CN102983266B - A kind of internal and external electrode is the thermoelectric conversion element of metal wire - Google Patents
A kind of internal and external electrode is the thermoelectric conversion element of metal wire Download PDFInfo
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- CN102983266B CN102983266B CN201210472636.7A CN201210472636A CN102983266B CN 102983266 B CN102983266 B CN 102983266B CN 201210472636 A CN201210472636 A CN 201210472636A CN 102983266 B CN102983266 B CN 102983266B
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Abstract
The invention discloses the thermoelectric conversion element that a kind of internal and external electrode is metal wire, the thermo-electric converting material comprising interior electrode, external electrode and arrange therebetween, wherein, electrode is metal wire, 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.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 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 wires as interior electrode 1, interior electrode 1 outer-heating electric transition material 3, then be wrapped in thermo-electric converting material 3 surface with another wires and form external electrode 2, external electrode 2 and interior electrode 1 pick out joint with connecting line 6, just constitute single entry line formula thermal cell, it is the structure heated from outside to inside, is applicable to the conversion of various common thermoelectricity.
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. internal and external electrode is a manufacture method for the thermoelectric conversion element battery of metal wire, and in this thermoelectric conversion element battery, electrode, external electrode and the thermo-electric converting material that arranges therebetween, is characterized in that,
Interior electrode is metal wire, 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. manufacture method 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
0.3, LaFe
11.5zr
1.2pb
0.3.
3. manufacture method as claimed in claim 1, is characterized in that, described interior electrode and dispatch from foreign news agency very iron or copper.
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|---|---|---|---|
| CN201210472636.7A CN102983266B (en) | 2012-11-20 | 2012-11-20 | A kind of internal and external electrode is the thermoelectric conversion element of metal wire |
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| CN102983266B true CN102983266B (en) | 2016-02-17 |
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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 |
| CN103746068A (en) * | 2014-01-26 | 2014-04-23 | 海安县申菱电器制造有限公司 | Thermoelectric converter with metal wires as internal electrode and external electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101055914A (en) * | 2007-04-25 | 2007-10-17 | 乔君旺 | Thermoelectrical conversion battery |
| CN201038193Y (en) * | 2007-04-25 | 2008-03-19 | 乔君旺 | Thermoelectric conversion battery |
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| WO2008067815A2 (en) * | 2006-12-04 | 2008-06-12 | Aarhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
| JP2008305987A (en) * | 2007-06-07 | 2008-12-18 | Sumitomo Chemical Co Ltd | Thermoelectric conversion module |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101055914A (en) * | 2007-04-25 | 2007-10-17 | 乔君旺 | Thermoelectrical conversion battery |
| CN201038193Y (en) * | 2007-04-25 | 2008-03-19 | 乔君旺 | Thermoelectric conversion battery |
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