WO2005064698A1

WO2005064698A1 - Thermoelectric generator

Info

Publication number: WO2005064698A1
Application number: PCT/JP2004/019194
Authority: WO
Inventors: Ryoji Funahashi
Original assignee: National Institute Of Advanced Industrial Science And Technology
Priority date: 2003-12-26
Filing date: 2004-12-22
Publication date: 2005-07-14
Also published as: JP4595123B2; JPWO2005064698A1

Abstract

A thermoelectric generator comprises a thermoelectric generating module and a catalyst burning heat source. The thermoelectric generating module is composed by using thermoelectric conversion devices connected in series where one end of a p-type thermoelectric conversion material is electrically connected to one end of an n-type thermoelectric conversion material and by connecting the unconnected end of the p-type thermoelectric conversion material of thermoelectric conversion device to the unconnected end of the n-type thermoelectric conversion of another thermoelectric conversion device. The catalyst burning heat source is disposed so as to heat one surface of the thermoelectric generating module. The thermoelectric generator is a power supply suitable for the power supply of portable devices and excellent in portability, and can supply power with a stable performance for a long time.

Description

Specification

Thermoelectric generator

Technical field

The present invention relates to a thermoelectric generator including a catalytic combustion heat source and a thermoelectric generation module.

Background art

[0002] With the development of portable electronic devices such as mobile phones and notebook computers, the development of small power supplies for supplying power to these devices is also progressing.

[0003] In recent years, the speed of improving the performance of electronic devices, such as the CPU (Central Processing Unit) of computers, has been remarkable, and the power consumption has increased dramatically in proportion to this. It has increased.

[0004] Small power supplies currently in practical use are mostly batteries. Their high performance, for example, high energy density, has not been able to sufficiently follow the progress of electronic devices. For this reason, there are adverse effects such as shortening the time that the device can be used with one charge, and insufficient power supply performance is a major factor that impairs the convenience of advanced equipment.

[0005] In the first place, a battery is a storage type power source, not an energy conversion type power source, and further improvement in energy density poses a problem in terms of safety. Therefore, there is a high expectation for the development of an energy conversion type compact power supply that can be used for a long time without charging and can be used as needed as a power supply instead of a battery. I am waiting.

[0006] Thermoelectric power generation is possible if a heat source is present, and the system is smaller and lighter because it does not require a turbine or electrolyte. It also requires less power, requires less noise, and requires less maintenance. This is a very good power generation method. For this reason, combining thermoelectric power generation modules with excellent performance and small and safe heat sources will enable continuous use of the power supply, greatly improving the convenience of electronic equipment.

[0007] Conventionally, various types of thermoelectric conversion materials used in thermoelectric power generation modules have been used. Most of the forces being developed contain toxic elements such as Te and Se. On the other hand, in recent years, thermoelectric conversion materials made of various oxidants have been reported as thermoelectric conversion materials having high safety and high durability even in high-temperature air (Patent No. 3069701, Japanese Patent No. 3443641, Japanese Patent No. 3089301, Japanese Patent No. 3472814, Japanese Patent No. 3472813, Japanese Patent Application Laid-Open No. 2003-282964, etc.).

[0008] As described above, new materials are being developed for thermoelectric conversion materials, but the efficiency is high!開発 At present, development of thermoelectric power generation modules required to realize thermoelectric power generation and small power supply units that combine them with heat sources is delayed. Disclosure of the invention

Problems to be solved by the invention

[0009] The present invention has been made in view of the current state of the prior art as described above, and its main purpose is to provide a power supply device excellent in portability suitable as a power supply for portable equipment and the like, An object of the present invention is to provide a novel thermoelectric generator capable of supplying power with stable performance for a long time. Means for solving the problem

[0010] The present inventors have intensively studied to achieve the above object. As a result, we developed a thermoelectric power generation module with excellent performance using composite oxides as p-type and n-type thermoelectric conversion materials, and by using this module in combination with a catalytic combustion type heat source, The present inventors have found that a small, lightweight, and highly portable power supply device that can be used stably over time can be obtained, and the present invention has been completed.

[0011] That is, the present invention provides the following thermoelectric generator.

1. Using a plurality of thermoelectric conversion elements electrically connecting one end of the p-type thermoelectric conversion material and one end of the n-type thermoelectric conversion material, and the unbonded one end of the P-type thermoelectric conversion material of the 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 to the unjoined end of the n-type thermoelectric conversion material of another thermoelectric conversion element,

A catalytic combustion heat source arranged to heat one surface of the thermoelectric generation module.

Thermoelectric generator provided.

2. Catalytic combustion heat source is generated in the catalytic combustion chamber filled with catalyst and in the catalytic combustion chamber 2. The thermoelectric generator according to the above item 1, comprising a heat transfer unit for transmitting heat energy to the thermoelectric generator module.

3. The thermoelectric generator according to the above item 2, wherein the catalytic combustion heat source further comprises a fuel container containing fuel to be supplied to the catalytic combustion chamber.

4. The thermoelectric generator according to item 2, wherein the catalytic combustion heat source further includes a preheater.

5. The thermoelectric generator according to item 3, wherein the catalytic combustion heat source further includes a preheater.

6.Power of p-type thermoelectric conversion material used in thermoelectric generation module General formula: Ca A ¹ Co A ² O (where a ¹ is Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, One or more elements selected from the group force of Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanoids are also selected, and A ² is Ti, V, Cr, Mn, Fe, One or more elements selected from the group consisting of Ni, Cu, Ag, Mo, W, Nb and Ta, 2.2≤a≤3.6; 0≤b≤0.8; 2.0≤c≤4.5; 0≤ d≤2.0; 8≤e≤10) and a general formula: Bi Pb M ¹ Co M ²⁰ (where M ¹ is

f g h i j k

, Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Ca, Sr, Ba, Al, Y and lanthanide M ² is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta, and 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. ) Is at least one oxide selected from the group consisting of composite oxides represented by

If the n-type thermoelectric conversion material has the general formula: Ln R ¹ Ni R ² O (where Ln is a lanthanoid

m n p q r

R ¹ is a group consisting of Na, K, Sr, Ca and Bi.One or more elements are selected.R ² is Ti, V, The group force consisting of Cr, Mn, Fe, Co, Cu, Mo, W, Nb and Ta is also one or more elements selected from the group consisting of 0.5≤m≤1.7; 0≤n≤0.5; 0.5≤p≤ 1.2; 0≤q≤0.5; 2.7≤r≤3.3. ), And a general formula: (Ln R ³ ) Ni R ⁴ O (where Ln is a member selected from lanthanoids or st 2 uw

Is two or more elements, R ³ is one or more elements selected from the group consisting of Na, K, Sr, Ca and Bi, and R ⁴ is Ti, V, Cr, Mn, Fe, Co, Cu, Mo, W, Nb and Group power consisting of Ta One or more elements selected from the group consisting of 0.5≤s≤1.2; 0≤t≤0.5; 0.5≤u≤1.2; 0≤v≤0.5; 3.6≤w≤4.4. 3. The thermoelectric generator according to item 1, wherein the thermoelectric generator is at least one selected oxide selected from the group consisting of the composite oxides represented by the formula (1).

7. Power of p-type thermoelectric conversion material used in thermoelectric generation module General formula: Ca A ¹ Co O (where a ¹ is Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, The group force consisting of Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanoids is also one or more elements selected from the group consisting of 2.2≤a≤3.6; 0≤b≤0.8; 8≤e ≤10) and a general formula: Bi Pb M ¹ Co Of 2

(Wherein, M ¹ is ^one or more elements selected from the group consisting of Sr, Ca, and Ba, and is 1.8≤f≤2.2; 0≤g≤0.4; 1.8≤h≤2.2; 8≤ k ≦ 10) at least one selected oxidizing compound consisting of a composite oxide represented by)

The n-type thermoelectric conversion material has the general formula: La R ¹ NiO (where R ¹ is mnr from Na, K, Sr, Ca and Bi

Is one or more elements selected from the group consisting of, 0.5≤m≤1.2; a 2. ⁷ ≤r≤3 ^3; 0≤n≤0.5.. ), A general formula: (La R ³ ) NiO (where R ³ is st 2 w

One or more elements selected from the group consisting of Na, K, Sr, Ca and Bi, and 0.5 ≤ s ≤ 1.2; 0 ≤ t ≤ 0.5; 3.6 ≤ w ≤ 4.4. ) And a general formula: L a R ⁵ Ni R ⁶ O (where R ⁵ is a small P selected from the group consisting of Na, K, Sr, Ca, Bi and Nd)

R ⁶ is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co and Cu; 0.5≤x≤1.2; 0≤y≤0.5 ; 0.5≤p≤ 1.2; 0.01≤q ≤0.5; 2.8≤r≤3.2. Item 2. The thermoelectric generator according to Item 1, which is at least one kind of acid selected from the group consisting of composite oxides represented by the formula (1).

8. The thermoelectric generator according to any one of the above items 1 to 17, wherein a cooling means is provided on a surface of the thermoelectric generation module opposite to a surface to be heated.

The thermoelectric generator of the present invention uses a plurality of thermoelectric conversion elements each formed by electrically connecting one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material, and uses the p-type thermoelectric conversion material of the thermoelectric conversion element. A thermoelectric power generation module comprising a plurality of thermoelectric conversion elements connected in series by a method of electrically connecting one unbonded end of the thermoelectric conversion element to an unbonded end of an n-type thermoelectric conversion material of another thermoelectric conversion element; and And a catalytic combustion heat source arranged to heat one surface of the thermoelectric generation module. Hereinafter, the thermoelectric generator of the present invention and its respective components will be specifically described.

(1) Catalytic combustion heat source

As the catalytic combustion heat source, any heat source can be used without particular limitation as long as it can heat one surface of the thermoelectric generation module by thermal energy generated by catalytic combustion.

[0015] Usually, it is possible to use a catalytic combustion type heat source provided with a catalytic combustion section filled with a catalyst and a heat transfer section for transmitting thermal energy generated in the catalytic combustion section to the thermoelectric power generation module.

[0016] The specific structure of the catalytic combustion section is not particularly limited, and various types of known catalytic combustors can be used. Usually, a combustor having a structure in which a catalyst component is supported on various substrates can be used.

As the catalyst component, any component can be used without particular limitation as long as it has a catalytic activity for a catalytic combustion reaction, that is, an oxidation reaction of a fuel component described later. In particular, it is preferable that one side of the thermoelectric power generation module can be heated to, for example, about 800 ° C. or more by the thermal energy generated by the catalytic combustion reaction. For example, precious metals such as Pt and Pd, acid oxides such as Coo and the like can be used as the catalyst component, but are not limited thereto.

3 4

is not. In consideration of durability at high temperatures, Pt fine particles, Pd fine particles, a mixture thereof and the like are particularly preferable.

[0018] As a substrate for supporting the catalyst component, it is preferable to use a material having sufficient strength and excellent heat resistance. For example, ceramic materials having excellent heat resistance such as alumina and zirconia, and metals having better heat resistance having a coefficient of thermal expansion close to those of these heat-resistant ceramics, for example, Fe—Cr— such as SUS—510 stainless steel A composite material or the like obtained by coating the surface of an A1-based ceramic with the above-described heat-resistant ceramic and sintering can be used as a base material. The shape of the substrate is not particularly limited, but it is preferable that the fuel gas flow be good and the contact area between the fuel and the catalyst component be large. For example, a substrate having a honeycomb structure can be used.

[0019] The fuel is not particularly limited as long as it is a substance capable of catalytic combustion, but is preferably a substance containing no toxic substances before and after combustion from the viewpoint of safety. For example, A hydrocarbon gas such as methane, ethane, propane, and butane, and an organic liquid such as methanol, ethanol, and ethyl ether can be used.

[0020] The fuel supply method is not particularly limited, and a fuel container containing a fuel may be connected to the fuel supply port of the catalytic combustion unit, and the fuel container and the catalytic combustion heat source may be integrated. Alternatively, a fuel container or the like provided separately from the catalytic combustion heat source may be used as a fuel supply source, and the fuel supply source and the fuel supply port of the catalytic combustion unit may be connected by a pipe such as a pipe or a hose.

[0021] In particular, when the fuel container and the catalytic combustion type heat source are integrated, the heat source device can be easily moved and used as a power source for a portable device that can be used even in a place where no fuel supply source exists. Can be used effectively.

[0022] The fuel contained in the fuel container may be in any state of gas, liquid and solid as long as safety against rupture or the like can be maintained. When a liquid or solid fuel is used, for example, it may be volatilized in a fuel container and brought into a gaseous state in advance. In order to supply gas to the catalytic combustion section, it is preferable to keep the inside of the fuel container at a higher pressure than the combustion section. In addition, since fuel decreases by combustion, a fuel supply port is usually provided in a fuel container. Further, a blower using a fan or the like may be mounted to promote the supply of the fuel gas to the catalytic combustion section. In this case, as the power of the fan, for example, electric energy generated by thermoelectric generation can be used.

[0023] The fuel gas is usually mixed with an oxygen-containing gas such as air or the like, and supplied to the catalytic combustion section as a fuel concentration suitable for catalytic combustion. For this reason, the catalytic combustion heat source is usually provided with a supply port for supplying an oxygen-containing gas such as air. If necessary, a mixing chamber for mixing the fuel gas and the oxygen-containing gas can be provided. Since the fuel concentration varies depending on the type of fuel, the type of catalyst substance, etc., it cannot be specified unconditionally. However, when used in a mixture with air, the concentration of the fuel gas is usually 0.5 to 10% by volume percentage. Should be within the range.

[0024] The heat conduction section is a section that transmits heat energy generated in the catalytic combustion section to the thermoelectric generation module. The heat conduction section may be provided in accordance with the shape of the catalytic combustion section so that heat energy can be efficiently transmitted to the thermoelectric generation module. For example, the heat conduction part As a plate-like shape, it can be installed so that the combustion gas that has reached a high temperature by catalytic combustion can be directly blown to the heat conducting part. Further, a structure may be adopted in which a heat conducting portion is disposed in parallel with the passage of the combustion gas, and heat is transferred by contact with the passing combustion gas. In this case, for example, the heat conducting portion can be installed as a cylinder such as a square or a circle so as to surround the passage of the combustion gas.

[0025] The material of the heat conducting portion is preferably chemically stable even in high-temperature air, and is not damaged by heating and cooling. In the case of using a high-temperature operating type oxidizing material as the thermoelectric conversion material, it is usually sufficient to heat the high-temperature part of the thermoelectric power generation module to about 400 to 800 ° C. It is preferably formed of a material that is stable even at about ° C, for example, ceramics such as alumina, and metals such as stainless steel, silver, and platinum having high high-temperature durability.

[0026] In order to start catalytic combustion, usually, the fuel gas or the catalytic combustion section is heated to a temperature required for the catalytic combustion reaction. The heating temperature varies depending on the type of the fuel, the type of the catalyst substance, and the like, but generally, the heating may be performed up to about 300 ° C. For this reason, a preheater for heating the fuel gas or the catalytic combustion section to the temperature required for catalytic combustion is usually installed in the catalytic combustion heat source. As the preheater, for example, a burner that burns fuel gas, a heater that stores excess power generated by thermoelectric generation in a capacitor or a battery, and generates heat by the power when restarting, etc. can be used. . In order to enhance the portability of the power supply device, it is preferable to integrate the preheater with the catalytic combustion type heat source.For example, when introducing the fuel gas from outside the catalytic combustion device, the preheating of the fuel gas is performed. The vessel may be installed outside the catalytic combustion heat source.

(2) Thermoelectric power generation module

As the thermoelectric generation module, for example, a plurality of thermoelectric conversion elements formed by electrically connecting one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material are used. Structure in which a plurality of thermoelectric conversion elements are connected in series by electrically connecting one end of the non-bonded type thermoelectric conversion material to the other end of the n-type thermoelectric conversion material of another thermoelectric conversion element Can be used.

[0028] The specific shape is not particularly limited, but may be determined by the above-described catalytic combustion heat source. For efficient heating, it is preferable that the area of the substrate surface to which the thermoelectric conversion material is bonded is large. Normally, a module having a plate-like structure as a whole is preferable.

[0029] The type of the p-type thermoelectric conversion material and the type of the n-type thermoelectric conversion material are not particularly limited. Each of the materials exhibits a positive Seebeck coefficient when a temperature difference is generated between both ends. And a material having a negative Seebeck coefficient may be used. In the present invention, it is particularly preferable to use a thermoelectric conversion material which can be used stably in high-temperature air and also has an oxidizing power.

[0030] Specifically, as the p-type thermoelectric conversion material, a composite oxide represented by Ca Co O, Ca Co

3 4 9 3 4

A composite oxide obtained by substituting a part of Ca and Z or Co of O with another element, Bi M Co 0 (M is

9 2 2 2 9

Sr, Ca or Ba), a complex oxide represented by Bi M Co 0 Bi and

Co-based layered oxides such as complex oxides in which a part of 222 or Z is substituted with other elements can be used. Ma

2

In addition, as an n-type thermoelectric conversion material, a composite oxidizing material represented by LnNiO (Ln is a lanthanoid) is used.

Three

, Such as complex oxides in which part of Ln and Z or Ni of LnNiO are replaced with other elements

Three

Composite oxide with skyte structure, Ln NiO with Ln of NiO

2 4 Complex oxide represented by Ln

A composite oxide having a layered perovskite structure, such as a composite oxide in which 24 and / or Z or Ni is partially substituted with another element, can be used.

[0031] These thermoelectric conversion materials will be described more specifically.

[0032] _¾ί ¾ίThermal _thunder橼 Material

The Ρ-type thermoelectric conversion material has the general formula: Ca A ¹ Co A ² O (where A ¹ is Na, K, Li, abcde

One or more elements selected from the group consisting of 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, Ag, Mo, W, Nb, and Ta; 2.2≤a≤3.6; 0≤ b≤0.8; 2.0≤c≤4.5; 0≤d≤2.0; 8≤e≤10. ) And a general formula: Bi Pb M ¹ Co M ²⁰ (where M ¹ is Na, K, Li, Ti, V, Cr, fghijk

Mn, Fe, Ni, Cu, Zn, Pb, Ca, Sr, Ba, Al, Y and one or more elements selected from a group of lanthanoids, and M ² is Ti, V, The group force consisting of Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta is also one or more elements selected, and 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. ) The at least one selected selected from the group consisting of the composite iris can be used. In each of the above general formulas, examples of the lanthanoid element include La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and the like.

[0033] The composite oxide represented by such a general formula is Ca CoO composed of Ca, Co and 0.

2 3 that the composition ratio, or Bi, rock-salt type composition ratio of configured Bi M ¹ 0 by M ¹ and 0 structure

2 2 4

And a CoO layer in which six 0s are octahedrally coordinated with one Co and two-dimensionally arranged so that the octahedra have sides with each other. ,

2

In the former case, a part of Ca of Ca CoO is replaced by A ^1, further part of Co in the layer and

twenty three

Some of Co in CoO layer is replaced by A ^2, part s the or Pb and Bi in the latter

2

It is replaced with a part, part of Co is replaced by M ^2!, Ru.

[0034] These composite oxides have a high Seebeck coefficient as a p-type thermoelectric conversion material, and also have good electric conductivity. For example, it has a Seebeck coefficient of about 100 VZK or more at a temperature of 100 K or more, and an electric resistivity of about 50 mΩcm or less, preferably about 30 mΩcm or less. We can get something that shows a tendency to decrease.

[0035] Among the above-mentioned complex oxidized products, an example of a preferred oxidized product is a compound represented by a general formula: Ca A ¹ Co O ab 4 e

(Wherein, A ¹ is, Na, K, Li, Ti , V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, also the group force consisting of Y及beauty lanthanoid is selected A complex oxide represented by the formula: Bi Pb M ¹ Co fgh 2, which is one or more of the following elements: 2.2 ≤ a ≤ 3.6; 0 ≤ b ≤ 0.8; 8 ≤ e ≤ 10.

O (wherein, M ¹ is a group consisting of Sr, Ca and Ba. One or more selected elements k

1.8≤f≤2.2; 0≤g≤0.4; 1.8≤h≤2.2; 8≤k≤10. )), At least one kind of oxide selected from the group consisting of the complex oxide represented by the formula (1). These oxides have, for example, a Seebeck coefficient of about 100 νΖκ or more at a temperature of 100 K or more and an electric resistivity of about 10 mΩcm or less.The Seebeck coefficient increases with increasing temperature, and the electric resistivity decreases. May be shown.

[0036] The composite oxide represented by each of the above general formulas may be either a single crystal or a polycrystalline sintered body.

[0037] The method for producing these complex oxidized products is not particularly limited as long as the method can produce a single crystal or a polycrystal having the above-mentioned composition. [0038] For example, 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 method, a laser 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 brazing method and a chemical 'vapor-deposition' method.

As an example of these methods, a method for producing the composite oxide of the present invention by a solid-phase reaction method will be described below.

[0040] The above-mentioned composite oxidized product 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. .

[0041] 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 1073 to 1373K (absolute temperature), — Bake for about 40 hours. When a carbonate, an organic compound, or the like is used as the raw material, it is preferable that the raw material be decomposed by calcining before firing, and then fired to form the target composite oxide. For example, when a carbonate is used as a raw material, it may be calcined at about 1073 to 1173 K (absolute temperature) 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 may be usually an oxidizing atmosphere such as an oxygen stream or air, but when the raw material contains a sufficient amount of oxygen, the firing may be performed in an inert atmosphere, for example. It is possible. The amount of oxygen in the resulting composite oxide can be controlled by the oxygen partial pressure during firing, the firing temperature, the firing time, etc., and the higher the oxygen partial pressure, the higher the oxygen ratio in the above general formula can be. .

[0042] In the glass annealing method via a glass precursor, first, a raw material is melted, rapidly cooled, and solidified. The melting conditions at this time may be any conditions that can uniformly melt the raw material.However, in order to prevent contamination of the melting vessel power and evaporation of the raw material components, for example, when using an aluminum crucible, It is preferable to melt by heating to about 1473-1673K (absolute temperature). The heating time is not particularly limited, and the heating may be performed until the raw material is uniformly melted. Usually, the heating time may be about 30 minutes to 1 hour. heating The means is not particularly limited, and any means such as an electric heating furnace and a gas heating furnace can be adopted. The atmosphere at the time of melting may be an oxygen-containing atmosphere such as in air or an oxygen gas stream of about 300 ml Zl or less.If the raw material contains a sufficient amount of oxygen, the atmosphere is melted in an inert atmosphere. Is also good.

[0043] The quenching condition is not particularly limited, but the quenching may be performed under such a condition that at least the surface portion of the formed solid becomes a glassy amorphous layer. For example, the melt may be poured onto a metal plate and rapidly cooled by means of upward compression. Usually, the cooling rate should be about 500K (absolute temperature) Z seconds or more, and preferably ³ κΖ seconds or more.

[0044] Next, by subjecting the solidified material formed by rapid cooling to a heat treatment in an oxygen-containing atmosphere, a target composite oxide grows as a fibrous single crystal from the surface of the solidified material.

The heat treatment temperature may be about 1153 to 1203 K (absolute temperature), and heating may be performed in an oxygen-containing atmosphere such as air or an oxygen stream. When heating in an oxygen stream, for example, heating may be performed in an oxygen stream having a flow rate of about 300 mlZ or less. The heat treatment time is not particularly limited, and may be determined according to the degree of growth of the target single crystal. Force Normally, the heating time may be about 60 to 1000 hours.

[0046] The mixing ratio of the raw materials can be determined according to the composition of the target 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, and Since an oxidized single crystal having a composition of a solid phase in phase equilibrium 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) which are in equilibrium with each other. it can.

[0047] The size of the composite oxide single crystal obtained by such a method is determined by a force that can vary depending on the type of the raw material, composition ratio, heat treatment conditions, and the like. For example, a length of about 10 to 1000 m and a width of 20 to 200 μm It has a fibrous shape of about m and a thickness of about 11 μm.

[0048] In any of the above-mentioned glass annealing method and the solid-phase reaction method via the glass precursor, 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 content Although the amount of oxygen increases, the change in the amount of oxygen contained Does not significantly affect the electrical characteristics of the.

[0049] The raw material is not particularly limited as long as it can form an oxide by firing, and a metal alone, an oxide, various conjugates (such as carbonates) and the like can be used. For example, Ca sources include calcium oxide (CaO), calcium chloride (CaCl 2), calcium carbonate (CaCO 3), and calcium nitrate.

twenty three

Shim (Ca (NO)), calcium hydroxide (Ca (OH)), dimethoxy calcium (Ca (OC

3 2 2

H)), diethoxy calcium (Ca (OC H)), dipropoxy calcium (Ca (OC H

3 2 2 5 2 3 7

))), Etc., and the source of Co may be oxidized cobalt (CoO

2

, Co O, Co O), cobalt chloride (CoCl), cobalt carbonate (CoCO), cobalt nitrate (C

2 3 3 4 2 3

o (NO)), cobalt hydroxide (Co (OH)), dipropoxy cobalt (Co (OCH)), etc.

The alkoxide conjugate of No. 3 232 732 can be used. Similarly, for other elements, elemental elements, oxides, chlorides, carbonates, nitrates, hydroxides, alkoxide compounds and the like can be used. Further, a compound containing two or more kinds of the constituent elements of the above-mentioned composite oxide is used.

[0050] n-type thermal lightning material

As the n-type thermoelectric conversion material, a general formula: Ln R ¹ Ni R ² O (where Ln is a lanthanoid force mnpqr

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 , Cr, Mn, Fe, Co, Cu, Mo, W, Nb and Ta are one or more elements selected from the group consisting of 0.5 ≤ m ≤ 1.7; 0 ≤ n ≤ 0.5; 0.5 ≤ p ≤1.2; 0≤q≤0.5; 2.7≤r≤3.3. ) And the general formula: (Ln R ³ ) Ni R ⁴ O (where Ln is the lanthanoid force selected st 2 uw

R ³ is one or more elements selected from the group consisting of Na, K, Sr, Ca and Bi, and R ⁴ is Ti, V, Cr, Group power consisting of Mn, Fe, Co, Cu, Mo, W, Nb and Ta One or more elements selected from the group consisting of 0.5≤s≤1.2; 0≤t≤0.5; 0.5≤u≤1.2; 0≤v≤0.5; 3.6≤w≤4.4. ) At least one kind of oxide selected from the group consisting of the complex oxides represented by the formula (1) can be used. In the above general formula, the m value is 0.5≤m≤1.7, and preferably 0.5≤m≤1.2. In addition, examples of the lanthanoid element include La-Ce-Pr, Nd, Sm, Eu-Gd, Tb-Dy-Ho, Er, Tm, and Lu. [0051] The composite oxide represented by each of the above general formulas has a negative Seebeck coefficient. When a temperature difference is generated between both ends of a material made of the oxide, a potential generated by a thermoelectromotive force is generated. Is higher on the high temperature side than on the low temperature side, indicating the properties as an n-type thermoelectric conversion material. Specifically, the composite oxide has a negative Seebeck coefficient at a temperature of 373 K or higher, and has a Seebeck coefficient of about 11 to 20 V / K at a temperature of 373 K or higher.

[0052] Further, the above-described composite oxide has a very low electric resistivity, and for example, has an electric resistivity of about 20 mΩcm or less at a temperature of 373 K or more. This comes out.

[0053] In the above-described composite oxidized product, the former has a crystal structure of a perovskite type, and the latter has a crystal structure generally called a layered perovskite.

The three are also called ABO structures. Part of substitution by R ¹ or R ³ either composite Sani匕物also Ln

twenty four

And a part of Ni is substituted with R ² or R ⁴ .

[0054] Among the n-type thermoelectric conversion materials described above, preferred examples of the composite oxide include:

General formula: La R ¹ NiO (where R ¹ is Na

It is one or more elements selected from the group consisting of mnr, K, Sr, Ca and Bi, where 0.5≤m≤1.2; 0≤n≤0.5; 2.7≤r≤3.3. ), A general formula: (La R ³ ) NiO (where R ³ is Na

st 2 w, K, Sr, Ca and Bi forces are also one or more elements selected. 0.5≤s≤1.2; 0≤t≤0.5; 3.6≤w≤4.4. ), A composite oxide represented by the general formula: La R ⁵ Ni R ⁶ O (where R ⁵ x P qr is at least one selected from the group consisting of Na, K, Sr, Ca, Bi and Nd) a element, R ⁶ is at least one of elemental selected Ti, V, Cr, Mn, Fe, from the group consisting of Co and Cu, 0.5≤x≤ 1.2; 0≤y≤0.5; 0.5 ≤p≤1.2; 0.01≤q≤0.5; 2.8≤r≤3.2.

Among these, the composite oxide represented by the general formula: La R ¹ NiO and the composite oxide represented by the general formula: (La R ³ ) N mnrst 2 iO are, for example, at a temperature of 100 K or more. -1-1-30mV / K see w

It has a Beck coefficient and exhibits low electrical resistivity. Further, for example, at a temperature of 100 K or more, the material can have an electric resistivity of about 10 mΩcm or less.

Further, the composite oxide represented by the general formula: La R ⁵ Ni R ⁶ O can be heated at a temperature of 100 ° C. or more.

P It has a negative Seebeck coefficient and exhibits a very low electrical resistivity with low electrical conductivity, and has an electrical resistivity of 10 mΩcm or less at a temperature of 100 ° C or more.

[0057] The polycrystalline sintered body of each of the above composite oxides can be manufactured by mixing and firing the raw materials so as to have the same metal component ratio as that of the target composite oxide. it can. That is, Ln in the above general formula,

By mixing and firing the raw materials so that the metal component ratio of R ⁴ and Ni is attained, a polycrystalline sintered body of the target composite oxide can be obtained.

[0058] The raw material is not particularly limited as long as it can form an oxidized product by firing, and may be a simple metal, an oxide, various oxidized products (such as a carbonate), or the like. For example, as the La source, lanthanum oxylan (La O), lanthanum carbonate (La (CO)), lanthanum nitrate (La (NO)), salt

2 3 2 3 3 3 3 Lanthanum hydride (LaCl), lanthanum hydroxide (La (OH)), alkoxide compound (dimethoxyla

3 3

(La (OCH)), Diethoxysilane (La (OCH)), Dipropoxylantan (La

3 3 2 5 3

(OC H)), etc.). Ni sources include nickel oxide (NiO), nickel nitrate (N

3 7 3

i (NO)), nickel chloride (NiCl), nickel hydroxide (Ni (OH)), alkoxide compound

3 2 2 2

Products (dimethoxynickel (Ni (OCH)), diethoxynickel (Ni (OCH)), dipropo

3 2 2 5 2

Xinickel (Ni (OC H)) or the like can be used. The same applies to other elements.

3 7 2

Compounds, chlorides, carbonates, nitrates, hydroxides, alkoxide compounds and the like can be used. Further, a compound containing two or more kinds of constituent elements of the composite acid oxidant of the present invention may be used.

The calcination temperature and the calcination time are not particularly limited as long as they are conditions under which the target composite oxide is formed. For example, in a temperature range of about 1123 to 1273 K (absolute temperature), It may be fired for about 40 hours. When a carbonate, an organic compound, or the like is used as the raw material, it is preferable that the raw material be decomposed by calcining before firing, and then fired to form a target composite oxide. For example, when a carbonate is used as a raw material, it may be calcined at about 873 to 1073 K (absolute temperature) for about 10 hours and then calcined under the above conditions.

[0060] The firing means is not particularly limited, and any means such as an electric heating furnace or a gas heating furnace can be adopted. The firing atmosphere may be usually an oxygen atmosphere, an oxidizing atmosphere such as in air, When the raw material contains a sufficient amount of oxygen, for example, calcination can be performed in an inert atmosphere.

[0061] The amount of oxygen in the resulting 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. But does not significantly affect the thermoelectric properties.

[0062] Similarly to the above-described composite oxide used as the p-type thermoelectric conversion material, for example, it can be manufactured as a single crystal by a method such as the flatus method.

[0063] Thermal lightning conversion element

The thermoelectric conversion element used in the present invention is one in which one end of the p-type thermoelectric conversion material and one end of the n-type thermoelectric conversion material are electrically connected. In this case, the sum of the absolute values of the thermoelectromotive forces of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material is, for example, at least about 60 μVZK at all temperatures in the range of 293 to 1073K (absolute temperature), preferably 100 μVZK. It is preferable to use a combination of thermoelectric conversion materials so as to be about μVZK or more. Further, both materials preferably have an electric resistivity of about 50 mΩcm or less, preferably about 8 mΩcm or less at all temperatures in the range of 293 to 1073 K (absolute temperature).

[0064] The shape, size, etc. of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material to be used are not particularly limited, but may vary depending on the size, shape, etc. of the target thermoelectric power generation module. First, it may be determined appropriately so as to exhibit necessary thermoelectric performance. For example, a rectangular parallelepiped material with a cross section of about 10 cm on a side and a length of about 100 m to 20 cm, or a cylindrical material with a cross section of —10 cm and a length of about 100 m to 20 cm Can be used as

[0065] The specific method for electrically connecting one end of the p-type thermoelectric conversion material and one end of the n-type thermoelectric conversion material is not particularly limited, but may be 293-1073K (absolute) when joined. It is preferable to use a method that can maintain the characteristics in which the thermoelectromotive force of the element is 60 VZK or more and the electric resistance is 200 mΩ or less in the entire range of (temperature).

As a specific connection method, for example, as a method that can withstand use at high temperatures, one end of the P-type thermoelectric conversion material and one end of the n-type thermoelectric conversion material are bonded to a conductive material using a bonding agent. Method, one end of p-type thermoelectric conversion material and one end of n-type thermoelectric conversion material directly or conductive Examples thereof include a method of pressing or sintering through a material, a method of electrically contacting a p-type thermoelectric conversion material and an n-type thermoelectric conversion material using a conductive material, and the like. Hereinafter, these methods will be described more specifically.

[0067] The electric resistance generated by the connection depends on the connection method, the area of the joint, the type and size of the conductive material to be used, etc., but generally, the electric resistance of the joint occupying the resistance of the entire thermoelectric conversion element. It is preferable to set the connection conditions so that the resistance ratio is about 50% or less.It is more preferable to set it so that it is about 10% or less.It is more preferable to set it so that it is about 5% or less. More preferred.

FIG. 1 schematically shows an example of a heat conversion element obtained by bonding one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material to a conductive material using a bonding agent. It is a drawing. In FIG. 1, the (a-1) type device is obtained by bonding one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material to a substrate using a bonding agent. As a bonding agent, the ability to use metal paste, solder, etc.Especially, as a material that is chemically stable without melting even at a high temperature of about 1073K and can maintain low resistance, such as gold, silver, platinum, etc. It is preferable to use a noble metal base. At the time of bonding, the bonding agent may be solidified while applying pressure in order to bring the substrate and the thermoelectric conversion material into close contact. As the substrate, it is preferable to use a material which is not oxidized even in air at a high temperature of about 1073K. For example, a substrate having an oxidized ceramic such as alumina may be used. The length, width, thickness, etc. of the substrate should be set appropriately according to the size of the module, electrical resistance, etc.

[0069] The (a-2) type element shown in Fig. 1 uses a conductive ceramic substrate as a substrate. In this case, a bonding agent is applied only to an adhesive portion between the substrate and the thermoelectric conversion material. However, when using insulating ceramics, a conductive bonding agent is used between the bonded part of the p-type thermoelectric conversion material and the bonded part of the n-type thermoelectric conversion material as in (a-1) type. It is necessary to electrically connect the p-type thermoelectric conversion material and the n-type thermoelectric conversion material by a method of connection, a method of providing a metal coating on insulating ceramics such as the type (a-3).

[0070] As the conductive ceramic used in the (a-2) type element, it is preferable to use a material that is not oxidized even in air at a high temperature of about 1073K. Further, the length, width, thickness, and the like of the substrate may be appropriately set according to the size of the module, electric resistance, and the like. [0071] The metal coating used in the (a-3) type element may be any metal coating that is not oxidized in high-temperature air and has low electric resistance. For example, silver formed by a vapor deposition method or the like may be used. Precious metal coatings such as gold and platinum can be used.

The (a-4) type element in FIG. 1 is one in which one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material are connected by a conductive wire. The same bonding agent as that of the (a-1) type element can be used for connecting the conductive wires. As the conductive wire, it is preferable to use a material which is not oxidized even in the air at a high temperature of about 1073K. For example, a gold, silver, platinum wire or the like can be used. The length and shape of the conductor may be appropriately selected according to the size of the module, electric resistance, and the like.

FIG. 2 is a drawing schematically showing an example of a thermoelectric conversion element obtained by electrical connection by sintering or crimping.

[0074] The (s-1) type element in Fig. 2 is a thermoelectric conversion element in which an end of a p-type thermoelectric conversion material and an end of an n-type thermoelectric conversion material are directly sintered and connected. For example, after sintering one surface of the p-type thermoelectric conversion material and one surface of the n-type thermoelectric conversion material, a cut is made in the sintered surface using a diamond cutter or the like, and a part of both materials is cut. Can be obtained by separating The length of the cut is not particularly limited, and may be appropriately determined based on necessary electric resistance, voltage, mechanical strength, and the like. As for the contact area between the two materials, the larger the area, the lower the electrical resistance of the entire device.On the other hand, if the length of the separated part of the thermoelectric conversion material is short, the temperature difference between the high temperature area and the low temperature area As the voltage becomes smaller, the generated voltage S becomes smaller, so it is necessary to decide appropriately taking these points into consideration.

[0075] The (s-2) type element in FIG. 2 is used to prevent reaction between thermoelectric conversion materials and maintain high mechanical strength when forming the element by sintering or pressure bonding. This is a device obtained by sintering or crimping with a conductive material such as a metal sheet, a metal net, a binder, conductive ceramics, etc. arranged on the device. In this case, as the metal sheet, the metal net or the like, any material can be used without particular limitation as long as it can prevent a reaction between the materials and has a low resistance. Usually, the thickness is preferably about 100 m. As the binder, for example, a noble metal paste or the like used in the bonding method using the binder can be used. The conductive ceramics include, but are not particularly limited to, plate-shaped conductive ceramics having an appropriate thickness. Can be used.

The (s-3) type element in FIG. 2 uses conductive ceramics as a substrate, and is joined to one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material by sintering. The (s4) type element uses the same metal sheet or metal net as the (s2) type element, through which one end of the p-type thermoelectric conversion material and one end of the n-type thermoelectric conversion material are electrically conductive. It is bonded to a conductive ceramic substrate by sintering. The (s-5) type element is composed of two oxide plates having the same shape and area as the cross section of each of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material, such as a metal sheet and a metal net. They are joined to a p-type thermoelectric conversion material and an n-type thermoelectric conversion material by sintering via a conductive substance. The oxidizing plate is not particularly limited as long as it can be bonded to the thermoelectric conversion material to be bonded by sintering, and does not deteriorate power generation characteristics even when used at a high temperature for a long time. Can be used. In particular, it is preferable to use an oxide having the same crystal structure as the thermoelectric conversion material to be joined. The composition is more preferably the same as the thermoelectric conversion material to be joined. Although the thickness of the oxide plate is not particularly limited, it is usually about 11 to 13 mm.

When the element shown in FIG. 2 is manufactured by a sintering method, the adhesion between materials can be further improved by firing under pressure by a method such as hot press sintering.

FIG. 3 is a drawing schematically showing an example of a thermoelectric conversion element obtained by bringing a p-type thermoelectric conversion material and an n-type thermoelectric conversion material into electrical contact using a conductive material.

[0079] The (c1) -type element in Fig. 3 is formed by making a hole in a p-type thermoelectric conversion material and an n-type thermoelectric conversion material, and penetrating a conductive material into the hole to form a P-type thermoelectric conversion material and an n-type thermoelectric conversion material. Is a thermoelectric conversion element electrically connected. As the conductive material, it is preferable to use a material that is chemically stable and does not melt even at a high temperature of about 1073K and has low resistance. For example, in addition to the above-described metal sheets, metal nets, and the like, conductive ceramics in the form of plates and rods; insulating ceramics such as alumina are coated with gold, silver, or the like by a vapor deposition method to impart conductivity. A plate-like or rod-like material can be used.

[0080] The (c-2) -type thermoelectric conversion element is configured such that various conductive materials such as a conductive wire are fixed to an end of a p-type thermoelectric conversion material and an end of an n-type thermoelectric conversion material with a clip or the like, and electrically connected. These are connected thermoelectric conversion elements. The material of the clip is, for example, It is preferable to use metals such as gold, and insulating ceramics such as alumina, which are preferable to use a suitable material. As the conductive material, any material can be used as long as it can electrically connect the p-type thermoelectric conversion material and the n-type thermoelectric conversion material with low resistance. For example, various metals and conductive ceramics can be used. The length, width, thickness, etc. of the conductor material should be determined appropriately according to the module size, electrical resistance, etc.

[0081] The mechanism for fixing the conductor material is not particularly limited. For example, the conductor material may be fixed by sandwiching the conductor material with a clip of a panel type, a screw type, or the like.

[0082] The (c-3) -type thermoelectric conversion element is a thermoelectric conversion element in which the above-described various conductive materials are screwed and electrically connected to the end of the p-type thermoelectric conversion material and the end of the n-type thermoelectric conversion material. Element. As the conductor material, the same materials as those used in the above (c-1) type element can be used.

[0083] Thermal lightning strike module

The thermoelectric generation module uses a plurality of the thermoelectric conversion elements described above, and connects 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 plurality of thermoelectric conversion elements are connected in series by an electrical connection method.

[0084] Normally, an unbonded end of the thermoelectric conversion element is adhered to the substrate using a bonding agent. The end of the P-type thermoelectric conversion material and the n-type thermoelectric conversion material of another thermoelectric conversion element are bonded together. And on the board! You have to connect.

FIG. 4 shows, as an example, a schematic diagram of a thermoelectric power generation module having a structure in which a plurality of (a-1) type elements are connected on a substrate using a bonding agent.

[0086] The thermoelectric power generation module in Fig. 4 uses an (a-1) type element as a thermoelectric conversion element such that the unjoined ends of the p-type and n-type thermoelectric conversion materials are in contact with the substrate. The thermoelectric conversion element is obtained by bonding the thermoelectric conversion element on the substrate so that the P-type thermoelectric conversion material and the n-type thermoelectric conversion material are connected in series using a bonding agent. is there.

[0087] The substrate is mainly used for the purpose of improving thermal uniformity and mechanical strength, maintaining electrical insulation, and the like. The material of the substrate is not particularly limited, but it is chemically stable at a high temperature of about 675 K or higher without causing melting, breakage, etc., and does not react with thermoelectric conversion materials, bonding agents, etc. However, it is preferable to use a material that has thermal conductivity. . By using a substrate 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. In addition, since 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.

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. For example, noble metal pastes such as silver, gold, and platinum, solders, platinum wires, and the like can be suitably used.

FIG. 5 is a schematic cross-sectional view of an example of a thermoelectric generation module using a (s-2) type element obtained by a contact method. For the ceramic substrate in the high-temperature part, the thermoelectric conversion element should be bonded using a bonding agent so that the p-type thermoelectric conversion material and the n-type thermoelectric conversion material are connected in series, similarly to the module in Fig. 4. .

On the low-temperature part side, for example, an insulating ceramic substrate such as alumina may be bonded to the thermoelectric conversion element using a bonding agent. As the bonding agent used for connecting the substrate on the low-temperature side, it is preferable to use a bonding agent having high thermal conductivity in order to release the heat transmitted through the high-temperature side force module to the low-temperature side force into the atmosphere. In addition, since it is necessary to maintain insulation between the elements, when applying a bonding agent to the entire substrate, it is necessary to use a bonding agent having good electrical insulation. As such a bonding agent, for example, a silicone bonding agent or the like can be used. Also, when the low-temperature part side of the thermoelectric conversion element is used in a non-contact state with a conductive substance, for example, when the low-temperature part side is used in contact with the atmosphere, it is not necessary to bond insulating ceramics to the low-temperature part side. It may be used with the thermoelectric conversion material exposed.

[0091] The number of thermoelectric conversion elements used in one module is not limited, and can be arbitrarily selected depending on required power. FIG. 4 shows a schematic structure of a module using 84 thermoelectric conversion elements. The output of the module is approximately equal to the output of the thermoelectric conversion element multiplied by the number of thermoelectric conversion elements used, and is a value.

[0092] The thermoelectric power generation module can generate a voltage by arranging one end of the module at the high temperature section and the other end of the module at the low temperature section. For example, in the modules shown in FIGS. 4 and 5, 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 power generation module The module is not limited to such an installation method.It is only necessary to arrange one end on the high-temperature side and the other end on the low-temperature side.For example, for the modules in Figs. 4 and 5, It is permissible to install with the side opposite to the low temperature section.

[0093] (3) Thermoelectric generator

The thermoelectric generator of the present invention includes a thermoelectric generator module and a catalytic combustion heat source, and the catalytic combustion heat source is arranged so as to heat one surface of the thermoelectric generator module. For example, the heat conduction part of the catalytic combustion type heat source should be installed so as to be in close contact with one surface of the thermoelectric power generation module.

[0094] The overall structure of the thermoelectric generator is not particularly limited! For example, as shown in an embodiment to be described later, a structure is adopted in which the combustion gas burned in the catalytic combustion unit is directly blown onto the heat conduction unit to heat the heat conduction unit, and this heat heats one surface of the thermoelectric power generation module. be able to. Further, the heat conducting portion may be provided in a structure surrounding the catalytic combustion portion, and the heat conducting portion may be heated by contact with the combustion gas passing through the catalytic combustion portion.

[0095] The heating temperature of the heat conduction section can be controlled by adjusting the fuel supply amount. For this reason, a fuel supply valve for controlling the flow rate of the supplied fuel is usually installed in the catalytic combustion section.

[0096] To increase the power generation efficiency, the surface opposite to the surface heated by the catalytic combustion heat source, that is, the low-temperature portion of the thermoelectric power generation module is cooled to increase the temperature difference between both ends of the thermoelectric conversion material. Just fine. The cooling means is not particularly limited, and various cooling means such as water cooling, air cooling, and cooling using an endothermic reaction can be applied. Especially, considering the light weight, air cooling is desirable. In the case of air cooling, for example, a fin, a heat bath (heat sink), or the like may be brought into close contact with a low-temperature surface of the thermoelectric generation module as a cooler. In this case, the module may be cooled by natural heat radiation. However, if a fin or a heat bath is forcibly cooled by attaching a fan, the power generation efficiency can be further improved. As the driving force of the fan, for example, exhaust gas generated by combustion can be used. If the exhaust gas is sufficiently cooled down to about room temperature, it may be blown directly to the fins.

[0097] Hereinafter, the thermoelectric generator of the present invention will be specifically described with reference to the drawings.

FIG. 6 is a drawing schematically showing an example of the thermoelectric generator of the present invention. Fig. 6 Thermoelectric generation In the electric equipment, a catalytic combustor is installed so as to be in close contact with one surface of the thermoelectric power generation module via a heating plate as a heat conducting part. The fuel tank is connected to the catalytic combustor via a preheating burner. A fuel supply valve and an air intake valve are provided at a connection portion between the fuel tank and the preheating burner, and a fuel replenishing port for replenishing fuel is provided in the fuel tank.

[0099] In the thermoelectric generator, a heat insulating material is arranged around the catalytic combustor to prevent a high temperature due to reaction heat. This facilitates use as a portable device.

[0100] A fin is provided as a cooler on the low-temperature side surface of the thermoelectric generation module, and a fan is further provided so that the fin can be forcibly cooled. With such a structure, the temperature difference between the surface heated by the combustion gas and the surface cooled by the fan increases, and efficient power generation becomes possible.

[0101] In the apparatus shown in Fig. 6, the fuel contained in the fuel tank is sent to the preheating burner section.

On the other hand, the air introduced by opening the air intake valve is also sent to the preheating burner together with the fuel.

[0102] The preheat burner is used to heat the catalytic combustor. After the catalytic combustor is heated to a temperature required for catalytic combustion, the supply of fuel to the preheat burner is stopped.

[0103] Next, the gas mixture of fuel and air is sent to the catalytic combustor, where catalytic combustion of the gas mixture occurs. The burned gas is blown to a heating plate, which is a heat conducting portion, and the thermoelectric power module in contact with the heating plate is heated by the heat energy of the combustion gas. Combustion gas is discharged as exhaust gas from a combustion gas discharge port via a pipe connected to the catalytic combustor.

[0104] In the thermoelectric generator of the present invention, the power generation amount can be increased by increasing the number of modules or increasing the heating temperature. For example, the thermoelectric power module with the above-mentioned structure can generate power of about 100 mW or more per unit volume when the high temperature part is heated to about 300 ° C or more. For this reason, for example, a small and lightweight device with a size of about 3cm X 3cm X 5cm-30cm X 30cm X 20cm and a weight of about lOOg-about 5kg, can generate a power of about 0.1-50W. Obtainable. The invention's effect

The thermoelectric generator of the present invention is a combination of a thermoelectric generator module having excellent thermoelectric conversion performance and a catalytic combustion heat source.

[0106] The thermoelectric generator having such a structure can be used as a portable power source by integrating a fuel container, and electric energy can be easily obtained at places where various devices are used. In addition, even small and lightweight devices can obtain power up to about 50W.

[0107] Therefore, the thermoelectric generator of the present invention can be effectively used as a power source suitable for carrying, for example, a power source for portable devices such as a mobile phone and a notebook computer.

Brief Description of Drawings

FIG. 1 is a drawing schematically showing an example of a heat conversion element obtained by bonding a thermoelectric conversion material to a conductive material using a bonding agent.

FIG. 2 is a drawing schematically showing an example of a thermoelectric conversion element obtained by electrically connecting by sintering or crimping.

FIG. 3 is a drawing schematically showing an example of a thermoelectric conversion element obtained by electrically contacting a thermoelectric conversion material using a conductive material.

FIG. 4 is a schematic diagram of a thermoelectric power generation module having a structure in which a plurality of (a-1) type devices are connected on a substrate.

FIG. 5 is a schematic cross-sectional view of an example of a thermoelectric power generation module using a (s-2) type element.

FIG. 6 is a drawing schematically showing an example of the thermoelectric generator of the present invention.

FIG. 7 is a graph showing the power generation characteristics of the power generator obtained in Example 1.

FIG. 8 is a graph showing the relationship between the open-circuit voltage of the thermoelectric conversion elements of Reference Examples 1, 63, and 75 and the temperature of the high-temperature part.

FIG. 9 is a graph showing the relationship between the electric resistance of the thermoelectric conversion element of Reference Example 1 and Reference Example 75 and the temperature of the high-temperature part.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the thermoelectric generator of the present invention will be described more specifically. [0110] Example 1

A thermoelectric generator having the structure shown in FIG. 6 was manufactured under the following conditions.

_[0111] Ό heat栾椽material

A p-type thermoelectric conversion material represented by a composition formula: Ca Bi Co O was produced by the following method.

2.7 0.3 4 9.2

First, calcium carbonate (CaCO 2), bismuth oxide (Bi 0) and cobalt oxide (Co 0)

3 2 3 3 4

It was weighed so that Ca: Bi: Co (atomic ratio) = 2.7: 0.3: 4 and mixed well. The obtained mixture was placed in an alumina crucible, fired in air at 1073 K (800 ° C.) for 10 hours, and the obtained fired product was sufficiently mixed using an agate mortar and a pestle.

[0113] This powder was formed into a disc having a diameter of about 20mm and a thickness of about 2 to 10mm under pressure, a gold sheet was spread on an alumina boat, and the formed body was placed on the gold sheet. It was baked for 20 hours in an air stream (300 ml / min). Next, the obtained sintered body was ground using an agate mortar and a pestle.

[0114] The obtained powder was pressed into a 30 mm square, 5 mm thick square plate, and subjected to hot press sintering in air at 1123 K (850 ° C) under air under uniaxial pressure of lOMPa for 20 hours. . The obtained hot-press sintered body was cut 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.

[0115] n-type thermal lightning material

An n-type thermoelectric conversion material represented by a composition formula: La Bi NiO was produced by the following method.

0.9 0.1 3.1

[0116] First, lanthanum nitrate (La (NO) 6Η), bismuth nitrate (Bi (NO) 5Η) and dinitrate

3 3 2 3 3 2

Weigh nickel (Ni (N〇) · 6Η〇) so that La: Bi: Ni (atomic ratio) = 0 · 9: 0 · 1: 1 · 0

3 2 2

It was completely dissolved in distilled water in a pot and mixed. Next, the distilled water was evaporated to dryness while stirring with a magnetic stirrer.

[0117] The precipitate was heated and baked in air at 1073K (800 ° C) for 10 hours to thermally decompose nitrate.

Next, the fired product was mixed with an agate mortar and pestle.

[0118] The obtained powder was press-formed into a disk having a diameter of 2 cm and a thickness of about 2 to 10 mm, and then a platinum sheet was laid on an alumina boat, and the formed body was placed thereon, and the powder was placed at 1273 K (1000 ° C ), And calcined in an oxygen stream (300 ml / min) for 20 hours. The obtained sintered body was ground using an agate mortar and pestle. This powder was pressed again to the above-mentioned size and baked under the same conditions. The body was ground using an agate mortar and pestle.

[0119] The obtained powder was pressed into a 30 mm square, 5 mm thick square plate, and subjected to hot press sintering in air at 1173K (900 ° C) under uniaxial pressing of lOMPa for 20 hours. . The obtained hot-press sintered body was cut 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.

_[0120] Ό type heat lightning栾椽material connection Shirubekaminariken paste

In the above-mentioned process of manufacturing a type III thermoelectric conversion material, after firing at 1153K (880 ° C) for 20 hours, the powder obtained by grinding is further ball-milled using an agate pot and balls. For 10 minutes. Observation of the obtained oxide powder with a scanning electron microscope revealed that more than 80% of the particles were in the range of 110 μm in particle diameter.

[0121] This oxide powder was added to a commercially available silver paste (trade name: H-4215, manufactured by Shoei Chemical Co., Ltd.) to obtain a conductive paste for bonding a P-type thermoelectric conversion material. The silver paste used was 85% by weight of silver powder, 1% by weight of bismuth borosilicate glass, 5% by weight of ethyl cellulose, 4% by weight of terbinol, and 5% by weight of butyl carbitol acetate. Was 6.25 parts by weight with respect to 100 parts by weight of the silver powder in the silver paste.

[0122] n-type thermal lightning paste

In the production of the n-type thermoelectric conversion material described above, the powder obtained by firing twice at 1273K (1000 ° C) for 20 hours and then pulverizing twice was further ball-milled for 10 minutes using an agate pot and balls. Crushed. Observation of the obtained powdery powder with a scanning electron microscope revealed that 80% or more of the particles had a particle size of 110 μm.

[0123] 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 the silver paste used and the amount of the oxidized powder added are the same as those of the conductive paste for connecting a p-type thermoelectric conversion material.

[0124] Thermal lightning conversion element

The above-mentioned P-type thermoelectric conversion material and n-type thermoelectric conversion material were connected to a conductive substrate, and a pair of p-type thermoelectric conversion materials and an n-type thermoelectric conversion material were manufactured.

[0125] As the conductive substrate, a 5 mm x 8 mm, 5 mm x 8 mm surface of a lmm-thick alumina plate was A substrate on which a paste was uniformly applied and dried to form a conductive film of a silver paste was used.

[0126] 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 were applied to the 4 mm X 4 mm surfaces of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material, respectively. After placing the surface coated with the conductive paste of each thermoelectric conversion material on the silver paste-coated surface of the above alumina substrate, and heating it at 373K (100 ° C) for about 10 to 30 minutes, The conductive paste was dried and solidified by heating in air at 800 ° C) for 15 minutes. Next, in order to reinforce the connection portion between the substrate and each thermoelectric conversion material, an insulating ceramic paste containing alumina as a main component was applied to the connection portion and dried to produce a thermoelectric conversion element.

[0127] Thermal lightning strike module

Using an alumina plate with a size of 2 cm x 2 cm and a thickness of lmm as the substrate, 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 of the other thermoelectric conversion element The thermoelectric conversion elements were joined on a substrate such that the thermoelectric power conversion modules were connected to each other to obtain a thermoelectric power generation module in which ten thermoelectric conversion elements were connected in series. Silver paste was used as the bonding agent.

[0128] Sintered heat source

The catalytic combustor has a honeycomb structure (2 cm X 2 cm X lcm) with 30 lmm-square ventilation holes made by applying and sintering alumina on a SUS-510 stainless steel substrate. In this case, platinum and palladium fine particles having a particle size of 100 μm or less were supported at a weight ratio of 1: 1.

[0129] In addition to the catalytic combustor, the catalytic combustion type heat source includes a heating plate, a preheating burner, and a fuel tank. A fuel supply valve and an air supply are provided at a junction between the preheating burner and the fuel tank. An intake valve is provided.

[0130] The main body of the thermoelectric generator is made of SUS-310 stainless steel, and a heat insulating material is inserted between the peripheral portion of the catalytic combustor and the outer wall.

[0131] The preheating burner is a burner having a structure for burning fuel gas. The heating plate is SUS

-Made of 310 stainless steel plate. [0132] Liquid fuel butane is stored as fuel in the fuel tank.

[0133] Thermal lightning generator

The thermoelectric generator is configured such that a heating plate of a catalytic combustion type heat source is fixed to the alumina substrate surface of the above-described thermoelectric generator module with screws so that the heating plate is in close contact with the alumina substrate, and the alumina substrate is heated by thermal energy due to catalytic combustion. Te ru.

[0134] Aluminum cooling fins are provided on the other surface of the thermoelectric power generation module, and a fan is provided above the cooling fins. This fan is configured to rotate by blowing exhaust gas generated by combustion onto a wind fan located above the fan, and to blow the air to the fins to improve the cooling efficiency of the fins.

[0135] Thermal lightning method

First, a gas mixture of liquid butane and air contained in a fuel tank was supplied to a preheating burner, and the catalyst combustor was heated by the combustion heat of the preheating burner. After the temperature of the catalytic combustor rose to 300 ° C or more, the supply of fuel to the preheating burner was stopped, and the heating by the preheating burner was stopped.

[0136] Next, fuel and air were supplied to the catalytic combustor to start catalytic combustion.

[0137] The heating plate was heated by spraying the combustion gas generated by catalytic combustion on the heating plate, and the heat used to heat the substrate surface of the thermoelectric power generation module.

[0138] On the other hand, the exhaust gas after combustion was discharged from the combustion gas discharge port, and a part thereof was used for rotation of the fan.

[0139] By the above method, the alumina substrate surface of the thermoelectric power generation module was heated, and a voltage was generated between the conductors connected to both ends of the thermoelectric power generation module due to the temperature difference from the opposite surface of the module.

FIG. 7 is a graph showing power generation characteristics when the high-temperature portion of the thermoelectric generation module is heated at 400 ° C. In this graph, the output showed a parabolic dependence on the current value. The external resistance at which the output reached its maximum value almost coincided with the internal resistance of the module. From these results, it is clear that the generator of Example 1 is designed to sufficiently exhibit the characteristics of the thermoelectric module.

[0141] Example 2 In a thermoelectric generator having the same structure as in Example 1, a large carrier of 28 cm X 28 cm X 5 cm was used as an alumina carrier of a catalytic combustor, and a SUS-310 stainless plate of 28 cm X 28 cm X 3 cm was used as a heating plate. .

[0142] As the thermoelectric generation module, the thermoelectric generation modules used in Example 1 were connected in series.

A module having a size of 26 cm X 26 cm X 7 mm with nine pieces bonded was used.

[0143] The overall size of the obtained thermoelectric generator was 30 cm X 30 cm X 20 cm.

It has a much higher output than the one power generator.

[0144] Example 3

A thermoelectric generator having a structure similar to that of Example 1 was manufactured except that an electric heater having an output of 2 kW was used as a preheater of a catalytic combustor. As a power source for supplying power to the heater, a capacitor that can charge surplus power during operation of the thermoelectric generator was installed. This capacitor is replaceable, and when charging is insufficient, an already charged capacitor can be used as a starting power source.

[0145] After heating the catalytic combustor to about 300 ° C using this electric heater and supplying fuel and air to the catalytic combustor, power can be generated in the same manner as in the thermoelectric generator of Example 1. For

[0146] Hereinafter, specific examples of thermoelectric conversion elements that can be used in the thermoelectric generator of the present invention will be shown as reference examples. By using the thermoelectric conversion element of each of the reference examples described later in place of the thermoelectric conversion element used in the first embodiment, a thermoelectric generator having excellent performance as in the first embodiment can be obtained.

[0147] Reference Example 1-1 62

Using calcium carbonate, bismuth oxide and cobalt oxide as raw materials, the chemical formula: Ca

2.7

The raw materials are mixed so as to have the same element ratio as that of the complex oxidized product represented by Bi Co O, and

0.3 4 9.4

At atmospheric pressure, it was calcined at 1073K for 10 hours. Next, the obtained fired product was pulverized, shaped, and fired in an oxygen gas flow of 300 ml / min at 1153K for 20 hours. Then, the obtained fired product is pulverized and press-formed, and subjected to hot press sintering at 1123 K for 20 hours under uniaxial pressure of lOMPa in air to obtain a composite oxidized product for a p-type thermoelectric conversion material. Was prepared.

[0148] On the other hand, using the respective nitrates of La, Bi and Ni as raw materials, the chemical formula is represented by La Bi NiO. The raw materials are mixed so as to have the same element ratio as that of the composite acidified product, dissolved in distilled water and mixed with stirring in an alumina crucible, and the resulting aqueous solution is heated to evaporate the water and dried. Hardened. The dried product was heated in the atmosphere at 873K for 10 hours, and the obtained fired product was pulverized and mixed, then molded under pressure, and fired at 1273K for 20 hours in an oxygen gas flow of 300 ml / min. Next, the fired product was pulverized, mixed, and press-molded, and again fired in an oxygen gas flow of 300 ml / min at 1273K for 20 hours, and the obtained fired product was pulverized and pressure-molded. Thereafter, hot-press sintering was performed at 1173 K for 20 hours under uniaxial pressure of 10 MPa in air to produce a composite oxide for an n-type thermoelectric conversion material.

[0149] Each of the composite oxide for the p-type thermoelectric conversion material and the composite oxide for the n-type thermoelectric conversion material obtained by the above-described method has a plane parallel to the pressing axis during hot pressing by 4 mm. It was cut into a rectangular parallelepiped shape with a length of 4 mm and a length of 5 mm in the pressurized surface to produce a p-type thermoelectric conversion material and an n-type thermoelectric conversion material. For each of the p-type thermoelectric conversion material and n-type thermoelectric conversion material obtained in this way, apply a silver paste to the 4 mm X 4 mm surface, apply them to the surface, apply silver paste on the surface, length 8 mm, width It was set up in parallel on a 5 mm, lmm thick alumina substrate.

[0150] Next, in order to dry and solidify the silver paste, a heat treatment was performed in air at 1073K for 15 minutes to produce a (a-1) type thermoelectric conversion element of Fig. 1 (Reference Example 1).

[0151] Further, in the same manner as in Reference Example 1, except that the composite oxidized products having the compositions shown in Tables 1 and 2 below were used as the p-type thermoelectric conversion material and the n-type thermoelectric conversion material, respectively. The (a-1) type thermoelectric conversion element (Reference Example 2-62) was produced. The firing temperature for producing each oxide is changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering is also changed in the range of 1123 to 1173 °. Was changed.

[0152] Tables 1 and 2 below show the thermoelectromotive force and electric resistance of the obtained thermoelectric conversion element at 973Κ and the output at 973Κ and a temperature difference of 600Κ.

[0153] In all the reference examples including the reference example described later, the thermoelectromotive force obtained by dividing the voltage by the temperature difference between the high and low temperature ends was 60 µVZK or more in the temperature range of 293 to 1073K.

[Table 1] Adhesive type (a-1) type

] Adhesive type (a-1) type

¾ 'l63— 65 Using a p-type thermoelectric conversion material and n-type thermoelectric conversion material with the same composition and shape as those used in Reference Example 1, apply a silver paste to the 4 mm X 4 mm surface of each thermoelectric conversion material, length 8 mm, width 5 mm And placed upright on a 2 mm thick conductive substrate (La Bi NiO).

0.9 0.1 3.1

[0157] Next, in order to dry and solidify the silver paste, a heat treatment was performed in air at 1073K for 15 minutes to produce a (a-2) type thermoelectric conversion element in FIG. 1 (Reference Example 63).

[0158] In addition, in the same manner as in Reference Example 63 except that a composite oxide having a composition shown in Table 3 below was used as the p-type thermoelectric conversion material and the n-type thermoelectric conversion material, (a- Type 2) thermoelectric conversion elements were fabricated. The firing temperature for producing each oxide was changed in the range of 1073-1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 1231-1173K.

Table 3 below shows the thermoelectromotive force and electric resistance of the obtained thermoelectric conversion element at 973 K, and the output at 973 K and a temperature difference of 600 °.

[0160] [Table 3]

(a-2) type

[0161] Participants 66-68

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material with the same composition and shape as those used in Reference Example 1, apply a silver paste on the 4 mm X 4 mm surface of each thermoelectric conversion material, length 8 mm, width 5 mm The surface of a 2 mm-thick alumina substrate was placed in parallel on a conductive substrate coated with silver by a vapor deposition method.

[0162] Next, in order to dry and solidify the silver paste, a heat treatment was performed in air at 1073K for 15 minutes to produce a (a-3) type thermoelectric conversion element (Reference Example 66) in Fig. 1.

[0163] Also, as in Reference Example 66, the (a-3) type thermoelectric element of FIG. 1 was used as Reference Examples 67 and 68, except that a composite oxide having the composition shown in Table 4 below was used. A conversion element was manufactured. In addition, each The sintering temperature for producing the oxidized product was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0164] The thermoelectric conversion element obtained at 973K and the

Table 4 below shows the output at K and a temperature difference of 600Κ.

[0165] [Table 4]

(a-3) type

[0166] Reference Example 69—71

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, apply a silver paste to a 4 mm X 4 mm surface of each thermoelectric conversion material, length 10 mm, diameter 0 Place both ends of a 5mm platinum wire on the surface of each thermoelectric conversion material coated with silver paste, and perform heat treatment at 1073K for 15 minutes in air to dry and solidify the silver paste! ヽ, Fig. 1 The (a-4) type thermoelectric conversion element (Reference Example 69) was produced.

[0167] Also, as in Reference Example 69, the (a-4) type thermoelectric element shown in FIG. 1 was used as Reference Examples 70 and 71, except that a composite oxide having the composition shown in Table 5 below was used. A conversion element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0168] For the obtained thermoelectric conversion element, the thermoelectromotive force and electric resistance at 973K were measured,

Table 5 below shows the output at K and a temperature difference of 600 °.

[0169] [Table 5] (a-4) type

[0170] Participants 72-74

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, each of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material was 4 mm x 5 mm. The surfaces were brought into close contact with each other, and hot press sintering was performed at 1073K for 3 hours while pressing the surfaces perpendicularly.

[0171] Next, a cut was made at one end of the joining interface from one end of the material in a longitudinal direction (direction of 5 mm) to a length of 3 mm using a diamond cutter to separate the p-type thermoelectric conversion material from the n-type thermoelectric conversion material. did. By this method, a (s-1) type sintered element (Reference Example 72) shown in FIG. 2 was obtained.

[0172] Also, as in Reference Example 72, the (s-1) type thermoelectric element shown in FIG. 2 was used as Reference Examples 73 and 74, except that a composite oxide having the composition shown in Table 6 below was used. A conversion element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0173] For the obtained thermoelectric conversion element, the thermoelectromotive force and electrical resistance at 973K were

Table 6 below shows the output at K and a temperature difference of 600 °.

[0174] [Table 6] Sintered element (s-1) type

[0175] Participants 75-77

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, each of the p-type thermoelectric conversion material and the n-type thermoelectric conversion material was 4 mm x 5 mm. A 0.25-mm, 23-mesh Zinch silver mesh is sandwiched between the surfaces, and heat treatment is performed for 3 hours in air at 1073K while applying pressure vertically to the contact surface.The ρ-type thermoelectric conversion material and η-type The thermoelectric conversion materials were joined.

[0176] Next, the joining interface was cut from one end of the material in the longitudinal direction (direction of length 5mm) to a length of 3mm using a diamond cutter, and the p-type thermoelectric conversion material and the n-type thermoelectric conversion material were separated. separated. By this method, a (s-2) type sintered element (Reference Example 75) shown in FIG. 2 was obtained.

[0177] Also, in the same manner as in Reference Example 75, except that a composite oxide having the composition shown in Table 7 below was used as the p-type thermoelectric conversion material and the n-type thermoelectric conversion material, Type 2) thermoelectric conversion elements were fabricated. The firing temperature for producing each oxide was changed in the range of 1073-1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 1231-1173K.

Table 7 below shows the thermoelectromotive force and electric resistance of the obtained thermoelectric conversion element at 973 K, and the output at 973 K and a temperature difference of 600 °.

[Table 7] (s-2) type

[0180] Participants 78-80

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material with the same composition and shape as those used in Reference Example 1, a 4 mm X 4 mm surface of the ρ-type thermoelectric conversion material and a 4 mm X 4 mm La Bi Ni 8mm long, 5mm wide, 2mm thick so that it lies on both sides of the surface

0.9 0.1

Place the O conductive substrate and pressurize the contact surface in the vertical direction at 1073K in the air for 3 hours.

3.1

The (s-3) type thermoelectric conversion element shown in Fig. 2 was fabricated by bonding a ρ-type thermoelectric conversion material and an η-type thermoelectric conversion material to a conductive substrate.

[0181] Also, as in Reference Example 78, the (s-3) type thermoelectric element of FIG. 2 was used as Reference Examples 79 and 80, except that a composite oxide having the composition shown in Table 8 below was used. A conversion element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0182] For the obtained thermoelectric conversion element, the thermoelectromotive force and electrical resistance at 973Κ

Table 8 below shows the output at the temperature difference of 600 °.

[0183] [Table 8]

(s-3) type

Reference example Thermoelectromotive force 抵抗 Resistance output

P-type material n-type material

No. (V / K) (mQ) (mW)

973K

973K 973K

Temperature difference 600K

78 CI ₂ JDI ₀₃ CO ₄ O ₉₄ La ₀₉ Bi ₀₁ NiO3., 150.0 35.0 46

_{_{_{79 Ca 3 Co 4 0 89 LaNi0}}} 3, 140.0 40.0 35

80 ^Ca 2.6 ^NA 0.2 ^BL 0.2CO ₄ O ₉₃ La ₀₉ Bi ₀₁ NiO ₃₂ 140.0 35.0 40 [0184] Reference Example 81—83

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, the 4 mm X 4 mm surface of the ρ-type thermoelectric conversion material and the 4 mm X 4 of the n-type thermoelectric conversion material A 0.25mm diameter, 23 mesh Zinch silver mesh is placed on the surface of each mm, and the conductivity of La Bi NiO of length 8mm, width 5mm, and thickness 2mm is placed on both sides.

0.9 0.1 3.1

The substrate is placed, heat-treated in air at 1073K for 3 hours while applying pressure vertically to the contact surface, and sintered, and the conductive substrate is bonded to the ρ-type and η-type thermoelectric conversion materials. A (s-4) type thermoelectric conversion element (Reference Example 81) in FIG. 2 was produced.

[0185] Further, in the same manner as in Reference Example 81, except that a composite oxidized product having the composition shown in Table 9 below was used as Reference Examples 82 and 83, the (s-4) type thermoelectric element of FIG. A conversion element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0186] For the obtained thermoelectric conversion element, the thermoelectromotive force and electrical resistance at 973Κ

Table 9 below shows the output at a temperature difference of 600 °.

[Table 9]

(s-4) type

[0188] Examples of participants 84—86

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, apply one-sided force to the 4 mm X 5 mm side surface of each material in the longitudinal direction (length 5 mm). A hole with a diameter of 1 mm was drilled at a position 2 mm from the left and right ends to the opposite side of the material. By inserting a 1.2mm diameter silver wire into this hole and connecting the p-type and n-type thermoelectric conversion materials, the (c-1) type A replacement element (Reference Example 84) was produced.

[0189] Further, in the same manner as in Reference Example 84, except that a composite oxide having the composition shown in Table 10 below was used as Reference Examples 85 and 86, the (c1) type thermoelectric conversion of FIG. An element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0190] For the obtained thermoelectric conversion element, the thermoelectromotive force and electric resistance at 973K were measured,

Table 10 below shows the output at K and a temperature difference of 600Κ.

[0191] [Table 10]

Contact element

(c-1)

Type

[0192] Participants 87- 89

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, attach a silver panel-type clip to the upper surface (4 X 4 mm surface) of each material. A 0.5-mm-diameter, 10-mm-long wire made of silver was fixed and connected to a p-type thermoelectric conversion material and an n-type thermoelectric conversion material. Reference Example 87) was produced.

[0193] In addition, the same procedure as in Reference Example 87 was carried out except that the composite oxidized products having the compositions shown in Table 11 below were used as Reference Examples 88 and 89, and the thermoelectric conversion of the (c2) type in FIG. An element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K. [0194] For the obtained thermoelectric conversion element, the thermoelectromotive force and electric resistance at 973K were measured,

Table 11 below shows the output at K and a temperature difference of 600 °.

[0195] [Table 11]

(c-2) type

[0196] Participants 90-92

Using a P-type thermoelectric conversion material and an n-type thermoelectric conversion material having the same composition and shape as those used in Reference Example 1, a female thread was cut on the upper surface (4 mm X 4 mm surface) of each material. On the other hand, a conductive substrate made of La Bi NiO with a length of 8 mm, a width of 5 mm, and a thickness of 2 mm with two holes

0.9 0.1 3.1

Is placed on both materials such that the positions of the holes match the positions of the threads of the thermoelectric conversion material, and the conductive substrate is screwed to the P-type thermoelectric conversion material and the n-type thermoelectric conversion material. (S-3) type thermoelectric conversion element (Reference Example 90) shown in FIG.

[0197] Also, as in Reference Example 90, the thermoelectric conversion of the (c3) type in FIG. An element was manufactured. The firing temperature in producing each of the oxidized products was changed in the range of 1073 to 1273K depending on the composition, and the temperature of hot press sintering was also changed in the range of 123 to 1173K.

[0198] The thermoelectric conversion element obtained at 973 K

Table 12 below shows the output at K and a temperature difference of 600Κ.

[0199] [Table 12] (c-3) type

[0200] Special cases, test cases ί

For each of the thermoelectric conversion elements obtained in Reference Examples 1, 63 and 75, the junction of each element was heated by an electric furnace, and the other end was cooled to evaluate the power generation characteristics. Figure 8 is a graph showing the relationship between the generated voltage (open-circuit voltage) and the temperature of the high-temperature part when the high-temperature part is 300-1000 100 and the low-temperature part is 293-400Κ. The generated voltage (open-circuit voltage) tended to increase as the temperature of the high-temperature part rose.

When the generated voltages of these elements are compared, the generated voltage of the elements of Reference Examples 1 and 63 tends to be higher than the generated voltage of the element of Reference Example 75. This is 5 mm, which is the same as the length of the ρ-type thermoelectric conversion material and the η-type thermoelectric conversion material in the elements of Reference Examples 1 and 63 in which the substrate is bonded to the upper surface of the material. On the other hand, the element of Reference Example 75, in which the side of the material was cut by sintering, was affected by the 3 mm separation length between the p-type thermoelectric conversion material and the n-type thermoelectric conversion material. Can be thought of. In other words, the longer the material is separated from the lower temperature side, the greater the temperature difference between them, and the higher the generated voltage.

[0202] Fig. 9 is a graph showing the relationship between the electric resistance and the temperature of the high-temperature part for the devices of Reference Examples 1 and 75. As is clear from this, a tendency was observed that the electrical resistance decreased with increasing temperature.

[0203] Participants 93-97

Using 84 thermoelectric conversion elements obtained in Reference Example 1, these were placed on an alumina substrate of 8 cm in length, 6 cm in width, and lmm in thickness such that the unbonded surfaces of the elements were in contact with each other, and silver paste was used. Then, a p-type end and an n-type end of each element were alternately connected to produce a thermoelectric conversion module (Reference Example 93) shown in FIG. [0204] Instead of the thermoelectric conversion element obtained in Reference Example 1, the thermoelectric conversion element obtained in Reference Example 75, 63, 81, or 84 was used. 97 thermoelectric conversion modules were fabricated.

[0205] For each of the obtained thermoelectric conversion modules, the alumina substrate was used as the high temperature part, the junction between the p-type thermoelectric conversion material and the n-type thermoelectric conversion material was used as the low temperature part, the high temperature part was used as 973K, and the low temperature part was used. Table 13 shows the open-circuit voltage, internal resistance, and maximum output when the temperature difference is 600 ° C. Here, the open-circuit voltage is the voltage generated when a temperature difference is applied to the module without applying an external resistor. The output reached its maximum when loaded with the same resistance as the internal resistance of the module.

[0206] In all the reference examples, when the high temperature part was set to 973 97, an output of 0.5 W or more was obtained.

[Table 13]

[0208] Further, with respect to an example of a thermoelectric conversion material that can be used in the thermoelectric generator of the present invention, a production example and physical properties of the obtained oxide are shown as reference examples, and the thermoelectric generator used in the thermoelectric generator of the present invention is shown. It shows that it is effective as a conversion material.

[0209] Reference Example 98

General formula: Ca A ¹ Co A ² O or general formula: p-type thermoelectric transformer represented by Bi Pb M ¹ Co M ²⁰

a b c d e f g h i j k

A composite oxide having properties as a replacement material was produced by the following method.

[0210] As the raw material, a carbonate or oxide containing a constituent element of the target composite oxide was used, and the raw materials were mixed so as to have the same element ratio as the composition formula shown in Table 14-Table 81. It was calcined at 1073K for 10 hours at atmospheric pressure. Next, the obtained fired product was pulverized, molded, and fired in an oxygen gas flow of 300 ml / min for 20 hours. Then the resulting firing The material was pulverized and press-formed, and subjected to hot press sintering for 20 hours under uniaxial pressure of lOMPa in air to produce a composite oxide for a p-type thermoelectric conversion material. The firing temperature for producing each oxide was changed in the range of 1073 to 1273K depending on the composition, and further, the temperature of hot press sintering was changed in the range of 123 to 1173K.

[0211] Table 14 and Table 81 below show the measurement results of the Seebeck coefficient at 700 ° C, the electric resistivity at 700 ° C, and the thermal conductivity at 700 ° C for each of the obtained iridani products.

[0212] [Table 14]

15]

16]

17]

18]

19]

20]

twenty one]

twenty two]

twenty three]

twenty four]

twenty five]

26]

_{_{_{_{Bi 2 Pb 0. 2 Sr L8}}}} Cr 0. 2 Co 2 0 g 207 8.6 0.8 r 190 8.7 1.3

BisPbo.sSr! ₈ Fe ₀₂ Co ₂ 0 ₉ 198 8.3 1.4

_{_{_{Bi 2 Pb 02 Sr L 8 Ni}}} 0. 2 Co 2 0 9 199 9.0 1.1

_{_{_{_{Bi 2 Pb 0. 2 Sr l}}}} 8 Cu 0. 2 Co 2 0 9 201 7.9 1.0

_{_{_{_{Bi 2 Pb 0. 2 Sr 18}}}} Zn 0. 2 Co 2 0 9 210 8.1 1.3

_{_{Bi, Pb 02 Sr u 8 Pb}} 0. 2 Co 2 0 9 206 8.0 0.9

Bi ₂ Pb ₀₂ Sr _{L 8} Ca ₀₂ Co ₂ 0 ₉ 205 7.8 1.1

Bi ₂ Pb ₀₂ Sr! ₈ Ba ₀₂ Co ₂ 0 ₉ 198 7.2 1.4

_{_{_{_{Bi 2 Pb 0. 2 Sr 18}}}} Al a2 Co 2 0 g 195 9.0 1.2

Bi ₂ Pb ₀₂ Sr _L8 Y ₀₂ Co ₂ 0 ₉ 200 7.8 0.9

B ^ Pb Si s and _{_{_{a 0. 2 Co 2 (¾}}} 203 7.5 1.1

Bi ₂ Pb ₀₂ Sr _LS Ce ₀₂ Co ₂ 0 ₉ 201 8.6 1.2

_{_{_{_{Bi 2 Pb 02 Sr L8 Pr 0}}}} . 2 Co 2 0 9 208 8.2 0.9

Bi ₂ Pb ₀₂ Sr ₁₈ Nd ₀₂ Co ₂ 0 ₉ 198 7.9 1.1

Bi ₂ Pb ₀₂ Sr! GSmo ₂ Co ₂ 0 ₉ 199 6.9 1.2

207 8.1 1.4

Bi ₂ Pb ₀₂ Sr _{h 8} Gd ₀ _ ₂ Co ₂ 0 ₉ 198 9.0 0.8

_{_{_{Bi 2 Pb, 2 Sr L8 Dy}}} 0. 2 Co 2 0 9 201 8.2 1.3

Bi ₂ Pb ₀₂ Sr _ls Ho ₀ , ₂ Co ₂ 0 ₉ 200 7.9 1.2

198 8.6 1.1

_{_{_{BigPbo.gSr! 8 Yb 0. 2 Co}}} 2 0 9 205 9.1 1.0

Bi ₂ Ca ₂ Co ₂ 0 ₉ 205 7.4 1.1

Bi aj ₈ Na ₀₂ Co ₂ 0 ₉ 198 7.8 0.9

_{_{_{Bi 2 Ca! 8 K 0.}}} 2 Co 2 0 9 195 7.7 0.8

Bi ₂ Cai _g Li ₀₂ Co ₂ 0 <, 200 8.0 1.0

_{_{_{Bi 2 Ca L8 Ti. 2 Co}}} 2 0 9 205 8.2 1.3

Bi ₂ Ca, _g V ₀₂ Co ₂ 0 ₉ 198 7.9 1.2

Bi, Ca _L8 Cr ₀₂ Co ₂ 0 ₉ 199 9.1 0.7

Bi ₂ Ca _L8 Mn ₀₂ Co ₂ 0 ₉ 210 8.4 1.3

Bi ₂ Ca, _.s Fe ₀ o ₂ 0 ₉ 200 8.6 1.4

Bi2Ca _L8 Ni ₀₂ Co ₂ 0 ₉ 207 8.2 1.1

Bi ₂ Cai ₈ Cu ₀₂ Co ₂ 0 ₉ 198 7.9 1.0

Bi ₂ Ca ₁₈ Zn _{0i 2} Co ₂ 0 ₉ 196 8.6 1.3

Bi ₂ Ca _L8 Pb ₀₂ Co, 0 ₉ 200 9.1 0.9

Bi ₂ Ca ₁₈ Sr ₀₂ Co ₂ 0 ₉ 198 6.9 1.1 27]

[9220]

f6T6lO / 1OOi <If / X3d S 869W0 / S00Z OAV 29]

30]

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a p

_{_{_{_{Bi 2 Pb 0. 2 Sr L8}}}} La a 2 Co! Jio A 205 7.9 1.3

Bi ₂ Pb ₀ 2Sr _{l 8} Ce _{0 2} 0ο ₍ ₉ Ti ₀ A 198 9.1 0.9

_{_{_{Bi 2 Pb 0 2 Sr ,. 8}}} Pr 0. 2 Co! 9 Ti 0 A 195 8.4 1. 1

_{_{_{_{Bi 2 Pb 0. 2 Sr L8}}}} Nd 0. 2 Co 'Jio A 200 8.6 1.4

Bi2Pbo.2Sr sSmo.2COi.9Ti A 203 7.8 1.2

_{_{_{Bi 2 Pb 0 2 Sr LS Eu}}} 0. 2 Co, 9 Ti 0 A 201 9.0 0.9

_{_{_{_{Bi 2 Pb 0. 2 Sr L8}}}} Gd 0 2 Co 1 Ji 0 A 208 8.2 1.1

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8Dy 0. 2 Co L9 Ti 0 A 201 8.3 1.2

_{_{_{_{Bi2Pb 0. 2 Sr L8 Ho 0}}}} .2Co L9 Ti 0 190 8.6 0.9

_{_{_{_{Bi 2 Pb 0. 2 Sr 1}}}} 8 Er 0 2 Co! Ji 0 A 198 8.7 1. 1

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8Yb 0 .2Co ', 9Tio A. 199 8.3 1.2

Bi ₂ Ca ₂ Co! ₉ Ti ₀ .A 200 7.9 1.3

BiaCaLgNao. ^. J.A 206 8.1 1.0

Bi ₂ Ca! ₈ K ₀₂ Co! ₉ Ti ₀ o ₉ 205 8.0 0.9

Bi ^ Cau in, ₂ Co ₁₉ 1 i .A 198 7.8 1.1

_{_{_{Bi 2 Ca L8 Ti a 2 Co}}} s Ti 0 ,, o 9 201 7.2 1.0 o 9 196 9.0 1.2

Bi2Cai.8Cro.2COi.9Tic .A 202 7.8 1.1

Bi ₂ Ca ₁₈ Mn _{0 2} Co _L9 Ti _c .A 203 7.5 0.9

Bi ₂ Ca _L8 Fe _{0 2} Co _L9 Ti _c .A 205 8.6 0.8

_{_{_{_{Bi 2 Ca La Ni 0. 2}}}} Co L9 Ti c ■ A 198 8.2 1.0

B i ₂ Ca _{L 8} Cu _{0 2} Co! _G Ti _c ., O ₉ 195 7.9 1.3

_{_{_{_{Bi 2 Ca L8 Zn 0. 2}}}} Co L9 Ti c .A 200 6.9 1.2

.A 205 8.1 0.7

_{_{_{_{Bi 2 Ca L8 Sr 0. 2}}}} Co i-9 Ti .A 198 7.5 1.3

Bi ₂ Ca _L8 Ba _{0> 2} Co _L9 Ti .A 199 8.6 1.4

_{_{.A 210 8.2 1.1 1 2 Ca L}} 8 Y 0 2 Co, 9 Ti 0, 0 9 202 7.9 1.0 2Ca L 8 La 0 2Co L g Ti, A 204 6.9 1.3

) .A 197 8.1 0.9

_{_{_{Bi 2 Ca 1 8 Pr 0.}}} 2 Co 1. 9 Ti, .A 190 9.0 1.1

Bi ₂ Ca _ls Nd _{0 2} Co _L9 Ti) .A 198 8.2 1.4

BiaCa! ₈ Sm _{0 2} Co ₁₉ Ti xA 199 7.9 1.2

Bi ₂ Ca _{1 8} Eu _{0 2} Co! ₉ Ti.A 201 8.6 0.9

Bi ₂ Ca ,. ₈ Gd _{0 2} Co ₁₉ Ti 207 9.1 1.1 1 2Ca _LS Oy ₀ , ₂ Co _L9 Ti A 190 6.9 1.2 32]

Bi ₂ Ca _L8 Ho _{0 2} Co _L9 Ti _c • A 198 7.4 0.9

Bi ₂ Ca ₁₈ Er _{0 2} Coi. ₉ Ti _c .A 199 7.8 1.1

Bi ₂ Ca, ₈ Yb _{0 2} Co ₁₉ Ti _c ., O ₉ 201 7.7 1.2

Bi ₂ Pb ₀ ₂ Ca ₂ Co _L9 Ti ₀ .o ₉ 206 8.2 0.8

_{_{_{_{Bi 2 Pb 0 2 Ca L8 Na}}}} 0i 2 Coi .Ji t • A 205 7.9 1.3

Bi ₂ Pb ₀ ₂ Ca _{L 8} K ₀ 2Co _L Ti ₀ .A 198 8.0 1.2

Bi ₂ Pb ₀ SCSLS then i .2Co! .Jic .A 195 8.1 1.1

A 200 7.5 0.8

Bi ₂ Pb ₀ ₂ Ca! ₈ V _{0 2} Co _L Jio.A 203 8.6 1.3

Bi ₂ Pb ₀ sCai g 2C0 .Ji (.A 201 8.2 1.4

_{_{_{_{Bi 2 Pb 0 2 Ca LS Mn}}}} 0. 2 Co .A 208 7.9 1.1

_{_{_{_{Bi 2 Pb 0 2 Ca L8 Fe}}}} 0. 2 Co .J c ,, o 9 198 6.9 1.0

Bi ₂ Pb ₀ 2CaL.gNio.2Co! .Jic.A 199 8.1 1.3

_{_{_{_{Bi 2 Pb 0 2 Ca L8 Cu}}}} 0. 2 Co .Ji .A 200 9.0 0.9

Bi ₂ Pb ₀

g 2C0 .Ji ₍ • A 206 8.2 1.1

_{_{_{_{Bi 2 Pb 2 Ca L8 Pb 0}}}} . 2 Co. Ic .A 205 7.9 1.4

A 198 8.6 1.2

Bi ₂ Pb ₀ .Jit .A 201 9.1 0.9

_{_{_{_{Bi 2 Pb 0 2 Ca L8 Al}}}} 0. 2 Co .A 196 6.9 1.1

Bi ₂ Pb _s Ti _0. 202 7.4 1.2

Bi ₂ Pb ₀ .A 203 7.8 0.9

Bi ₂ Pb ₀ .Jic .A 202 7.7 1.1

Bi ₂ Pb ₀ ₂ Ca [ ₈ Pr _{0 2} Co .Ji ₍ .A 203 8.0 1.2

_{_{_{_{Bi 2 Pb 0 2 Ca, 8}}}} Nd 0 2 Co .Ji t., 0 9 208 8.2 1.4

Bi ₂ Pb ₀ ₂ Ca ₁₈ Sm ₀ _ ₂ Co. ₉ Ti ₍ .A 198 7.9 0.8

Bi ₂ Pb ₂ Ca _1-8 Eu ₀ _ ₂ Co. ₉ Ti ₍ .A 199 9. 1 1.3

_{_{_{_{Bi 2 Pb 0 2 Ca L8 Gd}}}} 0. 2 Co. 9 Ti (.A 201 8.4 1.2

_{_{_{_{Bi 2 Pb 0 2 Ca li8 Dy}}}} 0 <2 Co. 9 Ti (.A 207 8.6 1.1

_{_{_{Bi 2 Pb 0 Ca [s Ho}}} 0 2 Co. 9 Ti (.A 190 7.8 0.8

_{_{_{_{Bi 2 Pb 2 Ca L8 Er 0}}}} . 2 Co ■ A 198 9.0 0.7

_{_{_{_{Bi 2 Pb 0 2 Ca L8 Yb}}}} 0. 2 Co. 9 Ti (.A 199 8.2 1.3

Bi ₂ Ba ₂ Co _L9 Ti ₀ _.A 190 8.6 1. 1

Bi ₂ Ba _L8 Na _{0 2} Co _L9 Ti _c ■ A 198 8.7 1.0

Bi ₂ Ba! ₈ K ₀ _ ₂ Co _L9 Ti _0- fi 199 8.3 1.3

Bi ₂ Ba! ^ ° l.chome1 (.A 201 9.0 0.9 33]

34]

35]

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_{_{_{_{Bi 2 Pb 0. 2 Ca l}}}} , s Ni 0. 2 Co L9 V 0,, 0 9 202 8.1 1.1

_{_{_{_{Bi 2 Pb 0. 2 Ca KS}}}} Cu 2 C L9 V 0, 204 8.0 0.8

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Zn 0. 2 Co L 9 V 0. ^ 9 197 7.8 1.3

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Pb 0. 2 Co ]. ^ ₉ 190 7.2 1.4

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Sr 0 <2 Co 1> 9 V 0 <^ 9 198 9.0 1.1

B i ₂ Pb ₀ , ₂ Ca _{L s} Ba ₀ _ ₂ Co _L. ₉ V _0. _L 0 ₉ 199 7.8 1.0

201 7.5 1.3

_{_{_{... Bi 2 Pb 0 2}}} Ca 1 .8Y 0 2 Co L9 V 0 1 0;, 207 8.6 0.9

_{_{_{_{Bi 2 Pb 0. 2 Ca 8}}}} La 0. 2 Co L 9 V 0. Fi 9 190 8.2 1.1

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Ce 0. 2 Co L 9 V 0. Fi 9 198 7.9 1.4

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Pr 0. 2 Co L 9 V 0. Fi 9 199 6.9 1.2

_{_{_{_{Bi 2 Pb 0 + 2 Ca L}}}} 8 Nd 0. 2 Co L 9 V 0. A 201 8.1 0.9

BisPbo.sCauSnio.jCo'.sVo.iOg 210 9.0 1.1

BiaPbo jCaLgEuo jCo!

206 8.2 1.2

_{_{_{Bi 2 Pb 0. 2 Ca ,.}}} 8 Gd 0. 2 Co L 9 V 0., 0 9 205 7.9 0.9

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Dy 0. 2 Co L9 V 0. ^ 9 198 8.6 1.1

_{_{_{B i 2 Pb 0. 2 Ca}}} L 8 Ho 0. 2 Co L 9 V 0. Fi 9 195 9.1 1.2

BiaPbo.sCaLgEro.sCoLgVo.A 200 6.9 1.4

BijPbo.sCai.sYbo. ₂ Co _L9 V _0. , 0 ₉ 203 7.4 0.8

Bi ₂ Ba ₂ Co _L9 V ₀ ^ ₉ 208 7.7 1.2

198 8.0 1.1

_{_{_{Bi 2 Ba 1 8 K 0 .2Co}}} L9 V 0 (0 9 199 8.2 1.4

Bi ₂ Ba ₁₈ Lio.2Co ₁₉ V ₀ ! Θ ₉ 200 7.9 1.2

199 9.1 0.9

_{_{_{Bi 2 Ba 1 8 V 0.}}} 2 Co 1 9 V 0 1 0 9 210 8.4 1.1

_{_{_{Bi 2 Ba L8 Cro. 2 Co}}} 1. 9 V 0. 1 0 9 202 8.6 1.2

_{_{_{_{Bi 2 Ba L8 Mn 0. 2}}}} Co L9 V 0. L 0 9 204 8.2 0.9

Bi ₂ Ba _{1 8} Fe ₀ .aCo Vo.A 197 7.9 1.1

_{_{_{_{Bi 2 Ba L8 Ni 0. 2}}}} Co L gV 0, 0 9 190 8.6 1.2

Bi ₂ Ba _L8 Cu ₀ .aCOi.gVo.iOg 198 9.1 1.4

_{_{_{_{Bi 2 Ba L8 Zn 0. 2}}}} Co L9 V 0 A 199 6.9 0.8

BiaBaLgPbo.aCoLgVdOg 201 7.4 1.3

_{_{_{_{Bi 2 Ba L8 Ca 0 .2Co LS}}}} V 0 1 0 9 207 7.8 1.2

BiaBaLgSrc.sCoLgVo.iOg 190 7.7 1.1

_{_{_{_{Bi 2 Ba ls Al 0. 2}}}} Co L9 V 0 ^ 0 9 198 8.0 0.8 38]

39]

"^ Q ² T g

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[0 挲] [8S20] OOZdf / e :) d 69 8691790 / S00Z OAV 41]

42]

43]

45]

46]

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57]

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[8S 挲] [9 0] f6l6l0 / ^ 00Zdf / X3d Z8 8691 ^ 90 / SOOi OAV 59]

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Cu 0. 2 Co L 9 Ag 0. 0 9 197 8.6 1.2

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} s Zn 0. 2 Co ,. 9 Ag 0. A 190 7.8 1.4

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Pb 0. 2 Co h 9 Ag 0. Fi 9 198 9.0 0.8

_{_{_{_{Bi 2 Pb 0. 2 Sr 8}}}} Ca 0. 2 Co 9 Ag 0. Fi 9 199 8.2 1.3

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Ba 0 2 Co L 9 Ag 0., 0 9 201 8.3 1.2

_{_{_{_{Bi 2 Pb 0. 2 Sr L8}}}} Al 0i 2 Co 9 Ag 0. Fi 9 207 8.4 1. 1

_{_{_{_{Bi 2 Pb 0. 2 Sr L8}}}} Y 0, 2 Co 1 9 Ag 0. Fi 9 190 8.6 0.8

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 La 0. 2 Co ,, 9 Ag 0. Fi g 198 8.2 0.7

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Ce 0 2 Co L 9 Ag 0. A 199 7.9 1.3

201 8.6 0.8

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Nd 0. 2 Co L 9 Ag 0. A 210 9. 1 1.3

_{_{_{B i 2 Pb 0. 2 Sr}}} 8 Sm 0. 2 Co L 9 Ag 0, 0 9 206 6.9 1.2

_{_{_{_{Bi 2 Pb 0. 2 Sr 8}}}} Eu 0. 2 Co L 9 Ag 0. I0 9 205 7.4 1.1

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Gd 0. 2 Co h 9 Ag 0. Fi 9 198 7.8 0.8

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Dy 0. 2 Co! 9 Ag 0., 0 9 195 7.7 1.3

_{_{_{_{Bi 2 Pb 0. 2 Sr Lg}}}} Ho 0i 2 Co L9 Ag 0. A 200 8.0 1.4

_{_{_{_{Bi 2 Pb 0. 2 Sr L}}}} 8 Er 0. A. 9 Ag 0. A 203 8.2 1. 1

_{_{_{Bi 2 Pb 0. 2 Sr ,.}}} 8 Yb 0. 2 Co L 9 Ag 0., 0 9 200 7.9 1.0

_{_{_{_{Bi 2 Ca 2 Co L9 Ag 0}}}} . 1 0 9 201 8.4 0.9

BigCa! GNao aCo! ₉ Ag _{0 1} 0 ₉ 208 8.6 1.1

_{_{_{_{Bi 2 Ca L8 K 0. 2}}}} Co t 9 Ag 0 ^ 9 198 7.8 1.4

199 9.0 1.2

Bi ₂ Ca, Ji ₀ 2Co ₁₉ Ag _{0 1} 0 ₉ 200 8.2 0.9

Bi ₂ Ca _L8 V _{0 2} Co ₁₉ Ag ₀ , 0 ₉ 206 8.3 1.1

_{_{Βί, Οβ;. 8 Cr 0}} 2 Co L9 Ag 0 1 0 9 205 8.6 1.2

Bi ₂ Cai. ₈ Mn _a2 Co ₁₉ Ag (, j0 ₉ 198 8.7, 0.9

_{_{_{Bi 2 Ca L8 Fe 0 .2Co ,.}}} 9 Ag 0., 0 9 206 8.3 1. 1

Bi ₂ Ca _L8 Ni _{0 2} Co _L9 Ag _0. (Og 198 9.0 1.2

BijCai.gCuo.jCo! ₉ Ag _0. ^ ₉ 207 7.9 1.4

Bi ₂ Ca! ₈ Zn _{0 2} Co ₁₉ Ag _{0 1} 0 ₉ 190 8.1 0.8

Bi ₂ Ca _L8 Pb _a2 Co _L9 Ag ₀ .fi _g 198 8.0 1.3

Bi ₂ Ca _L8 Sr _{0 2} Co! ₉ Ag _{0 1} 0 ₉ 199 7.8 1.2

_{_{_{Bi 2 Ca 1 8 Ba 0.}}} 2 Co 1 9 Ag 0., 0 9 201 7.2 1. 1

BiaCa! GAlo aCo! ₉ Ag _{0 1} 0 ₉ 210 9.0 1.4

_{_{_{_{Bi 2 Ca L8 Y 0. 2}}}} Co 1 9 Ag 0 1 0 9 206 8.2 1.2

_{_{_{_{Bi 2 Ca L8 La 0. 2}}}} Co tg Ag 0 1 0 9 205 7.9 0.9 60]

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fl 8 "Ζ S6T ¾i ° 0 ^Ζ ° ^E 3 ⁸ '' eg ² '° qd ³ τ g

ΐ 'Τ 9' 8 86T ⁶ o ^T 'i' ^l ° d ^z ° d ⁸ .'eg ^s ' ^{0 (} wg

6 '0 · 8 90Z ¾'' ⁰ οκ ^6Ί θ3 ^ζ ' ° u2 ⁸ '' Bg ⁵ ' ⁰ qd ^z "ta

ε 'ΐ Τ' 6 9 Z ¾ '' O op. 1. 1 ⁵ ' ⁰ η 1 ⁸ `` eg ² ' ° qj ^e i: a

0 ΐ Ζ '01Z ⁶ 0 ^l ° opi ⁶ '03 ^s ' eg ² "qj g

τ · ΐ ^ '8 10Z ⁶ 0 ^T ' ^D. w ⁶ ·, 03 ^ζ . j ^s ' eg "" qj g

\ "ΐ 0'6 661 ⁶ 0 '°° Vf' ° 3 ^Z ° ^u Vi ^sl ^ 9 ⁸ ° qd ^e T g

ε "ΐ 8" Ζ 861 ¾! ° oj¾ ⁶ ' ^t OQ ^Z ' ° J3 ^S 'eg ² ' ° qj ^z i: g

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^{ΐ · ΐ · 8 LOZ 6 o} T '° f Ί ο ζ' ° TI 8 '^ a 5' ° d s Ta

Ζ ΐ ΐ ΐ6 10Z ¾ '° oj¾ ^{6 Ί} 03 ^ζ ' ° i ⁸ Bg ^s ° qj ^z ]: g

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fl 8 L 061 ⁶ 0 ' ⁰ ο ^ ^βΊ θ3¾9 ² ' ° qj ^e i: g ΐ 'Τ fS OS' °° Ovf '' ⁰ 3 ⁵ ° ¾λ ⁸ ' ¹ ΐ 3

6 Ό 1 66 ZOZ '° ⁰ W ^{6, 0} 3 ^e ° -ia ^B ' ^Β 9 ^ζ ΐ9

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1 ZS 66T ¾ '' ° ο [¾ ⁶ '^ ο s' ° AQ ⁸ ' eg ^ g

^{6 0'8 OOZ 6 0 '' °} ορ [6 Ί ο one ^{^{^{ζ "° 9 8 Ί Β9 ζ}}} τ9

Ζ 'ΐ L' L 66T ¾ '° o [¾ ^{6 l} 03 ^e ' ° ng ⁸ egZfg f \ 8'i.86T ¾ '' ⁰ ow ⁶ `` ^o 3 ^z "HIS ⁸ ' ^Ε 9 ^Ζ Τ9

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Bi ₂ Ca _{L 8} Ho _{0 2} Co _{L 9} Ta ₀ ^ ₉ 206 6.9 1.3

Bi Ca ₈ Er _{0 2} Co _{L 9} Ta ₀ 0 ₉ 205 7.4 0.9

BisCa! ₈ Yb _{0i 2} Co _L9 Ta _{0. I0} ₉ 198 7.8 1.1

_{_{_{Bi 2 Pb 0. 2 C Co}}} L. J¾i0 9 200 8.0 1.2

B i ₂ Pb _{0 2} Ca! _{_{_{_{g Na 0. 2 C 9 Ta}}}} 0 199 8.2 0.9

_{_{_{Bi 2 Pb 0. 2 Ca 8Ko.2CoL9Tao.iO9}}} 210 7.9 1. 1

Bi ₂ Pb _{0 2} Ca 【 ₈ i _{0 2} 0ο _{: 9} Ta ₀ 202 9.1 1.2

_{_{_{Bi 2 Pb 0 2 Ca 1 8}}} Ti 0. 2 Co 9 Ta 0 ^ 9 204 8.4 0.9

_{_{_{_{Bi 2 Pb 0. 2 Ca L8}}}} V 0. 2 Co L9 Ta i 0 9 197 8.6 1.1

_{_{_{_{Bi 2 Pb 0. 2 Ca h}}}} 8 Cr 0. 2 Co,. 9 Ta 0> A 190 8.2 1.2

B i ₂ Pb _{0 2} Ca _{L s} Mn _Q. ₂ Co, ₉ Ta _{0 L} 0 ₉ 198 7.9 1.4

_{_{_{Bi 2 Pb 0 2 Ca L 8}}} Fe 0. 2 Coj 9 Ta 0 j0 9 199 8.6 0.8

Bi ₂ Pb _{0 2} Ca _{L 8} Ni ₀ .sCO] ₉ Ta _{0 L} 0 ₉ 201 9.1 1.3

_{_{_{Bi 2 Pb 0 2 Ca L 8}}} Cu 0. 2 Co L 9 Ta 0 ^ 9 207 6.9 1.2

_{_{_{Bi 2 Pb 0> 2 Ca L8}}} Zn 0. 2 Co L9 Ta 0 1 0 9 190 7.4 1. 1

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} s Pb 0. 2 Co L 9 Ta 0. L 0 9 198 7.8 0.8

_{_{_{Bi 2 Pb 0 2 Ca L 8}}} Sr 0. 2 Co L 9 Ta 0 ^ 9 199 7.7 1.3

_{_{_{_{Bi 2 Pb 0. 2 Ca L8}}}} Ba 0. 2 Co L 9 Ta 0. ^ 9 201 8.0 1.4

Bi _₂ Pb ₀ ₂ Ca and _{_{_{_{S A1 0. 2 Co L 9}}}} Ta 0 ^ 9 210 8.2 1.1

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Y 0 2 Co L 9 Ta 0 t 0 9 206 7.9 1.0

205 9.1 1.3

_{_{_{Bi 2 Pb 0 2 Ca L 8}}} Ce 0 2 Co L 9 Ta 0, 0 9 198 8.4 0.9

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Pr 2 Co L 9 Ta 0. 195 8.6 1. 1

Bi ₂ Pb _{0 2} Ca _{L 8} Nd ₀ _ ₂ Co _h9 Ta ₀ _.L 0 ₉ 200 7.8 1.4

_{_{_{_{Bi 2 Pb 0. 2 Ca h}}}} 8 Sra 0. 2 Co L 9 Ta 0. A 203 9.0 1.2

_{_{_{_{Bi 2 Pb 0. 2 Ca h8}}}} Eu 0> 2 Co L 9 Ta 0 _ ^ 9 200 8.2 0.9

_{_{_{_{Bi 2 Pb 0. 2 Ca L8}}}} Gd 0. 2 Co Ta 0. 0 9 203 8.3 1.1

Bi ₂ Pb _{0 2} Ca, ₈ Dy _{a 2} Co _{L 9} Ta ₀ 0 ₉ 201 8.6 1.2

_{_{_{_{Bi 2 Pb 0. 2 Ca L8}}}} Ho 0. 2 Co L9 Ta 0,} 0 9 208 8.7 0.9

_{_{_{_{Bi 2 Pb 0. 2 Ca L}}}} 8 Er 0. O L 9 Ta 0 _ 198 8.3 1.1

199 9.0 1.2

Bi ₂ Ba ₂ Co _{1 9} Ta ₀ ^ ₉ 203 8.1 0.8

_{_{_{Bi 2 Ba, 8 Na 0.}}} 2 Co L 9 Ta 0 ^ 9 200 8.0 1.3

BijBa! GKo 203 7.8 1.2

_{_{_{Bi 2 Ba 1 8 Li 0.}}} 2 Co ,. 9 Ta 0 ^ Ο ,, 201 7.2 1.1

Bi ₂ B! ₈ Ti _{0 2} Co ₁₉ Ta ₀ 208 9.0 0.8

Bi ₂ Ba _L8 V ₀ , ₂ Co ₁₉ Ta ₀ A 198 7.8 0.7 80]

81]

[0280] As is clear from the above results, each of the oxides shown in Table 14-Table 81 has excellent properties as a p-type thermoelectric conversion material, and also has good conductivity. Therefore, it is considered that good thermoelectric power generation performance is exhibited also when these oxides are used in place of the p-type thermoelectric conversion material in the thermoelectric power generator of Example 1.

[0281] Reference Example 99

General formula: Ln R ¹ Ni R ² O or general formula: (Ln R ³ ) Ni R ⁴ O An n-type thermoelectric converter mnpqrst 2 uvw A composite oxide having properties as a replacement material is prepared by the following method. did.

[0282] As a raw material, a nitrate containing a constituent element of a target composite oxide was used. After complete dissolution and thorough mixing in an alumina crucible, the water was evaporated to dryness. Next, the precipitate was calcined in an air at 600 ° C for 10 hours in air to decompose nitrate. Thereafter, the fired product was pulverized, pressed, and fired in an oxygen stream of 300 mlZ for 20 hours to synthesize a composite oxide. The firing temperature and firing time were appropriately changed within the range of 700-1100 ° C so that the target oxide was formed.

[0283] Tables 82 to 128 below show the element ratio, the Seebeck coefficient at 700 ° C, the electric resistivity at 700 ° C, and the thermal conductivity at 700 ° C in each of the obtained composite oxides. Show.

[0284] [Table 82]

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La ₂ Ni0 ₄ -25 6.1 4.3

Ce ₂ Ni0 ₄ O -28 5.0 4.2

Pr ₂ Ni0 ₄ -28 7.0 4.3

Nd ₂ Ni0 ₄ -22 4.9 4.5

Sm ₂ Ni0 ₄ -20 5.0 4.6

Eu ₂ Ni0 ₄ -25 6.0 4.7

Gd ₂ Ni0 ₄ -27 5.2 4.4

Dy ₂ Ni0 ₄ - 30 7.0 4.9

Ho ₂ Ni0 ₄ -29 8.1 4.7

Er ₂ Ni0 ₄ -30 6.9 4.6

Yb ₂ Ni0 ₄ -28 6.7 4.6

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_{_{_{Yb L8 Ca 0. 2 Ni -26}}} 6.4 4.0

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_{_{_{_{Yb L8 Ca 02 Ni 0. 9}}}} Mo 0. L 0 4 -18 6.4 3.6

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Yb _L8 Ca ₀ • ₂ Ni ₃ beauty A -24 7.0 3.7

Yb ^ Ca ^ Ni cho -28 6.8 4.0

Yb ,. ₈ Bi _c , ₂ Ni 丄. .i0 ₄ -20 6.8 3.6

Yb 〖. ₈ Bi _c . ₂ Ni -26 5.9 4.1

_{_{_{. Yb L8 Bi c 2 Ni)}}} Cr 0 |!. 0 4 - 23 6.5 3.9

Yb _L8 Bi _c . ₂ Ni ₀₉ Mn ₀₁ 0 ₄ -22 7.0 4.6

Yb ^ Bic, ₂ Ni -19 6.8 4.3

Yb _L8 Bi _c . ₂ Ni 0.9CO0.〇 -17 5.8 4.0

Yb _Lg Bi _c , ₂ Ni-20 6.3 4.7

Yb ,. ₈ Bi ₀ , ₂ Ni .9MO0. -22 7.1 4.2

Yb, ₈ Bi _c . ₂ Ni A-20 6.4 4.3

Yb _{l 8} Bi _c , ₂ Ni ^ bo. -21 5.9 4.9

, ₂ Ni -23 6.4 3.9

[0331] As is clear from the above results, each of the oxides shown in Table 82 to Table 128 has excellent characteristics as an n-type thermoelectric conversion material, and also has good conductivity. Therefore, it is considered that good thermoelectric power generation performance is exhibited even when these oxides are used instead of the n-type thermoelectric conversion material in the thermoelectric power generator of Example 1.

Claims

The scope of the claims

[1] Using a plurality of thermoelectric conversion elements formed by electrically connecting one end of a p-type thermoelectric conversion material and one end of an n-type thermoelectric conversion material, and using an unbonded p-type thermoelectric conversion material of the thermoelectric conversion element A thermoelectric power generation module in which a plurality of thermoelectric conversion elements are connected in series by connecting one end to an unbonded end of an n-type thermoelectric conversion material of another thermoelectric conversion element,

Thermoelectric generator provided.

[2] Claim 1 wherein the catalytic combustion type heat source includes a catalytic combustion chamber filled with a catalyst and a heat transfer unit for transmitting thermal energy generated in the catalytic combustion chamber to a thermoelectric power generation module. A thermoelectric generator according to claim 1.

3. The thermoelectric generator according to claim 2, wherein the catalytic combustion heat source further comprises a fuel container containing fuel to be supplied to the catalytic combustion chamber.

4. The thermoelectric generator according to claim 2, wherein the catalytic combustion heat source further includes a preheater.

5. The thermoelectric generator according to claim 3, wherein the catalytic combustion heat source further comprises a preheater.

[6] p-type thermoelectric conversion material power used in thermoelectric generation module General formula: Ca A ¹ Co A ² O (Formula

In abcde, A ¹ is a kind of which group force consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and lanthanoid is selected A ² is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb, and Ta 2.2≤a≤3.6; 0≤b≤0.8; 2.0≤c≤4.5; 0≤d≤2.0; 8≤e≤10. ) And a general formula: Bi Pb M ¹ Co M ²⁰ (where M ¹ is

f g h i j k

One or more elements selected from the group consisting of Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Ca, Sr, Ba, Al, Y and lanthanoids Yes, M ² is one or more elements selected from the group consisting of Ti, V, Cr, Mn, Fe, Ni, Cu, Ag, Mo, W, Nb and Ta, and 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 selected from the group consisting of composite oxides represented by And

When the n-type thermoelectric conversion material has the general formula: Ln R ¹ Ni R ² O (where Ln is a lanthanoid selected from mnpqr

Is two or more elements, R ³ is one or more elements selected from the group consisting of Na, K, Sr, Ca and Bi, and R ⁴ is Ti, V, Cr, Group force consisting of Mn, Fe, Co, Cu, Mo, W, Nb and Ta One or more elements selected from the group consisting of 0.5≤s≤1.2; 0≤t≤0.5; 0.5≤u≤1.2; 0≤v≤0.5; 3.6≤w≤4.4. 2. The thermoelectric generator according to claim 1, wherein the thermoelectric generator is at least one selected oxide selected from the group consisting of the complex oxides represented by: P-type thermoelectric conversion material power used in thermoelectric generation module General formula: Ca A ¹ Co O (where ab 4 e

, A ¹ is a group force selected from Na, K, Li, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Pb, Sr, Ba, Al, Bi, Y and a lanthanoid force. Two or more elements, 2.2≤a≤3.6; 0≤b≤0.8; 8≤e≤10. ) And a general formula: Bi Pb M ¹ Co O (fgh 2 k, wherein M ¹ is ^one or more elements selected from the group consisting of Sr, Ca and Ba. The complex oxide force represented by 1.8 ≤ f ≤ 2.2; 0 ≤ g ≤ 0.4; 1.8 ≤ h ≤ 2.2; 8 ≤ k ≤ 10. Thing

One or more elements selected from the group consisting of 0.5≤m≤1.2; 0≤n≤0.5; 2.

7≤r≤3.3. ), A general formula: (La R ³ ) NiO (where R ³ is st 2 w

One or more elements selected from the group consisting of Na, K, Sr, Ca and Bi, and 0.5 ≤ s ≤ 1.2; 0 ≤ t ≤ 0.5; 3.6 ≤ w ≤ 4.4. Composite oxide represented by), and the general formula: ^{^{L a R 5 Ni R 6 O}} ( wherein, R ⁵ is small is selected Na, K, Sr, Ca, from the group consisting of Bi, and Nd

X P q r

R ⁶ is at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co and Cu; 0.5≤x≤1.2; 0≤y≤0.5 ; 0.5≤p≤ 1.2; 0.01≤q ≤0.5; 2.8≤r≤3.2. ) At least selected from the group consisting of composite oxides 2. The thermoelectric generator according to claim 1, wherein the thermoelectric generator is also a kind of acid.

[8] The thermoelectric generator according to any one of [17] to [17], wherein cooling means is provided on a surface of the thermoelectric power module opposite to a surface to be heated.