CN104157779A - High-efficient thermoelectric conversion device - Google Patents
High-efficient thermoelectric conversion device Download PDFInfo
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- CN104157779A CN104157779A CN201410412929.5A CN201410412929A CN104157779A CN 104157779 A CN104157779 A CN 104157779A CN 201410412929 A CN201410412929 A CN 201410412929A CN 104157779 A CN104157779 A CN 104157779A
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- Prior art keywords
- thermoelectric conversion
- thermo
- converting material
- electric converting
- cefe
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Abstract
The invention discloses a thermoelectric conversion device which comprises an inner electrode, an outer electrode, and thermoelectric conversion material arranged between the two electrodes. The thermoelectric conversion material is Ce(FexZryPbz) 13, wherein x is in the range of 0.70 to 0.95, y is in the range of 0.05 to 1-x, and z is in the range of 0.005 to 0.5. According to the device, the problems of low conversion efficiency and poor practical application effect of the thermoelectric conversion technology in the prior art are solved, and the thermoelectric conversion device has high thermoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of thermoelectric conversion element.
Background technology
Thermoelectric effect is when 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 when heating, thermoelectric effect material, is also thermo-electric converting material.With metal material, do the two poles of the earth, 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 to electronics, transform the electric current that has produced continuous circulation.Due to unilateal conduction structure, the thermocurrent in thermal cell has been played to forward promotion, the effect oppositely stoping.
It is electric energy that thermoelectric conversion element can utilize the thermal power transfer such as the 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 two metal electrodes and thermo-electric converting material, so area expansion instrument is set on the contact-making surface of two metal electrodes 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.
Thermoelectric conversion element of the present invention, comprises interior electrode, external electrode and the thermo-electric converting material arranging between the two, and wherein interior electrode is the metal wire being wrapped on insulated 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
11.5zr
1.5pb
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 is compared preceding another invention of the inventor and be take that thermoelectric conversion element that La is main composition thermo-electric converting material is taller goes out 2～3%.
Accompanying drawing explanation
Fig. 1 is the structural representation of thermoelectric conversion device of the present invention.
Fig. 2 is the cross-sectional cutaway view of Fig. 1.
Fig. 3 is the vertical profile cutaway view of Fig. 1.
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.In one embodiment, wherein interior electrode 1 is for to be wrapped in the metal wire on insulated tube, and external electrode 2 is metal wire, as Fig. 1.Interior electrode and external electrode can also be other forms.
The manufacture method of thermoelectric conversion element shown in Fig. 1 is: one is wrapped in metal wire on insulated tube as emitter 1, metal wire outer-heating electric transition material 3, it is thermoae 2 as adding that thermo-electric converting material is wound around metal wire outward again, forms a minor comonomer thermoelectric conversion element.The course of processing of thermo-electric converting material is with embodiment 1.With connecting line, several minor comonomer thermoelectric conversion elements are coupled together, form high voltage thermoelectric conversion element.
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
11.5zr
1.5pb
0.5, CeFe
10.8zr
1.7pb
0.3, CeFe
11.5zr
1.2pb
0.3.
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.
Thermo-electric converting material 3 can also be Ce (Fe
xhf
ypt
z) 13
Wherein: the scope of x is 0.80～0.90; The scope of y is 0.03～1-x; The scope of z is 0.005～0.45.
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 step c) sintering 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.
Preferably by the combined heated in closed container or in extruder by element and/or alloy, or by solid phase reaction in ball mill, carry out the reaction of step in a).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 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, using each element as powder, with selected stoichiometric proportion, mix, then melting.
In closed container, combined heated makes fixedly volatile element and controls stoichiometric proportion.Particularly, in the situation that using phosphorus, in open system, this will easily evaporate.
In the step in this method (b),
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 c) sintering and/or heat treatment, carry out thereafter steps d) quenching.
In the step (c) of this method,
The sintering of solid and/or heat treatment are at step c) in carry out, 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, step b) and the fast cooling step c that makes) 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 available excessively cold gas is if liquid nitrogen is by solid quenching.Other method of quenching is well known by persons skilled in the art.
By thermal cell is heated to different temperatures, measure, 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 when 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, compare with the thermoelectric conversion element that thermo-electric converting material well known in the prior art forms, 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.Because the structure of thermoelectric cell is different, material is different, different to the requirement 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. a thermoelectric conversion element, comprises interior electrode, external electrode and the thermo-electric converting material arranging between the two, it is characterized in that,
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
11.5zr
1.5pb
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, described interior electrode and dispatch from foreign news agency be iron or copper very.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410412929.5A CN104157779A (en) | 2014-01-26 | 2014-08-20 | High-efficient thermoelectric conversion device |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410038026 | 2014-01-26 | ||
| CN201410038026.5 | 2014-01-26 | ||
| CN201410412929.5A CN104157779A (en) | 2014-01-26 | 2014-08-20 | High-efficient thermoelectric conversion device |
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|---|---|
| CN104157779A true CN104157779A (en) | 2014-11-19 |
Family
ID=51883233
Family Applications (1)
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|---|---|---|---|
| CN201410412929.5A Pending CN104157779A (en) | 2014-01-26 | 2014-08-20 | High-efficient thermoelectric conversion device |
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|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100139730A1 (en) * | 2006-12-04 | 2010-06-10 | Aarhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
| CN102969439A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Thermoelectric conversion device |
| CN102983261A (en) * | 2012-11-20 | 2013-03-20 | 溧阳市生产力促进中心 | Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes sealed at one end |
-
2014
- 2014-08-20 CN CN201410412929.5A patent/CN104157779A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100139730A1 (en) * | 2006-12-04 | 2010-06-10 | Aarhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
| CN102969439A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Thermoelectric conversion device |
| CN102983261A (en) * | 2012-11-20 | 2013-03-20 | 溧阳市生产力促进中心 | Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes sealed at one end |
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Application publication date: 20141119 |
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