CN103779491A - Thermoelectric conversion device with metal tubes serving as inner electrode and outer electrode - Google Patents
Thermoelectric conversion device with metal tubes serving as inner electrode and outer electrode Download PDFInfo
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- CN103779491A CN103779491A CN201410038683.XA CN201410038683A CN103779491A CN 103779491 A CN103779491 A CN 103779491A CN 201410038683 A CN201410038683 A CN 201410038683A CN 103779491 A CN103779491 A CN 103779491A
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- thermoelectric conversion
- thermo
- converting material
- electrode
- electric converting
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Abstract
The invention discloses a thermoelectric conversion device with metal tubes serving as an inner electrode and an outer electrode. The thermoelectric conversion device comprises the inner electrode, the outer electrode and a thermoelectric conversion material arranged between the inner electrode and the outer electrode, wherein the inner electrode is one of the metal tubes, the outer electrode is the other metal tube, 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.
Internal and external electrode of the present invention is the thermoelectric conversion element of metal tube, 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 tube 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
llzr
l.5pb
0.5, CeFe
11.5zrPb
0.5, CeFe
l0.8zr
l.7pb
0.3, CeFe
ll.5zr
l.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 tube, and external electrode 2 is metal tube, as shown in Figure 1, 2, 3.
The manufacture method of this thermoelectric conversion element is: thermoae 2 as adding with a metal tube, add thermoae 2 outer-heating electric transition materials 3, and then form emitter 1 at another root metal tube of the surperficial overcoat of thermo-electric converting material 3, just form single entry tubular type thermal cell.It is mode of heating from inside to outside, and available hot water heats.Seal closure 4 is established at thermo-electric converting material 3 two ends, and charge pipe 5 is set on seal closure 4, and charge pipe 5 one end are communicated with thermo-electric converting material 3, and the other end connects feeder 7.Add thermoae 2 and emitter 1 on pick out joint with connecting line 6.Outside a single entry tubular type thermal cell, can overlap several single entry tubular type thermal cells, form compound tubular type thermal cell.On the interior emitter that adds thermoae and outermost of compound tubular type thermal cell, pick out joint with connecting line.Compound tubular type thermal cell can fully be changed heat, is relatively suitable for the thermoelectricity conversion of cogeneration power plant.
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
llzr
l.5pb
0.5, CeFe
ll.5zrPb
0.5, CeFe
l0.8zr
l.7pb
0.3, CeFe
ll.5zr
l.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
l1zr
l.55pb
0.45, CeFe
ll.5zr
l.15pb
0.45, CeFe
10.75zr
1.8pb
0.35, CeFe
10.8zr
l.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, mix with selected stoichiometric proportion each element as powder, 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 tube, 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 tube very,
Thermo-electric converting material is Ce (Fe
xzr
ypb
:)
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
llzr
l.spb
0.5, CeFe
ll.szrPb
0.5, CeFe
10.8zr
1.7pb
0.3, CeFe
ll.5zr
l.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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410038683.XA CN103779491A (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion device with metal tubes serving as inner electrode and outer electrode |
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|---|---|---|---|
| CN201410038683.XA CN103779491A (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion device with metal tubes serving as inner electrode and outer electrode |
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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 |
| CN1969399A (en) * | 2004-06-22 | 2007-05-23 | 阿鲁策株式会社 | Thermoelectric conversion element |
| CN102969440A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Thermoelectric conversion device with metal tubes as inner and outer electrodes |
-
2014
- 2014-01-26 CN CN201410038683.XA patent/CN103779491A/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 |
| CN1969399A (en) * | 2004-06-22 | 2007-05-23 | 阿鲁策株式会社 | Thermoelectric conversion element |
| CN102969440A (en) * | 2012-11-20 | 2013-03-13 | 溧阳市生产力促进中心 | Thermoelectric conversion device with metal tubes as inner and outer electrodes |
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Application publication date: 20140507 |