CN102969439B - A kind of thermoelectric conversion element - Google Patents
A kind of thermoelectric conversion element Download PDFInfo
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- CN102969439B CN102969439B CN201210471840.7A CN201210471840A CN102969439B CN 102969439 B CN102969439 B CN 102969439B CN 201210471840 A CN201210471840 A CN 201210471840A CN 102969439 B CN102969439 B CN 102969439B
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- thermo
- converting material
- electric converting
- conversion element
- thermoelectric conversion
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- 239000007769 metal material Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 230000000171 quenching effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 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
- 239000000376 reactant Substances 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052729 chemical element Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 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
- 230000005619 thermoelectricity Effects 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
- 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
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 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
- 238000012545 processing Methods 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
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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Abstract
The invention discloses a kind of thermoelectric conversion element, the thermo-electric converting material comprising interior electrode, external electrode and arrange therebetween, wherein, electrode is the metal wire be wrapped on insulated tube, and dispatch from foreign news agency is metal wire very, and wherein, thermo-electric converting material is La (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.It is low that this device solves thermoelectric generation technology transfer ratio in prior art, the problem of practical application effect difference, is the thermoelectric conversion element that a kind of conversion efficiency of thermoelectric is high.<!--1-->
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 of electric current can be induced thermoelectric effect material when heating, being also thermo-electric converting material.Do the two poles of the earth with metal material, two metal materials couple together by centre thermo-electric converting material, and be made thermoelectric conversion element.
Thermoelectric conversion element is one-way heat conduction structure, is first a metal electrode heating, and then gives another metal electrode by thermo-electric converting material heat conduction by the metal heated.Due to one-way heat conduction structure, small hot particle is made to transform the electric current creating continuous circulation to electronics.Due to unilateal conduction structure, forward is served to the thermocurrent in thermal cell and promotes, the effect oppositely stoped.
Thermoelectric conversion element can utilize solar energy, the thermal power transfer such as waste heat, underground heat of cogeneration power plant is electric energy, 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 poles and thermo-electric converting material, thus on the contact-making surface of two metal poles and thermo-electric converting material setting area expansion instrument, be mainly arranged on interior electrode, thus expansion contact area, make 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 find the metal material at more suitably thermo-electric converting material and the two poles of the earth, improving the transfer ratio of thermoelectric conversion element, is the problem that this area needs solution badly.
Summary of the invention
The present invention is low in order to solve thermoelectric generation technology transfer ratio in prior art, and the problem of practical application effect difference, provides the thermoelectric conversion element that a kind of conversion efficiency of thermoelectric is high.
Thermoelectric conversion element of the present invention, the thermo-electric converting material comprising interior electrode, external electrode and arrange therebetween, wherein, electrode is the metal wire be wrapped on insulated tube, and dispatch from foreign news agency is metal wire very, wherein,
Thermo-electric converting material is La (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 LaFe
11zr
1.5pb
0.5, LaFe
11.5zrPb
0.5, LaFe
10.8zr
1.7pb
0.3, LaFe
11.5zr
1.2pb
0.3.
Preferably, interior electrode and dispatch from foreign news agency very iron or copper.
Through experiment test, thermoelectric conversion element of the present invention and thermo-electric converting material well known in the prior art, the device that such as pyrite is made is compared, and conversion efficiency of thermoelectric significantly improves, between 20 ~ 50 DEG C, improve 10 ~ 15%, between 50 ~ 100 DEG C, improve 20 ~ 30%.
Accompanying drawing explanation
Fig. 1 is the structural representation of thermoelectric conversion device of the present invention.
Fig. 2 is Fig. 1 sectional view transversely.
Fig. 3 is Fig. 1 sectional view longitudinally.
Embodiment
Be described further the specific embodiment of the present invention below in conjunction with accompanying drawing, but should be appreciated that, embodiment, only for illustration of technical scheme of the present invention, is not used in and limits its protection range.
Thermoelectric conversion element of the present invention, the thermo-electric converting material 3 comprising interior electrode 1, external electrode 2 and arrange therebetween, wherein, electrode 1 is for being wrapped in the metal wire on insulated tube, and external electrode 2 is metal wire, as shown in Figure 1, 2, 3.
The manufacture method of this thermoelectric conversion element is: one is wrapped in metal wire on insulated tube as emitter 1, and metal wire outer-heating electric transition material 3, thermo-electric converting material is wound around metal wire outward again as adding thermoae 2, 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, composition 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, thus is heated by thermo-electric converting material.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, also can be aluminium or silver.Such as interior electrode 1 selects metallic iron, and external electrode 2 selects metallic copper.
Thermo-electric converting material 3 is La (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 LaFe
11zr
1.5pb
0.5, LaFe
11.5zrPb
0.5, LaFe
10.8zr
1.7pb
0.3, LaFe
11.5zr
1.2pb
0.3.
The manufacturing process of described thermo-electric converting material 3 comprises the steps:
A) La, Fe, Zr and Pb tetra-kinds of chemical elements are made to correspond to the stoichiometric reaction of its metal_based material in solid phase and/or liquid phase, formation La (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 from step c) sintering and/or heat treated solid with the cooldown rate quenching of at least 100K/s.
In the step (a) of this method,
With the stoichiometric proportion corresponding to thermo-electric converting material, the element be present in the latter's thermo-electric converting material and/or alloy are transformed in solid phase or liquid phase.
Preferably by by element and/or alloy in closed container or in an extruder combined heated, or undertaken by solid phase reaction in ball mill step a) in reaction.Particularly preferably carry out solid phase reaction, it especially carries out in ball mill.This reaction principle is known; See document cited above.Usually, the powder of the powder of each element be present 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 can by mixture grinding to obtain microcrystalline powder mixture.Preferably heated in ball mill by this mixture of powders, this causes pulverizing further and well mixing, and causes the solid phase reaction in mixture of powders.Or, each element is mixed as powder with selected stoichiometric proportion, then melting.
In closed container, combined heated makes fixing volatile element and controls stoichiometric proportion.Specifically, when using phosphorus, in open system, this will easily evaporate.
In the step (b) in this method,
By step a) in the solid that obtains suppressed before sintering and/or heat treatment.This makes density of material improve, and high density thermo-electric converting material is present in the latter's application.This is especially favourable, because the volume that there is magnetic field can reduce, this can be cost-saving considerably.Be compressed to that itself is known, available or carry out without compression aid.Any model being suitable for suppressing can be used.By compacting, the formed body of required three-dimensional structure can be obtained.Can step c be carried out after compacting) sintering and/or heat treatment, carry out steps d thereafter) quenching.
In the step (c) of this method,
The sintering of solid and/or heat treatment are in step c) in carry out, preferably first sinter at the temperature of 800-1400 DEG C, then heat-treat at the temperature of 500-750 DEG C.These values are particularly useful for formed body, and lower sintering and heat treatment temperature can be used for powder.Such as, then sintering can carry out at the temperature of 500-800 DEG C.For formed body/solid, sintering, more preferably at 1000-1300 DEG C, especially carries out at the temperature of 1100-1300 DEG C.Then heat treatment can such as be carried out at 600-700 DEG C.
Sintering preferably carries out 1-50 hour, more preferably 2-20 hour, especially 5-15 hour.Heat treatment preferably carries out 10-100 hour, more preferably 10-60 hour, especially 30-50 hour.Precise time can according to material adjustment to adapt to actual requirement.
Sintering/heat treatment causes granule boundary partial melting, makes material closely knit further.Therefore, step b) in melting 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 not being slowly cooled to ambient temperature after sintering and/or heat treatment, but during with high cooldown rate quenching, thermo-lag significantly can reduce and can realize thermoelectric effect.This cooldown rate is at least 100K/s.Cooldown rate is preferably 200-1300K/s, and preferred cooldown rate is 300-1000K/s.
Quenching realizes by any suitable cooling means, such as, pass through with water or liquid, aqueous if cooling water or ice/water mixture are by solid quenching.Such as, solid can be made to fall into ice-cooled water.Also cold gas can be used 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 current strength of different volumes, different area correspondence produced at different temperatures.Thermoelectric conversion element of the present invention can be electric energy various thermal energy.Its sensitiveness is good, and the variations in temperature in air can make thermal cell generation current change, and is a kind of collection converter of common heat, especially can obtains good thermoelectricity conversion effect when high-temperature heating, and can prolonged and repeatedly use.The experiment proved that, thermo-electric converting material of the present invention is adopted to make thermoelectric conversion element, compared with the thermoelectric conversion element formed with thermo-electric converting material well known in the prior art, conversion efficiency of thermoelectric significantly improves, between 10 ~ 50 DEG C, improve 5 ~ 10%, between 50 ~ 100 DEG C, improve 20 ~ 30%.The temperature of thermal cell inside can not unconfinedly increase, and the heating-up temperature of thermoelectric conversion element of the present invention is preferably limited within 100 degrees Celsius.Because the structure of thermoelectric device 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 of a kind of novelty being suitable for 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 DEG C.
Claims (3)
1. a thermoelectric conversion element, the thermo-electric converting material comprising interior electrode, external electrode and arrange therebetween, is characterized in that,
Interior electrode is the metal wire be wrapped on insulated tube, and dispatch from foreign news agency is metal wire very,
Thermo-electric converting material is La (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;
The manufacture method of described thermo-electric converting material comprises the steps:
A) La, Fe, Zr and Pb tetra-kinds of chemical elements are made to correspond to the stoichiometric reaction of its metal_based material in solid phase and/or liquid phase, formation La (Fe
xzr
ypb
z)
13reactant;
B) above-mentioned reactant is pressed into solid;
C) by above-mentioned solid sintering and/or heat treatment; Wherein, sinter at the temperature of 800-1400 DEG C, then heat-treat at the temperature of 500-750 DEG C; Sintering carries out 1-50 hour, and 10-100 hour is carried out in heat treatment;
D) will from step c) sintering and/or heat treated solid with the cooldown rate quenching of at least 100K/s.
2. device as claimed in claim 1, it is characterized in that, described thermo-electric converting material is LaFe
11zr
1.5pb
0.5, LaFe
11.5zrPb
0.5, LaFe
10.8zr
1.7pb
0.3or LaFe
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 very iron or copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210471840.7A CN102969439B (en) | 2012-11-20 | 2012-11-20 | A kind of thermoelectric conversion element |
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|---|---|---|---|
| CN201210471840.7A CN102969439B (en) | 2012-11-20 | 2012-11-20 | A kind of thermoelectric conversion element |
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| CN102969439A CN102969439A (en) | 2013-03-13 |
| CN102969439B true CN102969439B (en) | 2015-12-09 |
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| CN103762301A (en) * | 2014-01-26 | 2014-04-30 | 海安县申菱电器制造有限公司 | Thermoelectric conversion device with metal wire wound on insulation tube as inner electrode |
| CN104157779A (en) * | 2014-01-26 | 2014-11-19 | 海安县申菱电器制造有限公司 | High-efficient thermoelectric conversion device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1969354A (en) * | 2004-04-21 | 2007-05-23 | 昭和电工株式会社 | Process for producing a heusler alloy, a half heusler alloy, a filled skutterudite based alloy and thermoelectric conversion system using them |
| CN101055914A (en) * | 2007-04-25 | 2007-10-17 | 乔君旺 | Thermoelectrical conversion battery |
| EP1930960A1 (en) * | 2006-12-04 | 2008-06-11 | Aarhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
-
2012
- 2012-11-20 CN CN201210471840.7A patent/CN102969439B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1969354A (en) * | 2004-04-21 | 2007-05-23 | 昭和电工株式会社 | Process for producing a heusler alloy, a half heusler alloy, a filled skutterudite based alloy and thermoelectric conversion system using them |
| EP1930960A1 (en) * | 2006-12-04 | 2008-06-11 | Aarhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
| CN101055914A (en) * | 2007-04-25 | 2007-10-17 | 乔君旺 | Thermoelectrical conversion battery |
Non-Patent Citations (2)
| Title |
|---|
| 《Complex thermoelectric materials》;G.Jeffery Snyder;《nature materials》;20080229;第7卷;全文 * |
| 《High-performance nanostructured thermoelectric materials》;Jing-Feng Li 等;《NPG ASIA MATERIALS》;20101031;第2卷(第4期);全文 * |
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