wherein the partition plate is made of a heat-resistant resin having electrical insulation. 5. A bonding step of bonding a conductive metal electrode to an opposing surface of a substrate, and a thermoelectric semiconductor element arrangement for arranging a plurality of n-type and p-type thermoelectric semiconductor elements adjacent to each other via the metal electrode. The method for producing a thermoelectric element module according to claim 1, further comprising: an installation step; and an insulating coating forming step of applying an insulating coating to a surface other than a connection surface of each thermoelectric semiconductor element with an electrode. . 6. A thermoelectric semiconductor element arranging step of arranging a plurality of n-type and p-type thermoelectric semiconductor elements adjacent to each other, a connecting step of connecting upper and lower surfaces of the thermoelectric element by conductive electrodes, A thermoelectric element fixing step in which the center of the thermoelectric element is fixed to a partition plate, and an insulating coating forming step of applying an insulating coating to a surface other than the connection surface of each thermoelectric semiconductor element with an electrode, The method for manufacturing a thermoelectric element module according to claim 2.