WO2005036661A1 - 熱電変換材料接続用導電性ペースト - Google Patents
熱電変換材料接続用導電性ペースト Download PDFInfo
- Publication number
- WO2005036661A1 WO2005036661A1 PCT/JP2004/014680 JP2004014680W WO2005036661A1 WO 2005036661 A1 WO2005036661 A1 WO 2005036661A1 JP 2004014680 W JP2004014680 W JP 2004014680W WO 2005036661 A1 WO2005036661 A1 WO 2005036661A1
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- WIPO (PCT)
- Prior art keywords
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- thermoelectric conversion
- conversion material
- elements selected
- general formula
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 333
- 239000000463 material Substances 0.000 title claims abstract description 256
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 59
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052737 gold Inorganic materials 0.000 claims abstract description 36
- 239000010931 gold Substances 0.000 claims abstract description 36
- 229910052709 silver Inorganic materials 0.000 claims abstract description 36
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- 229910052802 copper Inorganic materials 0.000 claims description 79
- 229910052742 iron Inorganic materials 0.000 claims description 79
- 229910052748 manganese Inorganic materials 0.000 claims description 79
- 229910052759 nickel Inorganic materials 0.000 claims description 79
- 229910052720 vanadium Inorganic materials 0.000 claims description 77
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- 229910052700 potassium Inorganic materials 0.000 claims description 70
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- 229910052712 strontium Inorganic materials 0.000 claims description 68
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- 229910052747 lanthanoid Inorganic materials 0.000 claims description 51
- 150000002602 lanthanoids Chemical class 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 49
- 229910052721 tungsten Inorganic materials 0.000 claims description 48
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- 229910052758 niobium Inorganic materials 0.000 claims description 46
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- 229910052745 lead Inorganic materials 0.000 claims description 32
- 229910052725 zinc Inorganic materials 0.000 claims description 32
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- -1 AL Bi Inorganic materials 0.000 claims description 8
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- 230000002349 favourable effect Effects 0.000 abstract 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 49
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- 230000000052 comparative effect Effects 0.000 description 8
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
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- 229910018921 CoO 3 Inorganic materials 0.000 description 2
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- 239000004925 Acrylic resin Substances 0.000 description 1
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
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- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- JHLCADGWXYCDQA-UHFFFAOYSA-N calcium;ethanolate Chemical compound [Ca+2].CC[O-].CC[O-] JHLCADGWXYCDQA-UHFFFAOYSA-N 0.000 description 1
- AMJQWGIYCROUQF-UHFFFAOYSA-N calcium;methanolate Chemical compound [Ca+2].[O-]C.[O-]C AMJQWGIYCROUQF-UHFFFAOYSA-N 0.000 description 1
- OEPJXTZQPRTGCX-UHFFFAOYSA-N calcium;propan-1-olate Chemical compound [Ca+2].CCC[O-].CCC[O-] OEPJXTZQPRTGCX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- PAWJJGAENXYUFN-UHFFFAOYSA-N cobalt(2+);propan-1-olate Chemical compound [Co+2].CCC[O-].CCC[O-] PAWJJGAENXYUFN-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
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- 238000009434 installation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
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- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
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- 230000000171 quenching effect Effects 0.000 description 1
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- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/66—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2
- C01G53/68—Nickelates containing alkaline earth metals, e.g. SrNiO3, SrNiO2 containing rare earth, e.g. La1.62 Sr0.38NiO4
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/70—Nickelates containing rare earth, e.g. LaNiO3
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/81—Structural details of the junction
- H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Definitions
- the present invention relates to a conductive paste for connecting a thermoelectric conversion material, a thermoelectric conversion element obtained by using the paste, and a thermoelectric power generation module.
- thermoelectric conversion which directly converts heat energy to electric energy, is considered to be an effective means.
- Thermoelectric conversion utilizes the Seebeck effect, and is an energy conversion method that generates a potential difference by applying a temperature difference between both ends of a thermoelectric conversion material to generate power.
- thermoelectric generation In such power generation, thermoelectric generation, and thermoelectric power generation using thermoelectric conversion, one end of the thermoelectric conversion material is placed in a high-temperature section generated by waste heat, the other end is placed in the atmosphere, and external ends are placed on both ends. Electricity can be obtained simply by connecting a resistor, and there is no need for any moving devices such as motors and tarpins required for general power generation. Therefore, the cost is low, there is no emission of gas due to combustion, etc., and power generation can be performed continuously until the thermoelectric conversion material deteriorates. In addition, since thermoelectric generation can generate power at a high output density, the generator (module) itself can be reduced in size and weight, and can be used as a mobile power source for mobile phones and notebook computers.
- thermoelectric power generation is expected to play a part in solving one of Enesolegi's concerns that may be of concern in the future.
- a thermoelectric conversion module composed of thermoelectric conversion materials that have high conversion efficiency and excellent heat resistance and chemical durability is required.
- thermoelectric conversion materials that have high conversion efficiency and excellent heat resistance and chemical durability.
- thermoelectric conversion elements that connect a pair of P-type thermoelectric conversion materials and n-type thermoelectric conversion materials, or thermoelectric elements that integrate thermoelectric conversion elements A power generation module or generator is required.
- thermoelectric conversion elements and thermoelectric power generation modules are behind the development of thermoelectric conversion materials themselves.
- thermoelectric generation using high-temperature waste heat of 673 K (400 ° C) or higher gold, silver, etc. are generated by joining a thermoelectric conversion material using solder, since oxidation and melting occur.
- Noble metal pastes such as platinum are used as joining materials.
- an oxide is used as a substrate material, thermoelectric conversion material, or the like, the use of a noble metal paste agent causes a large difference in the coefficient of thermal expansion from the noble metal in the paste. As a result, the internal resistance of the module increases and the mechanical strength decreases. Also, since the metal and the oxide are in contact with each other at the junction, there is a problem that the interface resistance is large.
- the present invention has been made in view of the above-mentioned state of the art, and its main purpose is to connect a thermoelectric conversion material made of an oxide with low resistance, and to repeatedly generate electricity at a high temperature.
- Another object of the present invention is to provide a connection material for a thermoelectric conversion material and a thermoelectric conversion element obtained by using the connection material, in which the performance of the thermoelectric generation module hardly deteriorates even when the connection is made.
- thermoelectric conversion element when a conductive paste containing a noble metal powder and a specific composite oxide is used as a connection material for a thermoelectric conversion material, the junction of the thermoelectric conversion element must have appropriate conductivity and be heated to a high temperature. It has been found that even when power generation is repeated, peeling of the connection portion is unlikely to occur, and good thermoelectric conversion performance can be maintained for a long period of time. Thus, the present invention has been completed.
- the present invention provides the following conductive base for connecting a thermoelectric conversion material, a thermoelectric conversion element, a thermoelectric power generation module, and a thermoelectric power generation method.
- (b) General formula: B if P b gM CO Ok (where M 1 is selected from the group consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Ca, Sr, Ba, AUY and lanthanides the is one or more elements, M 2 is, Ti, V, Cr, Mn , Fe, Ni, Cu, Mo, W, one selected from the group consisting of Nb and Ta, or two or more on 1.8 ⁇ f ⁇ 2.2; 0 ⁇ g ⁇ 0.4; 1.8 ⁇ h ⁇ 2.2;
- L n is one or more elements selected from lanthanides
- R 1 is one or more elements selected from the group consisting of Na, K, Sr, Ca and Bi
- R 2 is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni> Cu, Mo, W, Nb and Ta, and 0.5 ⁇ m ⁇ l.2; 0 ⁇ n ⁇ 0.5; 0.5 ⁇ p ⁇ 1.2; 0 ⁇ q ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.
- thermoelectric conversion material A conductive paste for connecting a thermoelectric conversion material, comprising:
- thermoelectric conversion material according to the above item 1 which contains 0.5 to 20 parts by weight of the oxide powder described in the item (i) based on 100 parts by weight of the conductive metal powder described in the item (ii). Conductive paste for connection.
- thermoelectric conversion material for connection of a thermoelectric conversion material according to item 1, further comprising a glass component and a resin component.
- M 1 is, Na, K, Li, Ti, V, cr, Mn, Fe, Ni, Cu, Zn, Pb, Ca, Sr, Ba, Al, and one or more elements selected from the group consisting of Y and lanthanides
- M 2 is, Ti, V, One or more elements selected from the group consisting of Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta, 1.8 ⁇ f ⁇ 2.2; 0 ⁇ g 0.4; 1.8 ⁇ h ⁇ 2.2; 1.6 ⁇ i ⁇ 2.2; 0 ⁇ j ⁇ 0.5; 8 ⁇ k ⁇ 10.
- At least one oxide powder selected from the group consisting of:
- At least one conductive metal powder selected from the group consisting of gold, silver, platinum, and alloys containing at least one of these metals;
- a conductive paste for connecting a P-type thermoelectric conversion material comprising:
- the oxide powder has the general formula: C a a AC o 4 O e (where A 1 is Na, K :, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb , Sr, Ba, Al, Bi, Y and lanthanoida, one or more elements selected from the group consisting of: 2.2 ⁇ a ⁇ 3.6; 0 ⁇ b ⁇ 0.8; 8 ⁇ .
- thermoelectric conversion according to item 4 wherein the oxide powder according to item (i) is contained in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the conductive metal powder described in item (ii). Conductive paste for material connection.
- thermoelectric conversion material for connecting a p-type thermoelectric conversion material according to the above item 4, further comprising a glass component and a resin component.
- Ln is one or more elements selected from lanthanides
- R 1 is one or more elements selected from the group consisting of Na, K :, Sr, Ca and Bi Yes
- R 2 is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta, and 0.5 ⁇ m ⁇ l. 2; 0 ⁇ n ⁇ 0.5; 0.5 ⁇ p ⁇ 1.2; 0 ⁇ q ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.
- Ln is one or more elements selected from lanthanoids
- R 3 is, Na, K
- R 4 is a group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta
- At least one oxide powder selected from the group consisting of composite oxides represented by
- At least one conductive metal powder selected from the group consisting of gold, silver, platinum, and alloys containing at least one of these metals;
- a conductive paste for connecting an n-type thermoelectric conversion material comprising:
- the oxide powder has the general formula: L amRinN i 0 r (where R 1 is one or more elements selected from the group consisting of Na, K, Sr, Ca, and Bi; .... 5 ⁇ m ⁇ l 2; 0 ⁇ n ⁇ 0. 5; 2. 7 ⁇ r ⁇ 3 a 3) a composite oxide represented by the general formula: (L a s R 3 t ) 2 N I_ ⁇ w (where, R 3 is, Na, K, Sr, and one or more elements selected from the group consisting of Ca and Bi, 0. 5 ⁇ s ⁇ l 2;. 0 ⁇ t ⁇ 0. 5; 3. 6 ⁇ w ⁇ 4.4.
- the paste for connecting an n-type thermoelectric conversion material according to the above item 8 which is at least one selected from the group consisting of composite oxides represented by:
- the conductive paste for connecting an n-type thermoelectric conversion material according to item 8 further comprising a glass component and a resin component.
- thermoelectric conversion element in which one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material are connected to a conductive substrate using a conductive paste, respectively.
- the P-type thermoelectric conversion material has the general formula: CaaAibCOeASdOe (where A 1 is
- a 2 is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta, and 2.2 ⁇ a ⁇ 3.6 0 ⁇ b ⁇ 0.8; 2 ⁇ c ⁇ 4.5; 0 ⁇ d ⁇ 2; 8 ⁇ e ⁇ 10.
- Composite oxide represented by or the general formula: B i f P 0 iM 2 jO k (where M 1 is Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Ca, Sr, Ba, Al, Y and run is one or more elements selected from the group consisting of a type M 2 are selected Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, from the group consisting of Nb and Ta Or two or more elements, 1.8 ⁇ f ⁇ 2.2; 0 ⁇ g ⁇ 0.2 4 1.8 ⁇ h ⁇ 2.2 2. 1.6 ⁇ i ⁇ 2.2; 0 ⁇ j ⁇ 0 5; 8 ⁇ k ⁇ 10.) D, which consists of a complex oxide represented by
- the n-type thermoelectric conversion material has the general formula: L nmR (Where L n is one or more elements selected from lanthanoids, and R 1 is one or more elements selected from the group consisting of Na, K :, Sr, Ca and Bi R 2 is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta, and 0.5 ⁇ m ⁇ l.2; 0 ⁇ n ⁇ 0.5; 0.5 ⁇ p ⁇ 1.2; 0 ⁇ q ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.
- the conductive paste used to connect the P-type thermoelectric conversion material and the n-type thermoelectric conversion material to the conductive substrate is the conductive paste described in item 1 above. Is a paste of nature,
- thermoelectric conversion element characterized by the above-mentioned.
- thermoelectric conversion element in which one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material are connected to a conductive substrate using a conductive paste, respectively.
- the P-type thermoelectric conversion material has the general formula: C (Where A 1 is selected from the group consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanide A 2 is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta.
- thermoelectric conversion material made of a composite oxide represented by the general formula: L During i p R 2 Q O r (wherein, Ln is one or more elements selected from the run-evening Neu de, R 1 is, Na, K :, Sr, from the group consisting of Ca and Bi R 2 is one or more selected from the group consisting of Ti, V, Cr> Mn, Fe, Ni, Cu, Mo, W, Nb and Ta 0.5 ⁇ m ⁇ l.
- the conductive paste used to connect the P-type thermoelectric conversion material to the conductive substrate is: (i) General formula: C a aA! BC OcASdOe (where A 1 is Na, K, Li, ⁇ , V, Cr, ⁇ , Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and one or more elements selected from the group consisting of lanthanides; A 2 is Ti, V , Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta are one or more elements selected from the group consisting of: 2.2 ⁇ a ⁇ 3.6; 0 ⁇ b ⁇ 0 ...
- LnmRinN i p R 2 Q O r wherein, L n is one or two or selected from Rantanoido R 1 is one or more elements selected from the group consisting of Na, K, Sr, Ca and Bi, and R 2 is Ti, V,, Mn, Fe , Ni, Cu, Mo, W, Nb and Ta are one or more elements selected from the group consisting of 0.5 ⁇ m ⁇ 1.2; 0 ⁇ n ⁇ 0.5; 0.5 ⁇ p ⁇ 1.2; 0 ⁇ q ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.)
- At least one oxide powder selected from the group consisting of composite oxides represented by the following formula: and (ii) gold, silver, platinum, and an alloy containing at least one of these metals
- thermoelectric conversion element characterized by the above-mentioned.
- thermoelectric conversion element in which one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material are connected to a conductive substrate using a conductive paste, respectively.
- thermoelectric conversion material has the general formula: C a a in AC o 4 O e (wherein, A 1 is, Na, K, Li, Ti , V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, One or more elements selected from the group consisting of Sr, Ba, Al, Bi, Y and lanthanoids; 2.2 ⁇ a ⁇ 3.6; 0 ⁇ b ⁇ 0.8; 8 ⁇ e ⁇ 1 0) composite oxides represented by, or the general formula:.
- the n-type thermoelectric conversion material has the general formula: L i 0 (wherein, R 1 is one or more elements selected from the group consisting of Na, K :, Sr, Ca, and Bi; 0.5 ⁇ m ⁇ 1.2; 0 ⁇ n ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.) Or a general formula: (L a s R 3 t ) 2 N i O w (where R 3 is , Na, K, Sr, Ca and Bi are one or more elements selected from the group consisting of: 0.5 ⁇ s ⁇ l. 2; 0 ⁇ t ⁇ 0.5; 3.6 ⁇ w ⁇ 4.4.) It consists of a composite oxide represented by
- the conductive paste used to connect the P-type thermoelectric conversion material to the conductive substrate is: (i) General formula: C a 3 ⁇ ⁇ 3 0 4 ⁇ e (where A 1 is Na, K, Li , Ti, V, Cr, Mn, It is one or more elements selected from the group consisting of Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y, and lanthanides; 2.2 ⁇ a ⁇ 3.6; 0 ⁇ b ⁇ 0.8; 8 ⁇ e ⁇ 10.
- the conductive paste used to connect the n-type thermoelectric conversion material to the conductive substrate is a conductive paste used to connect the n-type thermoelectric conversion material to the conductive substrate.
- L i O r (wherein, R 1 is, Na, K :, Sr, is one or more elements selected from the group consisting of Ca and Bi, 0. 5 ⁇ m ⁇ l 2;. 0 ⁇ n ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.) and a general formula: (L a s R 3 t ) 2 N i O w (where R 3 Is one or more elements selected from the group consisting of Na, K, Sr, Ca and Bi; 0.5 ⁇ s ⁇ l.2; 0 ⁇ t ⁇ 0.5; 3.6 ⁇ w ⁇ 4.4.) At least one oxide powder selected from the group consisting of the composite oxides represented by), and) gold, silver, platinum, and at least one of these metals A conductive paste containing at least one kind of conductive metal powder selected from the group consisting of alloys.
- thermoelectric conversion element characterized by the above-mentioned.
- thermoelectric conversion elements described in 1 and 2 above, connect the unbonded end of the p-type thermoelectric conversion material of the thermoelectric conversion element to the unbonded end of the n-type thermoelectric conversion material of another thermoelectric conversion element.
- a thermoelectric power generation module in which a plurality of thermoelectric conversion elements are connected in series by a method of connecting them on a board.
- thermoelectric generation module according to the above item 15 is arranged in a high-temperature section, and the other end is arranged in a low-temperature section.
- thermoelectric conversion elements described in 13 above, connect the unbonded end of the p-type thermoelectric conversion material of the thermoelectric conversion element to the unbonded end of the n-type thermoelectric conversion material of another thermoelectric conversion element.
- thermoelectric generation module according to the above item 17 is arranged in a high-temperature part and the other end is arranged in a low-temperature part.
- thermoelectric conversion material connection paste of the present invention will be described in detail.
- the conductive paste for connecting a thermoelectric conversion material of the present invention includes at least one conductive metal powder selected from the group consisting of gold, silver, platinum, and an alloy containing at least one of these metals; It contains an oxide powder as an essential component.
- conductive metal powder selected from the group consisting of gold, silver, platinum, and an alloy containing at least one of these metals; It contains an oxide powder as an essential component.
- noble metals such as gold, silver, and platinum, alloys containing at least one of these noble metals, and the like can be used.
- an alloy for example, an alloy containing about 30% by weight or more, preferably about 70% by weight or more of a noble metal such as gold, silver, or platinum can be used. Further, an alloy containing two or more noble metal components may be used.
- the conductive metal powders can be used alone or in combination of two or more.
- the particle size of the conductive metal powder is not particularly limited, but usually, it is preferable that about 80% or more of the metal powder has a particle size in the range of about 0.1 to 30 im.
- oxide powder at least one oxide powder selected from the group consisting of the composite oxides described in (a) to (d) below is used.
- the conductive metal powder is used.
- these oxide powders have good conductivity and can provide good conductivity to a connection portion.
- examples of the lanthanoid element include La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and the like.
- examples of preferred composite oxides include the following composite oxides.
- Alpha 1 is, Na, K, Li, Ti ⁇ V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr , Ba, Al, Bi, Y and one or more elements selected from the group consisting of lanthanoids; 2.2 ⁇ a ⁇ 3.6; 0 ⁇ b ⁇ 0.8; 8 ⁇ e ⁇ 10
- Composite oxide represented by 2 Q 0 r, and the general formula: (Ln s R 3 t) 2 N i u R 4 v O w composite oxides table, the one of single crystal or polycrystal But it's fine.
- the method for producing these composite oxides is not particularly limited, as long as it can produce a single crystal or a polycrystal having the above-described composition.
- a single crystal production method such as a flux method, a zone melt method, a pulling method, a glass anneal method via a glass precursor, a solid state reaction method, a powder production method such as a sol-gel method, a sputtering ring method, and a laser abrasion method.
- a composite oxide having a crystal structure having the above composition may be produced by a known method such as a thin film production method such as a chemical vapor deposition method or a chemical vapor deposition method.
- the above-described composite oxide can be produced, for example, by mixing and firing the raw materials so as to have the same element component ratio as the target composite oxide.
- the firing temperature and the firing time are not particularly limited as long as the desired composite oxide is formed. For example, in the temperature range of about 700 to 120 ° C., the firing temperature and It may be fired for about 40 hours.
- a carbonate, an organic compound, or the like is used as the raw material, it is preferable to calcine the raw material before firing to decompose the raw material, and then to fire to form the target composite oxide.
- a carbonate is used as a raw material, it may be calcined at about 700 to 900 for about 10 hours and then calcined under the above conditions.
- the firing means is not particularly limited, and any means such as an electric heating furnace and a gas heating furnace can be adopted.
- the firing atmosphere is usually an oxidizing atmosphere such as an oxygen stream or air, but if the raw material contains a sufficient amount of oxygen, for example, the firing can be performed in an inert atmosphere. .
- the amount of oxygen in the produced composite oxide can be controlled by the oxygen partial pressure during firing, the firing temperature, the firing time, and the like. The higher the oxygen partial pressure, the higher the oxygen ratio in the above general formula .
- the raw material powder be fired as a pressed compact in order to efficiently advance the solid-phase reaction. In this case, the obtained compact may be pulverized into a powder having a required particle size.
- the melting condition at this time may be any condition as long as the raw material can be uniformly melted.However, in order to prevent contamination from the melting vessel and evaporation of the raw material components, for example, when using alumina rutupo, It is preferable to heat to about 1200 to 140 to melt. There is no particular limitation on the heating time, and heating may be performed until the raw material is uniformly melted. The heating time may be generally about 30 minutes to 1 hour.
- the heating means is not particularly limited, and any means such as an electric heating furnace and a gas heating furnace can be employed.
- the atmosphere at the time of melting may be an oxygen-containing atmosphere such as in air or an oxygen stream of about 300 ml / 1 or less, but if the raw material contains a sufficient amount of oxygen, an inert atmosphere is used. May be melted.
- the quenching condition is not particularly limited, but at least the surface portion of the solidified product is formed. What is necessary is just to quench rapidly on the condition that a part becomes a glassy amorphous layer.
- the melt may be poured on a metal plate and rapidly cooled by means of compression from above.
- the cooling rate may be about 500 ° C./sec or more, preferably 10 3 / sec or more.
- the solidified material formed by rapid cooling is heat-treated in an oxygen-containing atmosphere, whereby the composite oxide grows as a fibrous single crystal from the surface of the solidified material.
- the heat treatment temperature may be about 880 to 930 ° C., and heating may be performed in an oxygen-containing atmosphere such as air or an oxygen stream. In the case of heating in an oxygen stream, for example, heating may be performed in an oxygen stream having a flow rate of about 300 m 1 Z or less, but may be higher.
- the heat treatment time is not particularly limited and may be determined according to the intended degree of growth of the single crystal, but usually, the heating time may be about 60 to 1000 hours.
- the mixing ratio of the raw materials can be determined according to the desired composition of the composite oxide. Specifically, when a fibrous composite oxide single crystal is formed from the amorphous layer portion on the surface of the solidified product, the composition of the melt in the amorphous portion is defined as a liquid phase composition. Since an oxide single crystal having an equilibrium solid phase composition grows, the composition of the starting material can be determined by the relationship between the composition of the melt phase and the composition of the solid phase (single crystal) that are in equilibrium with each other.
- the size of the composite oxide single crystal obtained by such a method can vary depending on the type of raw material, composition ratio, heat treatment conditions, etc., for example, a length of about 10 to 1000, a width of about 20 to 200 m, and a thickness of about 20 to 200 m. It has a fibrous shape of about 1 to 5 m.
- the oxygen content of the obtained substance can be controlled by the oxygen flow rate during firing, and the higher the flow rate, the higher the oxygen content
- changes in the oxygen content do not significantly affect the electrical properties of the composite oxide.
- the raw material is not particularly limited as long as it can form an oxide by firing, and a simple metal, an oxide, various compounds (such as carbonates), and the like can be used.
- C a source calcium oxide (CaO), calcium chloride (C aC 1 2), calcium carbonate (CAC0 3), calcium nitrate (Ca (N0 3) 2) , hydroxide of calcium (Ca (OH) 2), dimethoxy calcium (Ca ( ⁇ _CH 3) 2), diethoxy calcium (Ca (OC 2 H 5) 2), dipropoxy calcium (Ca (OC 3 H r) 2) using the alkoxide compounds such as Can be.
- Co source The oxidizing cobalt (Co_ ⁇ , Co 2 0 3, C o 3 0 4), chloride Koparuto (C o C 1 2), carbonate Koba Belt (Co C0 3), cobalt nitrate (Co (N0 3) 2) , cobalt hydroxide (Co (OH) 2), di-propoxy cobalt (Co (OC 3 H 7) 2) using the alkoxide compounds such as Can be.
- elemental elements, oxides, chlorides, carbonates, nitrates, hydroxides, alkoxide compounds and the like can be used.
- a compound containing two or more constituent elements of the composite oxide may be used.
- the particle size of the powder is not particularly limited, but usually, about 80% or more of the oxide powder preferably has a particle diameter of about 50 m or less, and preferably about 1 to 10 m. Is more preferred.
- thermoelectric conversion material connection of the present invention The conductive paste for thermoelectric conversion material connection of the present invention
- At least one oxide powder selected from the group consisting of
- At least one conductive metal powder selected from the group consisting of gold, silver, platinum, and alloys containing at least one of these metals
- the conductive paste can usually contain a glass component, a resin component, and the like in addition to the oxide powder and the conductive metal powder described above.
- thermoelectric power generation when the paste is applied to the connection part and heated, It is a component that mainly exhibits binding power.
- a component capable of melting and exhibiting a bonding force when joined by heating, and a component capable of maintaining a sufficient bonding force without being melted may be used for thermoelectric power generation. .
- Such a glass component may be appropriately selected from glass components blended in a known conductive paste.
- a glass component for example, bismuth borosilicate glass, lead borosilicate glass, or the like can be used.
- the resin component imparts appropriate dispersibility, thixotropy, viscosity characteristics, and the like to the paste.
- the resin component for example, ethylcellulose, hydroxyethylcellulose, methylcellulose, nitrocellulose, an ethylcellulose derivative, an acrylic resin, a petalal resin, an alkyd phenol resin, an epoxy resin, a wood material and the like can be used. .
- the mixing ratio of each of these components is not particularly limited, and may be appropriately determined according to the desired conductivity, coefficient of thermal expansion, bonding force, viscosity characteristics, and the like.
- the content of the oxide powder is preferably about 0.5 to 20 parts by weight, more preferably about 1 to 15 parts by weight, based on 100 parts by weight of the conductive metal powder. .
- the content of the glass component may be, for example, about 0.5 to 10 parts by weight, and preferably about 1 to 7 parts by weight, based on 100 parts by weight of the conductive metal powder. It is also possible to use outside the range.
- the content of the resin component is not particularly limited either, and may be appropriately determined within a range in which appropriate workability and adhesiveness can be exhibited.
- the amount can be about 0.5 to 20 parts by weight, preferably about 1 to 10 parts by weight, more preferably about 1 to 5 parts by weight based on 100 parts by weight of the conductive metal powder. Is more preferable.
- other oxide powders may be added to the conductive paste of the present invention. The type and amount of the oxide powder may be determined as appropriate within a range that does not adversely affect the above-described effects.
- an n-type thermoelectric conversion material powder can be added to the p-type thermoelectric conversion material connection conductive paste.
- the conductive paste of the present invention may contain additives such as a solvent, a plasticizer, a lubricant, an antioxidant, and a viscosity modifier, which are blended in the known conductive paste.
- a solvent for example, terpineol, butyl carbyl] -yl acetate and the like can be used, and they may be appropriately mixed and used.
- the contents of these components may be appropriately determined according to the required properties.
- the solvent can be used in an amount of about 3 to 30 parts by weight, preferably about 5 to 20 parts by weight, based on 100 parts by weight of the conductive metal powder.
- thermoelectric conversion material for connecting any of a P-type thermoelectric conversion material and an n-type thermoelectric conversion material to a conductive substrate.
- thermoelectric conversion material connection paste described above to impart appropriate conductivity to the junction of the thermoelectric conversion material, and when power generation at high temperatures is repeated, Also, the peeling of the connection portion is less likely to occur, and good thermoelectric conversion performance can be maintained for a long time.
- the oxide powder when a P-type thermoelectric conversion material is connected to a conductive substrate, the oxide powder is represented by the general formula: C a a AC oc A 2 d O e (where AA 2 , a, b, c, d and e composite oxide represented by the same) above, and the general formula: B i f PbgMihCo iM in 2 JO k (wherein, M 1 M 2, fg, h, i, j and k are the same) It is preferable to use at least one oxide powder selected from the group consisting of composite oxides represented by These composite oxides have properties as a p-type thermoelectric conversion material.
- thermoelectric conversion material By using a paste containing the composite oxide to connect the P-type thermoelectric conversion material, Good conductivity can be imparted to the connection portion without impairing the thermoelectric characteristics of the thermoelectric conversion material, and the coefficient of thermal expansion of the connection portion can be approximated to the coefficient of thermal expansion of the thermoelectric conversion material.
- the oxide powder is represented by the general formula: R 2 , m, n, p, Q and r are the same as above. And a general formula: (Ln s R 3 t ) 2 Niu R 4 v O w (where L n, R 3 , R 4 , s, t, u and v are It is preferable to use at least one composite oxide powder selected from the group consisting of composite oxides represented by the following formula: These composite oxides have characteristics as an n-type thermoelectric conversion material.
- a paste containing the composite oxide for connection of the n-type thermoelectric conversion material the thermoelectric properties of the n-type thermoelectric conversion material can be improved. Without disturbing the connection Good conductivity can be imparted to the portion, and the coefficient of thermal expansion of the connection portion can be approximated to the coefficient of thermal expansion of the thermoelectric conversion material.
- thermoelectric conversion element of the present invention one end of a P-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material are respectively connected to a conductive substrate.
- a conductive paste for connecting the P-type thermoelectric conversion material to the conductive substrate and a conductive paste for connecting the n-type thermoelectric conversion material to the conductive substrate are represented by (i) (a).
- a composite oxide represented by O cASdOe (where A 1 , A 2 , a, b, c, d, and e are the same as above),
- At least one oxide powder selected from the group consisting of
- At least one conductive metal powder selected from the group consisting of gold, silver, platinum, and alloys containing at least one of these metals
- pastes having the same composition may be used, or pastes having different compositions may be used.
- pastes having the same composition are used, the operation of applying the paste becomes easy, and the thermoelectric conversion element can be manufactured efficiently.
- a general formula having characteristics as a P-type thermoelectric conversion material C A composite oxide represented by O cAZdOe (where A 1 , A 2 , a, b, c, d, and e are the same as above), and —general formula: B i (Wherein, M 1 M 2 , f, g, h, i, j, and k are the same as above), a paste containing at least one oxide powder selected from the group consisting of composite oxides represented by N-type thermoelectric conversion material to conductive substrate
- thermoelectric conversion material considering the production efficiency and the performance of the target thermoelectric conversion material, etc., whether to use the same paste for connecting the p-type thermoelectric conversion material and the connection for the n-type thermoelectric conversion material or to use different pastes It may be determined appropriately.
- thermoelectric conversion material is not particularly limited, but among the oxide powder to be mixed with the conductive paste for connecting the thermoelectric conversion material of the present invention, a general formula: C a (Where A 1 is selected from the group consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanoids A 2 is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Mo, W, Nb and Ta. Yes, 2.
- thermoelectric conversion material composed of a composite oxide represented by the following formula:
- thermoelectric conversion material is produced by the same production method as the composite oxide compounded in the above-mentioned conductive paste, for example, a flux method, a zone melt method, a pulling method, a glass annealing method via a glass precursor.
- a flux method for example, a flux method, a zone melt method, a pulling method, a glass annealing method via a glass precursor.
- Single crystal It can be produced by various methods such as a production method, a solid phase reaction method, a powder production method such as a sol-gel method, a sputtering method, a laser abrasion method, a thin film production method such as a chemical 'vapor' deposition method, and the like.
- part of Ca in Ca 2 CoO 3 is replaced by A 1
- part of Co in this layer and part of Co in the Co 0 2 layer are replaced by A 2 .
- some Bi is replaced by a part of Pb or M 1, a part of Co is substituted by M 2.
- these oxides When a temperature difference is applied to both ends of these oxides, the potential generated by the Seebeck effect is lower on the high temperature side than on the low temperature side, and exhibits properties as a p-type thermoelectric conversion material.
- These oxides have, for example, a Seebeck coefficient of about 100 V / K or more at a temperature of 100 K (absolute temperature) or more, and an electrical resistivity of about 1 ⁇ cm or less. At the same time, the Seebeck coefficient increases and the electrical resistivity tends to decrease.
- a preferred composite oxide represented by the general formula: C a 3 ⁇ 0 o 4 ⁇ e (wherein, A 1 is, Na, K, Li, Ti , V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanoids, and one or more elements selected from the group consisting of: . a ⁇ 3. 6; 0 ⁇ b ⁇ 0.
- n-type thermoelectric conversion material it is not particularly limited, among the oxide powder mixed into the thermoelectric varying ⁇ charge connection conductive paste of the present invention, the general formula: LnmR N i p R 2 q O r (where L n is one or more elements selected from lanthanides, and R 1 is one or more elements selected from the group consisting of Na, K :, Sr, Ca and Bi R 2 is Ti, V, CJ :, Mn, Fe, Ni, Cu, Mo, W, Nb or Ta One or more elements selected from the group consisting of: 0.5 m ⁇ l.2; 0 ⁇ n ⁇ 0.5; 0.5 ⁇ 1.2; 0 ⁇ q ⁇ 0. 5; 2.7 ⁇ r ⁇ 3.3.
- thermoelectric conversion material composed of a composite oxide represented by the following formula:
- thermoelectric conversion materials may be any of a polycrystalline sintered body and a single crystal body, and may be formed in a thin film shape.
- thermoelectric conversion material is produced by the same production method as the composite oxide compounded in the conductive paste described above, for example, a flux method, a zone melt method, a pulling method, a glass annealing method via a glass precursor, and the like.
- Manufacturing by various methods such as single crystal manufacturing method, solid state reaction method, powder manufacturing method such as sol-gel method, sputtering method, laser abrasion method, thin film manufacturing method such as chemical vapor deposition method, etc. Can be.
- the former has a crystal structure of perovskite type, the latter are generally those having a crystal structure called a lamellar base Robusukai Bok, generally former AB0 3 structure, the latter A 2 also referred to as B0 4 structure.
- part of Ln is substituted by R 1 or R 3
- part of Ni is substituted by R 2 or R 4 .
- These composite oxides have a negative Seebeck coefficient, that is, when a temperature difference is applied to both ends, the potential generated by the Seebeck effect is higher on the high temperature side than on the low temperature side. Shows properties as a conversion material.
- These composite oxides have, for example, a Seebeck coefficient of about -1 to -30 ⁇ / ⁇ at a temperature of 100 K or more, and show low electric resistivity. For example, at a temperature of 100 K or more, the material can have an electrical resistivity of about 10 OmQcm or less.
- L . i O r (wherein, R 1 is, Na, K, Sr, and one or more elements selected from the group consisting of Ca and Bi, 0. 5 ⁇ m ⁇ l 2; 0 ⁇ n ⁇ 0.5; 2.7 ⁇ r ⁇ 3.3.
- Composite oxide represented by) the general formula: (a type L a s R 3 t) 2 N i 0 W ( wherein, R 3 is where Barre selected from the group consisting of Na, K, Sr, Ca and Bi Or two or more elements, 0.5 ⁇ s ⁇ l.2; 0 ⁇ t ⁇ 0.5; 3.6 ⁇ w ⁇ 4.4.) be able to.
- the shape and size of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material to be used are not particularly limited, and the necessary thermoelectric conversion is performed according to the size and shape of the target thermoelectric power module. What is necessary is just to determine suitably so that performance may be exhibited.
- it is used as a rectangular parallelepiped material with a width and thickness of about 1 to 10 mm and a length of about 1 to 20 mm, and a cylindrical material with a diameter of about 1 to 10 mm and a length of about 1 to 20 mm. be able to.
- thermoelectric conversion material is obtained, for example, by molding an oxide powder obtained by the same method as the above-described method of manufacturing the oxide powder for connecting a thermoelectric conversion material, heating the resultant into a sintered body, According to the above, it can be obtained by cutting out and shaping into a predetermined shape using a diamond cutter or the like.
- the sintering method is not particularly limited, as long as a dense sintered body can be obtained.
- a hot press sintering method, a partial melting method, or the like can be employed.
- the sintering atmosphere is not particularly limited, and may be an oxidizing atmosphere such as the air or a vacuum atmosphere.
- the sintering temperature is not particularly limited either, but may be, for example, about 800 to 950.
- a substrate in which an insulating ceramic is provided with a metal coating, a conductive ceramic substrate, or the like can be used.
- the conductive ceramic a material that does not deteriorate even in air at a temperature of about 107 K (absolute temperature) and can maintain a low electric resistance for a long period of time is preferable.
- an n-type thermoelectric conversion material LaNi0 3 etc. it is possible to use an oxide-sintered body with a low electrical resistivity.
- the insulating ceramic it is preferable to use a material that is not oxidized even in air at a high temperature of about 1073 K.
- a substrate made of an oxide ceramic such as alumina can be used.
- the metal coating formed on the insulating ceramics any metal coating that does not oxidize in high-temperature air and has low electric resistance may be used.
- a coating of a noble metal such as silver, gold, or platinum may be formed by an evaporation method or the like.
- the length, width, thickness, and the like of the conductive substrate may be appropriately set according to the size of the module, electric resistance, and the like.
- the coefficient of thermal expansion of the conductive substrate is preferably close to the coefficient of thermal expansion of the thermoelectric conversion material.
- Figure 1 is a diagram schematically illustrating an example of a thermoelectric conversion element obtained by connecting one end of a P-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material to a conductive substrate using a conductive paste. It is.
- Each of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material may be connected to the conductive substrate using a conductive paste for connecting the thermoelectric conversion material having the same composition, or the p-type thermoelectric conversion material and the conductive paste may be used.
- the above-mentioned conductive paste for connecting the p-type thermoelectric conversion material is used for connection with the conductive substrate, and the above-mentioned conductive paste for connecting n-type thermoelectric conversion material is used for connecting the n-type thermoelectric conversion material to the conductive substrate. May be used.
- the specific composition of these conductive pastes may be selected according to the mechanical strength, contact resistance, and the like of the connection part required for the thermoelectric conversion element or the thermoelectric power generation module.
- the composition and amount of the oxide powder to be mixed in the conductive paste are determined by the type of the thermoelectric conversion material and the conductive substrate used. May be appropriately determined according to the conditions.
- a plurality of oxide powders may be added in consideration of the mechanical characteristics, electric characteristics, and the like of the connection portion.
- connection method may be the same as in the case where a conventional noble metal paste is used. Specifically, a conductive paste for connecting a thermoelectric conversion material is applied to a connection portion between the thermoelectric conversion material and the conductive substrate, and then dried and heated to solidify the conductive paste. P-type and n-type thermoelectric conversion materials can be connected.
- the amount of the paste applied is not particularly limited, and may be appropriately determined according to the specific composition of the paste so that the thermoelectric conversion material can be connected with sufficient strength.
- the joints should be formed so that the thickness of the paste before solidification is about 10 xm to 500 zzm and the thickness of the paste layer after solidification is about 1 tm to 200 im. Apply evenly You just have to put on the cloth.
- the heating conditions are not particularly limited, but usually, after heating at about 80 to 200 ° C for about 5 minutes to 1 hour to evaporate the organic solvent, about 500 to 900 ° C. Heat for about 5 minutes to 1 hour to fix the glass component.
- the conductive paste may be solidified while applying pressure in order to bring the substrate and the thermoelectric conversion material into close contact.
- thermoelectric generation module of the present invention uses a plurality of the thermoelectric conversion elements described above, and connects the unbonded end of the P-type thermoelectric conversion material of one thermoelectric conversion element to the n-type thermoelectric conversion material of another thermoelectric conversion element.
- a plurality of thermoelectric conversion elements are connected in series by a method of connecting to an unjoined end.
- thermoelectric conversion material and the end of the n-type thermoelectric conversion material of another thermoelectric conversion element are bonded to each other by bonding the unbonded end of the thermoelectric conversion element to the substrate using a bonding agent. May be connected on the substrate.
- FIG. 2 shows a schematic diagram of a thermoelectric conversion module having a structure in which a plurality of thermoelectric conversion elements are connected on a substrate using a bonding agent.
- thermoelectric conversion module shown in Fig. 2 uses a plurality of thermoelectric conversion elements so that the unbonded end of the p-type thermoelectric conversion material of the thermoelectric conversion element and the unbonded end of the n-type thermoelectric conversion material are in contact with the substrate. On the substrate so that the p-type thermoelectric conversion material of the thermoelectric conversion element and the n-type thermoelectric conversion material of another thermoelectric conversion element are connected in series. It was done.
- the substrate is used mainly for the purpose of improving the heat uniformity and the mechanical strength, and maintaining the electrical insulation.
- the material of the substrate is not particularly limited, it is chemically stable at a high temperature of about 675 K or more without melting, breakage, etc., and does not react with thermoelectric conversion materials, bonding agents, etc. It is preferable to use an insulating material having high thermal conductivity.
- the temperature of the high-temperature portion of the device can be made close to the temperature of the high-temperature heat source, and the generated voltage value can be increased.
- the thermoelectric conversion material used in the present invention is an oxide, it is preferable to use an oxide ceramic such as alumina as the substrate material in consideration of the coefficient of thermal expansion and the like.
- thermoelectric conversion element When the thermoelectric conversion element is bonded to the substrate, it is preferable to use a bonding agent that can be connected with low resistance.
- a noble metal paste such as silver, gold, or platinum, solder, or the like can be preferably used.
- a paste may be used in which a conductive oxide powder is added to a noble metal paste to make the coefficient of thermal expansion approximate to that of a thermoelectric conversion material. When such a paste is used, peeling of the connection portion can be prevented even when power generation at a high temperature is repeated.
- the oxide powder it is also possible to use the oxide powder to be mixed with the conductive paste for connecting the P-type thermoelectric conversion material or the conductive paste for connecting the n-type thermoelectric conversion material.
- thermoelectric conversion elements used for one module is not limited, and can be arbitrarily selected depending on required power.
- FIG. 2 shows a schematic structure of a module using 84 thermoelectric conversion elements. The output of the module is approximately the same as the output of one thermoelectric conversion element multiplied by the number of thermoelectric conversion elements used.
- thermoelectric conversion module of the present invention can generate a voltage by locating one end of the module at the high temperature section and the other end of the module at the low temperature section.
- the substrate surface may be arranged in the high-temperature section, and the other end may be arranged in the low-temperature section.
- the thermoelectric conversion module of the present invention is not limited to such an installation method, and one end may be arranged on the high-temperature side and the other end may be arranged on the low-temperature side.
- the high temperature part and the low temperature part may be reversed.
- thermoelectric conversion material As described above, by connecting the thermoelectric conversion material to the conductive substrate using the conductive paste of the present invention, a proper conductivity is imparted to the connection portion of the thermoelectric conversion element, and the coefficient of thermal expansion of the connection portion is reduced.
- the coefficient of thermal expansion of the thermoelectric conversion material can be approximated. As a result, even when power generation at a high temperature is repeated, it is possible to prevent peeling of the connection portion and maintain good thermoelectric conversion performance.
- thermoelectric conversion element having high thermoelectric conversion efficiency and excellent performance constituted by a thermoelectric conversion material excellent in thermal stability, chemical durability and the like.
- thermoelectric power generation modules using such thermoelectric conversion elements have excellent thermal durability, and do not break even when the high-temperature portion is rapidly cooled from about 100 K to room temperature.
- the power generation characteristics are not easily deteriorated.
- the thermoelectric conversion module of the present invention is not only compact and has a high output density, but also has a high resistance to thermal shock. Therefore, the thermoelectric conversion module can be used in factories, waste incinerators, thermal power plants, nuclear power plants, It can be used for thermoelectric power generation using heat of at least 473 K from the heat source. Furthermore, it can also be used as a power source for automobiles that undergo rapid temperature changes.
- heat can be generated from thermal energy of about 473 K or less, low-temperature heat of about 293 to 473 K such as solar heat, hot water, and body temperature can be used as the heat source. Therefore, by installing an appropriate heat source, it can be used as a power source that does not require charging for mobile devices such as mobile phones and notebook computers.
- FIG. 1 schematically shows an example of a thermoelectric conversion element obtained by bonding a thermoelectric conversion material to a conductive material using a conductive paste
- Fig. 2 shows multiple thermoelectric conversion elements connected on a substrate.
- FIG. 3 is a schematic view of a thermoelectric power generation module having a structure
- FIG. 3 is a diagram schematically illustrating the thermoelectric conversion element obtained in Example 1
- FIG. 4 is a view of a substrate (high-temperature part) of the thermoelectric conversion element of Example 1 and Comparative Example 1.
- FIG. 5 is a graph showing the relationship between the temperature and the open-circuit voltage Vo, FIG.
- FIG. 5 is a graph showing the relationship between the temperature of the substrate (high-temperature portion) of the thermoelectric conversion elements of Example 1 and the comparative example and the internal resistance Ro
- FIG. 7 is a graph showing the relationship between the maximum output of the thermoelectric conversion elements of Example 1 and the comparative example and the temperature of the high-temperature part (substrate).
- FIG. 7 is a thermoelectric generation module obtained by using the thermoelectric conversion elements obtained in Example 1.
- Fig. 5 is a graph showing the power generation characteristics.
- This powder is press-formed into a disc having a diameter of 20 mm and a thickness of 2 to 10 mm.
- a gold sheet is laid on an alumina port, and the formed body is placed on the gold sheet.
- Medium 300ml / ) For 20 hours.
- the obtained sintered body was ground using an agate mortar and a pestle.
- the obtained powder was formed into a 30 mm square, 5 mm thick square plate under pressure, and subjected to hot press sintering in air at 1123 K (850 ° C.) for 20 hours under uniaxial pressure of lOMPa.
- the resulting hot press sintered body was cut out into a rectangular parallelepiped having a surface perpendicular to the pressing surface of 4 mm square and a length along the pressing surface of 5 mm, and was molded to obtain a P-type thermoelectric conversion material.
- thermoelectric conversion materials Manufacture of n-type thermoelectric conversion materials
- the precipitate was heated and fired in air at 1073 K (800 ° C.) for 10 hours to thermally decompose nitrate. Next, the fired product was mixed with an agate mortar and pestle.
- the obtained powder is press-formed into a disc having a diameter of 2 cm and a thickness of about 2 to 10 mm. Then, a platinum sheet is laid on an aluminum port, and the formed body is placed thereon. It was baked for 20 hours in a stream (300 ml / min). The obtained sintered body was ground using an agate mortar and pestle. This powder was pressed again to the above-mentioned size, baked under the same conditions, and the obtained sintered body was ground using an agate mortar and pestle.
- the obtained powder was press-formed into a 30 mm square, 5 mm thick square plate, and subjected to hot press sintering in 1173K (900 ° C) air for 20 hours under uniaxial pressing of lOMPa.
- the obtained hot press sintered body was cut out into a rectangular parallelepiped having a surface perpendicular to the pressing surface of 4 mm square and a length along the pressing surface of 5 mm, and was molded to obtain an n-type thermoelectric conversion material.
- the powder obtained by powder milling was further subjected to pole milling using an agate pot and a pole for 10 minutes. went. Observation of the obtained oxide powder with a scanning electron microscope revealed that 80% or more of the particles were in the range of particle diameter of 1 to 1 O ⁇ m.
- a conductive paste for bonding a P-type thermoelectric conversion material was obtained.
- the silver paste used was silver powder (particle size: about 0.1 to 5 zm) 85% by weight, bismuth borosilicate glass 1% by weight, ethyl cellulose 5% by weight, terbineol 4% by weight, and butyl carbitol acetate
- the amount of the oxide powder was 6.25 parts by weight based on 100 parts by weight of the silver powder in the silver paste.
- thermoelectric conversion material production the powder obtained by baking at 1273K (1000 ° C) for 20 hours and pulverizing twice was repeated for another 10 minutes using an agate pot and a pole. Crushed. Observation of the obtained oxide powder with a scanning electron microscope revealed that more than 80% of the particles were in the particle size range of 1 to 10.
- This oxide powder was added to a commercially available silver paste to obtain a conductive paste for connecting an n-type thermoelectric conversion material.
- the type of silver paste used and the amount of oxide powder added are the same as those of the conductive paste for connecting a p-type thermoelectric conversion material.
- thermoelectric conversion material and n-type thermoelectric conversion material were connected to a conductive substrate to manufacture a thermoelectric conversion element using a pair of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material.
- a substrate having a 5 mm ⁇ 8 mm, 1 mm thick alumina plate coated uniformly with a silver paste on a 5 mm ⁇ 8 mm surface and dried to form a conductive film of a silver paste was used.
- the conductive paste for connecting the P-type thermoelectric conversion material and the conductive paste for connecting the n-type thermoelectric conversion material described above are applied to the 4 mm X 4 mm surfaces of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material, respectively.
- the surface coated with the conductive paste of each thermoelectric conversion material was placed in contact with the silver paste-coated surface of the alumina substrate, heated at 373K (100) for about 10 to 30 minutes, and then heated to 1073K (800
- the conductive paste was dried and solidified by heating in air for 15 minutes.
- the coating amount of the paste was such that the thickness before solidification was about 50. In this case, the thickness of the paste layer after solidification was about 20 / zm.
- thermoelectric conversion element an insulating ceramic paste containing alumina as a main component is applied to the connection portion and dried to obtain a thermoelectric conversion element.
- FIG. 3 shows a schematic diagram of the obtained thermoelectric conversion element.
- the substrate is heated to 328 to 1123K (55 to 850 ° C) using an electric furnace, and the opposite end is cooled by a cooler to 303 to 773K (30 to 500K). (° C), the open circuit voltage Vo and the electric resistance Ro were measured.
- the open-circuit voltage is the voltage generated between the low-temperature parts of the p-type thermoelectric conversion material and the n-type conversion material when a temperature difference is applied without applying external resistance (load) to the thermoelectric element.
- thermoelectric conversion element obtained in the same manner as in Example 1, the open-circuit voltage Vo and the electric resistance Ro were measured in the same manner. This is a comparative example.
- FIG. 4 is a graph showing the relationship between the temperature of the substrate (high-temperature portion) and the open circuit voltage Vo.
- the open-circuit voltage tends to increase as the temperature of the high-temperature portion increases. This is because the temperature difference between the low-temperature part and the high-temperature part can be increased by increasing the temperature in the high-temperature part, and the absolute value of the Seebeck coefficient tends to increase as the temperature rises. It seems to be due to. A similar tendency was observed in all examples described later.
- the open circuit voltage was 100 mV in Example 1, whereas the comparative example had a low value of 70 mV.
- the bonding interface was separated due to the difference in the coefficient of thermal expansion between the silver and the thermoelectric conversion material due to the connection of the thermoelectric conversion material using the silver paste. This is considered to be due to the fact that the specific oxide powder was blended into the conductive paste, so that the coefficient of thermal expansion of the connection portion and the thermoelectric conversion element were close to each other, and peeling was unlikely to occur.
- Fig. 5 is a graph showing the relationship between the temperature of the substrate (high-temperature part) and the internal resistance Ro.
- the internal resistance of the device of Example 1 was lower than the internal resistance of the device of Comparative Example. This is because in the device of Example 1, in addition to the prevention of peeling of the thermoelectric conversion material, and the inclusion of a specific oxide powder in the conductive paste, the interface between the connection portion and the thermoelectric conversion material was reduced. This is probably due to the decrease in resistance.
- Fig. 6 is a graph showing the relationship between the maximum output calculated using the open-circuit voltage Vo and the internal voltage Ro, and the temperature of the high-temperature section (substrate section). It can be seen that the device of Example 1 can obtain a higher output than the device of Comparative Example.
- FIG. 7 is a graph showing power generation characteristics of a thermoelectric power generation module obtained by using 10 sets of the thermoelectric conversion elements obtained in Example 1. Although the output estimated from the results in Fig. 6 could not be obtained, it was demonstrated that the operation of a small-sized motor was possible by using this module to generate thermoelectric power.
- the oxide powder, p-type thermoelectric conversion material and n-type thermoelectric conversion material to be mixed in the conductive paste for connecting the P-type thermoelectric conversion material and the conductive paste for connecting the n-type thermoelectric conversion material are shown in Tables 1 to 7 below.
- a thermoelectric conversion element was manufactured and the thermoelectric conversion performance was measured in the same manner as in Example 1 except that the material was used.
- the amount of the oxide powder added to the conductive paste is shown as parts by weight based on 100 parts by weight of the silver powder.
- each table shows the open circuit voltage at 973K in the high temperature part and 500 ⁇ in the low temperature part, and the internal resistance value at 973 ⁇ .
- the open-circuit voltage and the internal resistance both had values superior to those obtained when a thermoelectric conversion material having the same composition was bonded with a silver paste.
- ⁇ 8 is o W0jicF3 ⁇ 4 61
- P-type material Powder for p-type material (parts by weight) Open-circuit voltage Electrode resistance type Material / powder for n-type material (parts by weight) (mV) ( ⁇ )
- the oxide powders shown in Table 8 below were used as the oxide powder to be mixed into the ⁇ -type thermoelectric conversion material connection conductive paste and the ⁇ -type thermoelectric conversion material connection conductive paste.
- the paste was added to a paste (trade name: Au-4460, manufactured by Shoei Chemical Co., Ltd.) to prepare a conductive base.
- the amount of oxide powder added to 100 parts by weight of gold in each paste is also shown in each table.
- the materials shown in Table 8 were also used as the P-type thermoelectric conversion material and the n-type thermoelectric conversion material.
- the gold paste used was 85% by weight of gold powder (particle size: about 0.1 to 5 im), 1% by weight of bismuth borosilicate glass, 5% by weight of ethyl cellulose, 4% by weight of terbineol and 4% by weight of butyl carbitol acetate
- the amount of the oxide powder was 6.25 parts by weight with respect to 100 parts by weight of the silver powder in the gold paste.
- thermoelectric conversion element was produced in the same manner as in Example 1 except that the above-mentioned conductive paste and thermoelectric conversion material were used, and the thermoelectric conversion performance was measured in the same manner as in Example 1.
- Table 8 shows the open-circuit voltage and the internal resistance at 973K: 973K for the high-temperature part and 500K for the low-temperature part. In all of the examples, both the open-circuit voltage and the internal resistance were superior to those obtained when a thermoelectric conversion material having the same composition was bonded with a gold paste. Table 8
- Example P- type material P- type material powder (parts by weight)
- the oxide powders shown in Table 9 below were used as the oxide powders to be mixed into the conductive paste for connecting the ⁇ -type thermoelectric conversion material and the conductive paste for connecting the ⁇ -type thermoelectric conversion material.
- Paste (trade name: D-4001, manufactured by Shoei Chemical Co., Ltd.) A strike was prepared.
- Table 9 also shows the amount of the oxide powder added to 100 parts by weight of platinum in each paste.
- the materials shown in Table 9 were also used as the p-type and n-type thermoelectric conversion materials.
- the platinum paste used was 85% by weight of platinum powder (particle size: about 0.1 to 5 / m), 1% by weight of bismuth borosilicate glass, 5% by weight of ethyl cellulose, 4% by weight of terbineol and 4% by weight of butyl It was composed of 5% by weight of carbitol acetate, and the amount of the oxide powder was 6.25 parts by weight with respect to 100 parts by weight of the silver powder in the platinum paste.
- thermoelectric conversion element was manufactured in the same manner as in Example 1 except that the above-mentioned conductive paste and the thermoelectric conversion material were used, and the thermoelectric conversion performance was measured in the same manner as in Example 1.
- Table 9 shows the open-circuit voltage at 973K in the high temperature section and 500 ⁇ in the low temperature section, and the internal resistance at 973 97. In all of the examples, both the open-circuit voltage and the internal resistance were superior to those obtained when the thermoelectric conversion materials having the same composition were bonded with platinum paste.
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Abstract
Description
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EP04773613A EP1672709B1 (en) | 2003-10-08 | 2004-09-29 | Conductive paste for connecting thermoelectric conversion material |
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EP2975659B1 (en) * | 2014-07-17 | 2019-10-16 | TDK Electronics AG | Thermoelectric generator comprising a thermoelectric element |
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- 2004-09-29 JP JP2005514574A patent/JP4797148B2/ja active Active
- 2004-09-29 WO PCT/JP2004/014680 patent/WO2005036661A1/ja active Application Filing
- 2004-09-29 DE DE602004027152T patent/DE602004027152D1/de active Active
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JP2013063906A (ja) * | 2005-07-07 | 2013-04-11 | Yokohama National Univ | 配向制御したCo酸化物多結晶体の製法 |
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US10508324B2 (en) | 2008-01-23 | 2019-12-17 | Furukawa Co., Ltd. | Thermoelectric conversion material and thermoelectric conversion module |
JP2013143243A (ja) * | 2012-01-10 | 2013-07-22 | Noritake Co Ltd | 導電性接合材とこれを用いたセラミック電子材料の接合方法およびセラミック電子デバイス |
JP2014146583A (ja) * | 2013-01-30 | 2014-08-14 | Noritake Co Ltd | ペースト組成物と太陽電池 |
JPWO2015174462A1 (ja) * | 2014-05-16 | 2017-05-25 | 国立研究開発法人産業技術総合研究所 | 熱電変換素子及び熱電変換モジュール |
JP2019067987A (ja) * | 2017-10-04 | 2019-04-25 | 直江津電子工業株式会社 | 熱電変換素子及びその製造方法並びに熱電変換モジュール |
WO2021153550A1 (ja) | 2020-01-31 | 2021-08-05 | 国立研究開発法人産業技術総合研究所 | 熱電変換モジュール |
Also Published As
Publication number | Publication date |
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DE602004027152D1 (de) | 2010-06-24 |
JPWO2005036661A1 (ja) | 2006-12-28 |
EP1672709B1 (en) | 2010-05-12 |
EP1672709A4 (en) | 2008-01-16 |
EP1672709A1 (en) | 2006-06-21 |
US20070125412A1 (en) | 2007-06-07 |
US7732704B2 (en) | 2010-06-08 |
JP4797148B2 (ja) | 2011-10-19 |
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