CN103762300B - Thermoelectric conversion battery with metal plates as inner electrode and outer electrode - Google Patents
Thermoelectric conversion battery with metal plates as inner electrode and outer electrode Download PDFInfo
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- CN103762300B CN103762300B CN201410037093.5A CN201410037093A CN103762300B CN 103762300 B CN103762300 B CN 103762300B CN 201410037093 A CN201410037093 A CN 201410037093A CN 103762300 B CN103762300 B CN 103762300B
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Abstract
The invention discloses a thermoelectric conversion battery with metal plates as an inner electrode and an outer electrode. The thermoelectric conversion battery comprises the inner electrode, the outer electrode and thermoelectric conversion materials (3) arranged between the inner electrode and the outer electrode, the inner electrode is the metal plate, the outer electrode is the metal plate, and the thermoelectric conversion materials (3) are Ce(FexHfyPtz)13, wherein the x ranges from 0.85 to 0.90, the y ranges from 0.03 to 1-x, and the z ranges from 0.005 to 0.45. According to the thermoelectric conversion battery, the problems that in the prior art, the conversion efficiency of the thermoelectric conversion technology is low, and the actual application effect is poor are solved, and the thermoelectric conversion battery is high in thermoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of thermoelectrical conversion battery.
Background technology
Pyroelectric effect is when heating to material, can induce electric current, and current intensity increases with the increase of heat
Plus phenomenon.The material of electric current can be induced pyroelectric effect material in heating, also be thermo-electric converting material.Use metal material
Make the two poles of the earth, two metal materials are coupled together by centre thermo-electric converting material, and be made thermoelectrical conversion battery.
Thermoelectrical conversion battery is one-way heat conduction structure, is first a metal electrode to be heated, then again by the metal heating
Another metal electrode is conducted to heat by thermo-electric converting material.Due to one-way heat conduction structure, make small hot particle to
Electronics conversion creates the electric current of continuous circulation.Due to unilateal conduction structure, the thermocurrent in thermal cell is served with positive rush
Enter, the effect reversely stoping.
Thermoelectrical conversion battery can be converted to electric energy using heat energy such as solar energy, the waste heat of steam power plant, underground heat, its conversion efficiency
Depend primarily on thermo-electric converting material and the performance of the two poles of the earth metal material.In addition, conversion efficiency also with two metal poles and thermoelectricity
The contact area of transition material is relevant, so setting area expands dress on the contact surface with thermo-electric converting material for two metal poles
Putting, be mainly disposed on interior electrode, thus expanding contact area, making thermo-electric conversion reach optimum efficiency.If necessary, thermo-electric conversion
Battery can also be used in parallel or in series, and such as some groups of thermal cells are overlaped, so that heat is more fully changed
Effect.
But, in prior art, the conversion ratio of thermoelectrical conversion battery is relatively low, is not easily applied in practice in commercial production.Therefore
Find the metal material at more suitably thermo-electric converting material and the two poles of the earth, improve the conversion ratio of thermoelectrical conversion battery, be this area urgently
The problem that need to solve.
Content of the invention
The present invention is low in order to solve thermoelectric generation technology conversion ratio in prior art, the problem of practical application effect difference, carries
Supply a kind of high thermoelectrical conversion battery of conversion efficiency of thermoelectric.
The internal and external electrode of the present invention is the thermoelectrical conversion battery of metallic plate, including in electrode, external electrode and the two it
Between setting thermo-electric converting material, wherein interior electrode be metallic plate, dispatch from foreign news agency extremely metallic plate, wherein,
Thermo-electric converting material 3 is ce (fexhfyptz)13
Wherein: the scope of x is 0.85 ~ 0.90；The scope of y is 0.03 ~ l-x；The scope of z is 0.005 ~ 0.45.
Thermo-electric converting material is preferably cefe11hf1.55pt0.45, cefe11.5hf1.15pt0.45, cefe10.75hf1.8pt0.35,
cefe10.8hf1.85pt0.35.
Preferably, inner and outer electrodes are ferrum or copper.
Through experiment test, the thermoelectrical conversion battery of the present invention and thermo-electric converting material well known in the prior art, for example
The battery that pyrite is made is compared, and conversion efficiency of thermoelectric significantly improves, and improves 12 ~ 18%, at 50 ~ 100 DEG C between 20 ~ 50 DEG C
Between improve 22 ~ 32%.The pleasantly surprised discovery of the present inventor, using ce (fexhfyptz)13The conversion of the thermoelectric conversion element made
Efficiency compare the present inventor another front invention with la for the thermoelectric conversion element of main composition thermo-electric converting material also will
Exceed 2 ~ 3%.
Brief description
Fig. 1 is the structural representation of the thermoelectric conversion battery of the present invention.
Fig. 2 is Fig. 1 sectional view transversely.
Fig. 3 is Fig. 1 along longitudinal sectional view.
Specific embodiment
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described further, it is to be understood that embodiment is only used
In explanation technical scheme, it is not used in and limits its protection domain.
The thermoelectrical conversion battery of the present invention, including in electrode 1, external electrode 2 and the thermo-electric conversion material arranging therebetween
Material 3, wherein interior electric 1 is metallic plate, and external electrode 2 is metallic plate, as shown in Figure 1, 2, 3.
The manufacture method of this thermoelectrical conversion battery is: sets thermo-electric converting material 3 between two metallic plates, a metallic plate is
Heating pole 2, another metallic plate is emitter stage 1, and thermo-electric converting material periphery sets seal closure, and seal closure 4 arranges charge pipe 5,
Charge pipe 5 one end is connected with thermo-electric converting material 3, and the other end connects feeder 7, just constitutes single entry chip thermal cell, can be from
Upper and lower heating.The course of processing of thermo-electric converting material is with embodiment 1.Also compound knot can be combined into by thermobattery for single entry chip
Structure.
The interior electrode of the present invention is also referred to as emitter stage, and it receives the electronics from thermo-electric converting material.External electrode is also referred to as
Heating pole, after its temperature change, thermoelectric transition material conveys electronics, thus thermo-electric converting material is heated.Due to unidirectional
Electric structure, the effect that the thermocurrent in thermoelectric cell plays positive promotion, reversely stops.
Wherein, interior electrode 1, external electrode 2 are metal material.It is preferably ferrum or copper or aluminum or silver.For example interior electricity
Metallic iron is selected in pole 1, and external electrode 2 selects metallic copper.
Thermo-electric converting material 3 is ce (fexhfyptz)13
Wherein: the scope of x is 0.85 ~ 0.90；The scope of y is 0.03 ~ l-x；The scope of z is 0.005 ~ 0.45.
Thermo-electric converting material is preferably cefe11hf1.55pt0.45, cefe11.5hf1.15pt0.45, cefe10.75hf1.8pt0.35,
cefe10.8hf1.85pt0.35.
The manufacturing process of described thermo-electric converting material 3 comprises the steps:
A) make tetra- kinds of chemical elements of ce, fe, hf and pt with corresponding to its metal_based material in solid phase and/or liquid phase
Stoichiometric reaction, forms ce (fexhfyptz)13Reactant；
B) above-mentioned reactant is pressed into solid；
C) by above-mentioned solid sintering and/or heat treatment,
D) will be quenched with the cooldown rate of at least 100k/s from the solid of the sintering of step c) and/or heat treatment.
In the step (a) of this method,
In solid phase or liquid phase, the latter's thermo-electric conversion material be will be present in the stoichiometric proportion corresponding to thermo-electric converting material
Element in material and/or alloy conversion.
Preferably pass through element and/or alloy in hermetic container or in an extruder combined heated, or by ball milling
Solid state reaction in machine and carry out the reaction in step a).Particularly preferably carry out solid state reaction, it is carried out especially in ball mill.Logical
Often, will be present in the powder of the alloy of the powder of each element in the latter's thermo-electric converting material or two or more each elements
With powder-form with suitable weight than mixing.If necessary, also mixture can be ground to obtain microcrystalline powder mixing
Thing.Preferably this mixture of powders is heated in ball mill, this leads to pulverize further and well mix, and lead to powder to mix
Solid state reaction in compound.Or, each element is mixed with selected stoichiometric proportion as powder, then melts.
In hermetic container, combined heated makes fixing volatile element and controls stoichiometric proportion.Specifically, make
With in open systemss, this will easily evaporate in the case of phosphorus.
In the step (b) of this method,
The solid obtaining in step a) was suppressed before sintering and/or heat treatment.This makes density of material improve so that high
Density thermoelectric transition material is present in the latter's application.This is especially favourable, because the volume that there is magnetic field can reduce, this can
Considerably cost-effective.It is compressed to known per se, can carry out with or without compression aid.Can using any be suitable to suppress
Model.By compacting, can get the molded body of required three dimensional structure.Can carry out after compacting at sintering and/or the heat of step c)
Reason, the followed by quenching of step d).
In the step (c) of this method,
The sintering of solid and/or heat treatment are carried out in step c), preferably carry out first at a temperature of 700-1300 DEG C
Sintering, then carries out heat treatment at a temperature of 500-750 DEG C.These values are particularly suited for molded body, and relatively low sintering and
Heat treatment temperature can be used for powder, for example, carries out at a temperature of 500-700 DEG C.For molded body/solid, sintering is more preferably
At 900-1200 DEG C, carry out at a temperature of especially 1000-1100 DEG C.Then heat treatment can for example be carried out at 600-700 DEG C.
Sintering preferably carries out 20-30 hour, more preferably 25-30 hour.Heat treatment preferably carries out 50-70 hour, more preferably
60-65 hour.The accurate time can be adapted to actual requirement according to material.
Sintering/heat treatment leads to granule boundary partial melting so that material is closely knit further.Therefore, molten in step b)
Warm quick cooling makes the duration of step c) be considerably reduced.This also makes continuously to prepare 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 with high cooling
During speed quenching, thermo-lag can significantly reduce and can achieve pyroelectric effect.This cooldown rate is at least 100k/s.Cooldown rate is excellent
Elect 200-1300k/s as, preferred cooldown rate is 300-1000k/s.
Quenching can be realized by any suitable cooling means, for example pass through with water or liquid, aqueous as cooling water or ice/
Solid is quenched by aqueous mixtures.For example, solid can be made to fall in the water of ice cooling.Also can be with supercool gas such as liquid nitrogen by solid
Quenching.Other method of quenching are well known by persons skilled in the art.
Measured it is possible to obtain different volumes, different area in difference by thermal cell is heated to different temperatures
At a temperature of produced corresponding current strength.The thermoelectrical conversion battery of the present invention can be converted into electric energy various heat energy.
Its sensitivity is good, and the temperature change of in the air can make thermal cell produce curent change, is that a kind of collection of common heat turns
Change device, especially can obtain good thermo-electric conversion effect in high-temperature heating, and can be repeatedly used for a long.Through experiment card
Bright, the thermo-electric converting material using the present invention makes thermoelectrical conversion battery, with thermo-electric converting material shape well known in the prior art
The thermoelectrical conversion battery becoming is compared, and conversion efficiency of thermoelectric significantly improves, and improves 12 ~ 18%, at 50 ~ 100 DEG C between 10 ~ 50 DEG C
Between improve 22 ~ 32%.Temperature within thermal cell can not unconfined increase, the heating temperature of the thermoelectrical conversion battery of the present invention
Within degree is preferably limited to 100 degrees Celsius.Because the structure of thermoelectric cell is different, material is different, and the requirement to temperature is different.
As can be seen here, the material of the present invention is adapted for a kind of novel thermo-electric converting material of thermoelectrical conversion battery, its room
Interior temperature change can produce curent change, is especially remarkably improved thermo-electric conversion effect in the range of 50 ~ 100 DEG C for the heating-up temperature
Rate.
Claims (1)
1. a kind of internal and external electrode is the thermoelectrical conversion battery of metallic plate, including in electrode, external electrode and arrange therebetween
Thermo-electric converting material it is characterised in that
Interior electrode is metal tube, dispatch from foreign news agency extremely metallic plate,
Thermo-electric converting material is ce (fexhfyptz)13
Wherein: the scope of x is 0.85 ~ 0.90；The scope of y is 0.03 ~ l-x；The scope of z is 0.005 ~ 0.45；
The manufacturing process of described thermo-electric converting material comprises the steps:
A) make tetra- kinds of chemical elements of ce, fe, hf and pt anti-with the stoichiometric proportion corresponding to its metal_based material in solid phase
Should, form ce (fexhfyptz)13Reactant；
B) above-mentioned reactant is pressed into solid；
C) by above-mentioned solid sintering and heat treatment；
D) will be quenched with the cooldown rate of 300-1000k/s from the solid of the sintering of step c) and heat treatment；
In step a), solid state reaction is carried out in ball mill；
In step c), it is sintered 25-30 hour first at a temperature of 1000-1100 DEG C, then at 600-700 DEG C
At a temperature of carry out heat treatment 60-65 hour.
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| CN201410037093.5A CN103762300B (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion battery with metal plates as inner electrode and outer electrode |
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| CN201410037093.5A CN103762300B (en) | 2014-01-26 | 2014-01-26 | Thermoelectric conversion battery with metal plates as inner electrode and outer electrode |
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| CN103762300A CN103762300A (en) | 2014-04-30 |
| CN103762300B true CN103762300B (en) | 2017-01-18 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032710A (en) * | 1987-10-23 | 1989-05-03 | 贝尔-Irh有限公司 | Improved stable thermoelectric couple |
| CN101728477A (en) * | 2009-12-04 | 2010-06-09 | 北京工业大学 | Method for preparing CeyFe4Sb12/Ca3Co4O9(y=0.8-1.2) based block gradient thermoelectric material |
| CN101794858A (en) * | 2009-12-25 | 2010-08-04 | 北京工业大学 | P-type (Bi0.25Sb0.75)2Te3/CeyFe4Sb12(y=0.8-1.2)-based bulk gradient thermoelectric material and preparation method thereof |
| CN101952466A (en) * | 2007-12-19 | 2011-01-19 | 生物测定技术研发有限公司 | Method for producing a thermoelectric intermetallic compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102983265B (en) * | 2012-11-20 | 2015-11-25 | 溧阳市生产力促进中心 | A kind of internal and external electrode is the thermoelectrical conversion battery of metallic plate |
| CN102969443B (en) * | 2012-11-20 | 2015-12-02 | 溧阳市生产力促进中心 | A kind of internal and external electrode is the thermoelectrical conversion battery of metal wire |
| CN102983261B (en) * | 2012-11-20 | 2015-11-25 | 溧阳市生产力促进中心 | A kind of internal and external electrode is the thermoelectrical conversion battery of one end closed metal pipe |
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2014
- 2014-01-26 CN CN201410037093.5A patent/CN103762300B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032710A (en) * | 1987-10-23 | 1989-05-03 | 贝尔-Irh有限公司 | Improved stable thermoelectric couple |
| CN101952466A (en) * | 2007-12-19 | 2011-01-19 | 生物测定技术研发有限公司 | Method for producing a thermoelectric intermetallic compound |
| CN101728477A (en) * | 2009-12-04 | 2010-06-09 | 北京工业大学 | Method for preparing CeyFe4Sb12/Ca3Co4O9(y=0.8-1.2) based block gradient thermoelectric material |
| CN101794858A (en) * | 2009-12-25 | 2010-08-04 | 北京工业大学 | P-type (Bi0.25Sb0.75)2Te3/CeyFe4Sb12(y=0.8-1.2)-based bulk gradient thermoelectric material and preparation method thereof |
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Address after: 226631, No. 78, Xinjian East Road, Li Town, Nantong County, Jiangsu, Haian Patentee after: Nantong Mingnuo electric Polytron Technologies Inc Address before: 226631, No. 78, Xinjian East Road, Li Town, Nantong County, Jiangsu, Haian Patentee before: Nantong Mingnuo Machinery Co., Ltd. |