CN103779492A - Thermoelectric conversion device with metal tube serving as inner electrode and metal wire serving as outer electrode - Google Patents
Thermoelectric conversion device with metal tube serving as inner electrode and metal wire serving as outer electrode Download PDFInfo
- Publication number
- CN103779492A CN103779492A CN201410037955.4A CN201410037955A CN103779492A CN 103779492 A CN103779492 A CN 103779492A CN 201410037955 A CN201410037955 A CN 201410037955A CN 103779492 A CN103779492 A CN 103779492A
- Authority
- CN
- China
- Prior art keywords
- thermoelectric conversion
- thermo
- converting material
- electric converting
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 description 15
- 238000005245 sintering Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 9
- 239000007769 metal material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 230000000171 quenching effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000005619 thermoelectricity Effects 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 230000005676 thermoelectric effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention discloses a thermoelectric conversion device. The thermoelectric conversion device comprises an inner electrode, an outer electrode and a thermoelectric conversion material arranged between the inner electrode and the outer electrode, wherein the inner electrode is the metal tube, the outer electrode is the metal wire, the thermoelectric conversion material is Ce (FexZryPbz)13, the range of x is from 0.70 to 0.95, the range of y is from 0.05 to 1-x, and the range of z is from 0.005 to 0.5. The thermoelectric conversion device solves the problems that in the prior art, the conversion rate of the thermoelectric conversion technology is low and the practical application effect of the thermoelectric conversion technology is poor, and is high in thermoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of thermoelectric conversion element.
Background technology
Thermoelectric effect is in the time heating to material, can induce electric current, the phenomenon that current strength increases along with the increase of heat.The material that can induce electric current in the time of heating, thermoelectric effect material, is also thermo-electric converting material.Do the two poles of the earth with metal material, centre couples together two metal materials with thermo-electric converting material, and thermoelectric conversion element is made.
Thermoelectric conversion element is one-way heat conduction structure, is first a metal electrode to be heated, and then heat is conducted to another metal electrode by thermo-electric converting material by the metal heating.Due to one-way heat conduction structure, make small hot particle transform the electric current that has produced continuous circulation to electronics.Due to unilateal conduction structure, the thermocurrent in thermal cell is played to forward promotion, the effect oppositely stoping.
It is electric energy that thermoelectric conversion element can utilize the thermal power transfer such as waste heat, underground heat of solar energy, cogeneration power plant, and its conversion efficiency depends primarily on the performance of thermo-electric converting material and the two poles of the earth metal material.In addition, conversion efficiency is also relevant with the contact area of the two metal utmost points and thermo-electric converting material, so area expansion instrument is set on the contact-making surface of two metal utmost points and thermo-electric converting material, is mainly arranged on interior electrode, thereby expansion contact area, makes thermoelectricity conversion reach optimum efficiency.If desired, all right in parallel or series connection use of thermoelectric conversion element, as some groups of thermal cells are overlaped, makes heat obtain conversion effect more fully.
But the transfer ratio of prior art kind thermoelectric conversion element is lower, is difficult to be applied in industrial production.Therefore finding the more suitably metal material of thermo-electric converting material and the two poles of the earth, improve the transfer ratio of thermoelectric conversion element, is the problem that this area is needed solution badly.
Summary of the invention
The present invention is low in order to solve in prior art thermoelectric generation technology transfer ratio, and the problem that practical application effect is poor, provides the thermoelectric conversion element that a kind of conversion efficiency of thermoelectric is high.
Interior electrode of the present invention is metal tube and the very thermoelectric conversion element of metal wire of dispatch from foreign news agency, comprises interior electrode, external electrode and the thermo-electric converting material arranging between the two, and wherein interior electrode is metal tube, and dispatch from foreign news agency is metal wire very, wherein,
Thermo-electric converting material is Ce (Fe
xzr
ypb
z)
13,
Wherein: the scope of x is 0.70~0.95; The scope of y is 0.05~1-x; The scope of z is 0.005~0.5.
Thermo-electric converting material is preferably CeFe
11zr
1.5pb
0.5, CeFe
11.5zrPb
0.5, CeFe
10.8zr
1.7pb
0.3, CeFe
11.5zr
1.2pb
0.3.
Preferably, very iron or copper of interior electrode and dispatch from foreign news agency.
Through experiment test, thermoelectric conversion element of the present invention and thermo-electric converting material well known in the prior art, the device that for example pyrite is made is compared, and conversion efficiency of thermoelectric obviously improves, between 20~50 ℃, improve 12~18%, between 50~100 ℃, improve 22~32%.The discovery that the inventor is pleasantly surprised, adopts Ce (Fe
xzr
ypb
z)
13the conversion efficiency of the thermoelectric conversion element of making compare the inventor another in front invention the thermoelectric conversion element take Ce as main composition thermo-electric converting material taller go out 2~3%.
Accompanying drawing explanation
Fig. 1 is the structural representation of thermoelectric conversion device of the present invention.
Fig. 2 is that Fig. 1 is along horizontal sectional view.
Fig. 3 is Fig. 1 sectional view longitudinally.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further, but should be appreciated that, embodiment only limits its protection range for technical scheme of the present invention being described, being not used in.
Thermoelectric conversion element of the present invention, comprises interior electrode 1, external electrode 2 and the thermo-electric converting material 3 arranging between the two, and wherein interior electrode 1 is metal wire, and external electrode 2 is metal wire, as shown in Figure 1, 2, 3.
The manufacture method of this thermoelectric conversion element is: with a metal tube as an emitter 1, emitter 1 outer-heating electric transition material 3, then be wrapped in thermo-electric converting material 3 surface formations with metal wire and add thermoae 2, add thermoae 2 and emitter 1 on pick out joint with connecting line 6, just formed single entry pipeline thermal cell.
This thermoelectric conversion element has been strengthened heat radiation, and promotes heat one-way flow, to the effect of improving of thermoelectricity conversion tool, is also the mode outside in heating, and is applicable to various common thermoelectricity conversions.
Interior electrode of the present invention is also referred to as emitter, and it receives the electronics from thermo-electric converting material.External electrode is thermoae also referred to as adding, and after its variations in temperature, to thermo-electric converting material conveying electronic, thereby thermo-electric converting material is heated.Due to unilateal conduction structure, the thermocurrent in thermoelectric device plays the effect that forward promotes, oppositely stops.
Wherein, interior electrode 1, external electrode 2 are metal material.Being preferably iron or copper, can be also aluminium or silver.For example interior electrode 1 selects metallic iron, and external electrode 2 selects metallic copper.
Thermo-electric converting material 3 is Ce (Fe
xzr
ypb
z)
13
Wherein: the scope of x is 0.70~0.95; The scope of y is 0.05~1-x; The scope of z is 0.005~0.5.
Thermo-electric converting material is preferably CeFe
11zr
1.5pb
0.5, CeFe
11.5zrPb
0.5, CeFe
10.8zr
1.7pb
0.3, CeFe
11.5zr
1.2pb
0.3.
Thermo-electric converting material 3 can also be Ce (Fe
xhf
ypt
z)
13
Wherein: the scope of x is 0.85~0.90; The scope of y is 0.03~1-x; The scope of z is 0.005~0.45.
Thermo-electric converting material is preferably CeFe
11zr
1.55pb
0.45, CeFe
11.5zr
1.15pb
0.45, CeFe
10.75zr
1.8pb
0.35, CeFe
10.8zr
1.85pb
0.35.
The manufacturing process of described thermo-electric converting material 3 comprises the steps:
A) make Ce, Fe, Zr and tetra-kinds of chemical elements of Pb in solid phase and/or liquid phase with the stoichiometric reaction corresponding to its metal_based material, form Ce (Fe
xzr
ypb
z)
13reactant;
B) above-mentioned reactant is pressed into solid;
C) by above-mentioned solid sintering and/or heat treatment,
D) will be from sintering c) of step and/or heat treated solid with at least cooldown rate quenching of 100K/s.
In the step (a) of this method,
In solid phase or liquid phase, with the stoichiometric proportion corresponding to thermo-electric converting material, the element and/or the alloy that are present in the latter's thermo-electric converting material are transformed.
Carry out the reaction of step in a) preferably by the combined heated in closed container or in extruder by element and/or alloy, or by solid phase reaction in ball mill.Particularly preferably carry out solid phase reaction, it especially carries out in ball mill.On this reaction principle, be known; Referring to document cited above.Conventionally, the powder that is present in the powder of the each element in the latter's thermo-electric converting material or the alloy of two or more each elements is mixed with suitable weight ratio with powder-form.If necessary, also mixture can be ground to obtain microcrystalline powder mixture.Preferably this mixture of powders is heated in ball mill, this causes further pulverizing and well mixing, and causes the solid phase reaction in mixture of powders.Or, each element is made to this powder and mixes with selected stoichiometric proportion, then melting.
In closed container, combined heated makes fixing volatile element and controls stoichiometric proportion.Particularly, in the situation that using phosphorus, in open system, this will easily evaporate.
In the step (b) in this method,
The solid that step is obtained in a) was suppressed before sintering and/or heat treatment.This improves density of material, and high density thermo-electric converting material is present in the latter's application.This is especially favourable, because exist the volume in magnetic field to reduce, this can be cost-saving considerably.Be compressed to that itself is known, available or carry out without compression aid.Can use any model that is suitable for compacting.By compacting, can obtain the formed body of required three-dimensional structure.Compacting after can carry out step sintering and/or heat treatment c), carry out thereafter steps d) quenching.
In the step (c) of this method,
The sintering of solid and/or heat treatment are carried out in c) in step, preferably first at the temperature of 700-1300 ℃, carry out sintering, then at the temperature of 500-750 ℃, heat-treat.These values are particularly useful for formed body, and lower sintering and heat treatment temperature can be used for powder, for example, at the temperature of 500-700 ℃, carry out.For formed body/solid, sintering, more preferably at 900-1200 ℃, especially carries out at the temperature of 1000-1100 ℃.Then heat treatment can for example be carried out at 600-700 ℃.
Sintering preferably carries out 20-30 hour, more preferably 25-30 hour.50-70 hour, more preferably 60-65 hour are preferably carried out in heat treatment.Precise time can adapt to actual requirement according to material adjustment.
Sintering/heat treatment causes granule boundary partial melting, makes material further closely knit.Therefore, the melting of step in b) and fast cooling make step c) duration reduce considerably.This also makes continuous production thermo-electric converting material.
In the step (d) of this method,
When metal_based material is not slowly cooled to ambient temperature after sintering and/or heat treatment, but during with high cooldown rate quenching, thermo-lag can significantly reduce and can realize thermoelectric effect.This cooldown rate is 100K/s at least.Cooldown rate is preferably 200-1300K/s, and preferred cooldown rate is 300-1000K/s.
Quenching can realize by any suitable cooling means, for example, by water or liquid, aqueous if cooling water or ice/water mixture are by solid quenching.For example, can make solid fall into ice-cooled water.Also can use cold gas if liquid nitrogen is by solid quenching.Other method of quenching is well known by persons skilled in the art.
Measure by thermal cell is heated to different temperatures, just can obtain the corresponding current strength value that different volumes, different area produce under different temperatures.Thermoelectric conversion element of the present invention can be converted into electric energy various heat energy.Its sensitiveness is good, and airborne variations in temperature can make thermal cell generation current change, and is a kind of collection converter of common heat, especially in the time of high-temperature heating, can obtain good thermoelectricity conversion effect, and can prolonged and repeatedly use.The experiment proved that, adopt thermo-electric converting material of the present invention to make thermoelectric conversion element, compared with the thermoelectric conversion element forming with thermo-electric converting material well known in the prior art, conversion efficiency of thermoelectric obviously improves, between 10~50 ℃, improve 12~18%, between 50~100 ℃, improve 22~32%.The temperature of thermal cell inside can not unconfinedly increase, and the heating-up temperature of thermoelectrical conversion battery of the present invention is preferably limited in 100 degrees Celsius.Due to the structure difference of thermoelectric cell, material difference, to the requirement difference of temperature.
As can be seen here, material of the present invention is the thermo-electric converting material that is suitable for a kind of novelty of thermoelectric conversion element, and its indoor temperature change generated in case can change by generation current, especially can significantly improve the conversion efficiency of thermoelectric of heating-up temperature within the scope of 50~100 ℃.
Claims (3)
1. internal and external electrode is a thermoelectric conversion element for metal wire, comprises interior electrode, external electrode and the thermo-electric converting material arranging between the two, it is characterized in that,
Interior electrode is metal tube, and dispatch from foreign news agency is metal wire very,
Thermo-electric converting material is Ce (Fe
xzr
ypb
z)
13,
Wherein: the scope of x is 0.70~0.95; The scope of y is 0.05~1-x; The scope of z is 0.005~0.5.
2. device as claimed in claim 1, is characterized in that, described thermo-electric converting material is preferably CeFe
11zr
1.5pb
0.5, CeFe
11.5zrPb
0.5, CeFe
10.8zr
1.7pb
0.3, CeFe
11.5zr
1.2pb
0.3.
3. device as claimed in claim 1, is characterized in that, very iron or copper of described interior electrode and dispatch from foreign news agency.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410037955.4A CN103779492A (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion device with metal tube serving as inner electrode and metal wire serving as outer electrode |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410037955.4A CN103779492A (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion device with metal tube serving as inner electrode and metal wire serving as outer electrode |
Publications (1)
Publication Number | Publication Date |
---|---|
CN103779492A true CN103779492A (en) | 2014-05-07 |
Family
ID=50571523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410037955.4A Pending CN103779492A (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion device with metal tube serving as inner electrode and metal wire serving as outer electrode |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103779492A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001018884A1 (en) * | 1999-09-09 | 2001-03-15 | Symyx Technologies, Inc. | Improved thermoelectric material system |
CN101047223A (en) * | 2005-12-07 | 2007-10-03 | 株式会社东芝 | Thermoelectric material and thermoelectric conversion element using same |
CN102969442A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Thermoelectric conversion device with metal tube as inner electrode and metal wire as outer electrode |
-
2014
- 2014-01-26 CN CN201410037955.4A patent/CN103779492A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001018884A1 (en) * | 1999-09-09 | 2001-03-15 | Symyx Technologies, Inc. | Improved thermoelectric material system |
CN101047223A (en) * | 2005-12-07 | 2007-10-03 | 株式会社东芝 | Thermoelectric material and thermoelectric conversion element using same |
CN102969442A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Thermoelectric conversion device with metal tube as inner electrode and metal wire as outer electrode |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102969443B (en) | A kind of internal and external electrode is the thermoelectrical conversion battery of metal wire | |
CN102983261B (en) | A kind of internal and external electrode is the thermoelectrical conversion battery of one end closed metal pipe | |
CN103436723B (en) | A kind of quickly preparation high-performance Mg2the method of Si base thermoelectricity material | |
CN104263986B (en) | A kind of method of supper-fast preparation high-performance SnTe base thermoelectricity material | |
CN105671344B (en) | One step prepares high-performance CoSb3The method of base thermoelectricity material | |
CN100499193C (en) | Rare earth doping Mg2Si0.6Sn0.4 based thermoelectric material | |
CN107794387B (en) | A kind of supper-fast preparation β-Zn4Sb3The method of base block thermoelectric material | |
CN102983266B (en) | A kind of internal and external electrode is the thermoelectric conversion element of metal wire | |
CN107176589A (en) | One kind prepares nanosizing Mg3Sb2The new method of thermoelectric material | |
CN102983260B (en) | Thermoelectric conversion battery with inner electrode of metal tube and outer electrode of meal wire | |
CN102969439B (en) | A kind of thermoelectric conversion element | |
CN102969440B (en) | A kind of internal and external electrode is the thermoelectric conversion element of metal tube | |
CN105140383B (en) | Compound PbSe base thermoelectricity materials for mixing Sr and Na and preparation method thereof | |
CN104157778A (en) | Thermoelectric conversion battery with internal and external electrodes which are metal lines | |
CN102969442B (en) | A kind of interior electrode is metal tube and the thermoelectric conversion element of dispatch from foreign news agency very metal wire | |
CN102983267B (en) | A kind of internal and external electrode is the thermoelectric conversion element of one end closed metal pipe | |
CN107507909A (en) | A kind of porous p-type Bi2Te3Base thermoelectricity material and preparation method thereof | |
CN102983265B (en) | A kind of internal and external electrode is the thermoelectrical conversion battery of metallic plate | |
CN102969441B (en) | A kind of internal and external electrode is the thermoelectric conversion element of metallic plate | |
CN102983263A (en) | Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes | |
CN103779492A (en) | Thermoelectric conversion device with metal tube serving as inner electrode and metal wire serving as outer electrode | |
CN102983264A (en) | Thermoelectric conversion battery | |
CN103746069A (en) | Thermoelectric conversion battery with metal tube as internal electrode and metal wire as external electrode | |
CN103779491A (en) | Thermoelectric conversion device with metal tubes serving as inner electrode and outer electrode | |
CN103746068A (en) | Thermoelectric converter with metal wires as internal electrode and external electrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C12 | Rejection of a patent application after its publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140507 |