CN102983263A - Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes - Google Patents
Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes Download PDFInfo
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- CN102983263A CN102983263A CN2012104724484A CN201210472448A CN102983263A CN 102983263 A CN102983263 A CN 102983263A CN 2012104724484 A CN2012104724484 A CN 2012104724484A CN 201210472448 A CN201210472448 A CN 201210472448A CN 102983263 A CN102983263 A CN 102983263A
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- thermoelectric conversion
- converting material
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Abstract
The invention discloses a thermoelectric conversion battery with an inner electrode and an outer electrode of metal tubes, which 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 a metal tube, the outer electrode is another metal tube, and the thermoelectric conversion material 3 is La(FexHfyPtz)13, in which x is in the range of 0.85 to 0.90, y is in the range of 0.03 to 1-x, and z is in the range of 0.005 to 0.45. The battery solves the problems in the prior art that the thermoelectric conversion technology is low in conversion rate and bad in practical application effect, and is a thermoelectric conversion battery with high thermoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of thermoelectrical conversion battery.
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 also is thermo-electric converting material the thermoelectric effect material.Do the two poles of the earth with metal material, the centre couples together two metal materials with thermo-electric converting material, and thermoelectrical conversion battery is made.
Thermoelectrical conversion battery is the 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 of heating.Because the one-way heat conduction structure makes small hot particle transform the electric current that has produced continuous circulation to electronics.Because the unilateal conduction structure has played the forward promotion to the thermocurrent in the thermal cell, the effect that oppositely stops.
Thermoelectrical conversion battery can utilize the thermal power transfer such as the waste heat, underground heat of solar energy, cogeneration power plant to be 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 the two metal utmost points and thermo-electric converting material, so at the contact-making surface of two metal utmost points and thermo-electric converting material the enlarged areas device is set, mainly is arranged on the interior electrode, thereby the expansion contact area makes thermoelectric conversion reach optimum efficiency.In case of necessity, all right in parallel or series connection use of thermoelectrical conversion battery as some groups of thermal cells are overlaped, makes heat obtain more fully conversion effect.
But the transfer ratio of prior art kind thermoelectrical conversion battery is lower, is difficult to be applied in the industrial production.Therefore seeking the more suitably metal material of thermo-electric converting material and the two poles of the earth, improve the transfer ratio of thermoelectrical conversion battery, is the problem that this area is needed solution badly.
Summary of the invention
The present invention is low in order to solve in the prior art thermoelectric generation technology transfer ratio, and the problem that practical application effect is poor provides a kind of conversion efficiency of thermoelectric high thermoelectrical conversion battery.
Internal and external electrode of the present invention is the thermoelectrical conversion battery of metal tube, comprises interior electrode, external electrode and the thermo-electric converting material that arranges 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 3 is La (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 LaFe
11Hf
1.55Pt
0.45, LaFe
11.5Hf
1.15Pt
0.45, LaFe
10.75Hf
1.8Pt
0.35, LaFe
10.8Hf
1.85Pt
0.35
Preferably, very iron or copper of interior electrode and dispatch from foreign news agency.
Through experiment test, thermoelectrical conversion battery of the present invention and thermo-electric converting material well known in the prior art, for example the battery made of pyrite is compared, and conversion efficiency of thermoelectric obviously improves, between 20～50 ℃, improve 10～15%, between 50～100 ℃, improve 20～30%.
Description of drawings
Fig. 1 is the structural representation of thermoelectric conversion battery 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 is used for technical scheme of the present invention is described, is not used in and limits its protection range.
Thermoelectrical conversion battery of the present invention comprises interior electrode 1, external electrode 2 and the thermo-electric converting material 3 that arranges 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 thermoelectrical conversion battery is: thermoae 2 as adding with metal tube, add thermoae 2 outer-heating electric transition materials 3, and then form emitter 1 at another root metal tube of thermo-electric converting material 3 surperficial overcoats, 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 the seal closure 4, and charge pipe 5 one ends are communicated with thermo-electric converting material 3, and the other end connects feeder 7.Add thermoae 2 and emitter 1 usefulness connecting line 6 pick out joint.Can overlap several single entry tubular type thermal cells outside the single entry tubular type thermal cell, form compound tubular type thermal cell.Pick out joint with connecting line on the interior emitter that adds thermoae and outermost of compound tubular type thermal cell.Compound tubular type thermal cell can fully be changed heat, relatively is 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 also referred to as and adds thermoaely, after its variations in temperature, to the thermo-electric converting material conveying electronic, thereby thermo-electric converting material is heated.Because unilateal conduction structure, the thermocurrent in the thermoelectric cell play 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.For example interior electrode 1 selects metallic iron, and external electrode 2 selects metallic copper.
Thermo-electric converting material 3 is La (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 LaFe
11Hf
1.55Pt
0.45, LaFe
11.5Hf
1.15Pt
0.45, LaFe
10.75Hf
1.8Pt
0.35, LaFe
10.8Hf
1.85Pt
0.35
The manufacturing process of described thermo-electric converting material 3 comprises the steps:
A) make La, Fe, Hf and four kinds of chemical elements of Pt in solid phase and/or liquid phase with the stoichiometric reaction corresponding to its metal_based material, form La (Fe
xHf
yPt
z)
13Reactant;
B) above-mentioned reactant is pressed into solid;
C) with 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,
Element and/or the alloy that will be present in latter's thermo-electric converting material with the stoichiometric proportion corresponding to thermo-electric converting material in solid phase or liquid phase transform.
Carry out the reaction of step in a) preferably by the combined heated in closed container or in extruder with 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.Known on this reaction principle; Referring to document cited above.The powder that usually, will be present in the alloy of the powder of each element in latter's thermo-electric converting material or two or more each elements mixes with suitable weight ratio with powder-form.If necessary, also mixture can be ground to obtain the microcrystalline powder mixture.Preferably this mixture of powders is heated in ball mill, this causes further pulverizing and good the mixing, and causes the solid phase reaction in the mixture of powders.Perhaps, each element is mixed with selected stoichiometric proportion as powder, then melting.
Combined heated in closed container is so that fixing volatile element and control stoichiometric proportion.Particularly, this will evaporate easily in open system in the situation of using phosphorus.
In the step (b) in this method,
The solid that step obtains in a) was suppressed before sintering and/or heat treatment.This improves density of material, so that the high density thermo-electric converting material is present in latter's application.This is especially favourable, because exist the volume in magnetic field to reduce, this can save cost considerably.Be compressed to that itself is known, available or carry out without compression aid.Can use any model that is suitable for suppressing.By compacting, can obtain the formed body of required three-dimensional structure.The 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 at first under 800-1400 ℃ temperature, carry out sintering, then under 500-750 ℃ temperature, heat-treat.These values are particularly useful for formed body, and lower sintering and heat treatment temperature can be used for powder.For example, then sintering can carry out under 500-800 ℃ temperature.For formed body/solid, sintering especially carries out under 1100-1300 ℃ the temperature more preferably at 1000-1300 ℃.Then heat treatment can for example be carried out under 600-700 ℃.
Sintering preferably carried out 1-50 hour, and more preferably 2-20 hour, especially 5-15 hour.Heat treatment was preferably carried out 10-100 hour, and more preferably 10-60 hour, especially 30-50 hour.Precise time can adapt to actual requirement according to material adjustment.
Sintering/heat treatment causes the granule boundary partial melting, so that material is further closely knit.Therefore, the melting step b) and fast cooling make step c) the duration reduce considerably.This is also so that the 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 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 such as cooling water or ice/aqueous mixtures with the solid quenching.For example, can make solid fall into ice-cooled water.Also available excessively cold gas such as liquid nitrogen are with the 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 value of the correspondence that different volumes, different area produce under different temperatures.Thermoelectrical conversion battery of the present invention can be converted into electric energy to various heat energy.Its sensitiveness is good, and airborne variations in temperature can make the thermal cell generation current change, and is a kind of collection converter of common heat, especially can obtain good thermoelectric conversion effect when high-temperature heating, and can prolonged and repeatedly use.The experiment proved that, adopt thermo-electric converting material of the present invention to make thermoelectrical conversion battery, compare with the thermoelectrical conversion battery that thermo-electric converting material well known in the prior art forms, conversion efficiency of thermoelectric obviously improves, between 10～50 ℃, improve 5～10%, between 50～100 ℃, improve 20～30%.The temperature of thermal cell inside can not unconfinedly increase, and the heating-up temperature of thermoelectrical conversion battery of the present invention preferably is limited in 100 degrees centigrade.Because the structure of thermoelectric cell is different, material is different, and is different to the requirement of temperature.
This shows that material of the present invention is the thermo-electric converting material that is suitable for a kind of novelty of thermoelectrical conversion battery, 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 in 50～100 ℃ of scopes.
Claims (3)
1. an internal and external electrode is the thermoelectrical conversion battery of metal tube, comprises interior electrode, external electrode and the thermo-electric converting material that arranges 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 3 is La (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.
2. battery as claimed in claim 1 is characterized in that, described thermo-electric converting material is preferably LaFe
11Hf
1.55Pt
0.45, LaFe
11.5Hf
1.15Pt
0.45, LaFe
10.75Hf
1.8Pt
0.35, LaFe
10.8Hf
1.85Pt
0.35
3. battery as claimed in claim 1 is characterized in that, described interior electrode and dispatch from foreign news agency be iron or copper very.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104724484A CN102983263A (en) | 2012-11-20 | 2012-11-20 | Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104724484A CN102983263A (en) | 2012-11-20 | 2012-11-20 | Thermoelectric conversion battery with inner electrode and outer electrode of metal tubes |
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|---|---|
| CN102983263A true CN102983263A (en) | 2013-03-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779494A (en) * | 2014-01-26 | 2014-05-07 | 南通明诺机械有限公司 | Thermoelectric conversion battery with metal tubes serving as inner electrode and outer electrode |
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|---|---|---|---|---|
| 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 |
| US20100139730A1 (en) * | 2006-12-04 | 2010-06-10 | Aarhus Universitet | Use of thermoelectric materials for low temperature thermoelectric purposes |
| US20100170550A1 (en) * | 2007-06-07 | 2010-07-08 | Sumitomo Chemical Company, Limited | Thermoelectric conversion module and thermoelectric power generation system |
-
2012
- 2012-11-20 CN CN2012104724484A patent/CN102983263A/en active Pending
Patent Citations (4)
| 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 |
| 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 |
| US20100170550A1 (en) * | 2007-06-07 | 2010-07-08 | Sumitomo Chemical Company, Limited | Thermoelectric conversion module and thermoelectric power generation system |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103779494A (en) * | 2014-01-26 | 2014-05-07 | 南通明诺机械有限公司 | Thermoelectric conversion battery with metal tubes serving as inner electrode and outer electrode |
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Application publication date: 20130320 |