CN104120372A - Method for manufacturing high-performance thermoelectric material through cold forming - Google Patents
Method for manufacturing high-performance thermoelectric material through cold forming Download PDFInfo
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- CN104120372A CN104120372A CN201410157880.3A CN201410157880A CN104120372A CN 104120372 A CN104120372 A CN 104120372A CN 201410157880 A CN201410157880 A CN 201410157880A CN 104120372 A CN104120372 A CN 104120372A
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- thermoelectric material
- cold
- forming
- manufacture method
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
- H10N30/095—Forming inorganic materials by melting
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
Abstract
The invention aims to manufacture various thermoelectric materials without limitation of types of thermoelectric materials and provides an economical and environment-friendly method for manufacturing a high-performance thermoelectric material through cold forming. The method comprises an ingot casting manufacturing step for manufacturing ingot by cooling the melt thermoelectric material, a cold forming step for carrying out cold forming to the manufactured ingot so as to manufacture the thermoelectric material, and a thermal treatment step for carrying out thermal treatment to the manufactured thermoelectric material.
Description
Technical field
The present invention relates to utilize the high performance thermoelectric material manufacture method of cold-forming (cold working), more specifically, relate to after starting material ingot casting (ingot), it is carried out to cold-forming, thermal treatment, thereby be not subject to pyroelectric kind restriction and manufacture multiple thermoelectric material, and the environment amenable high performance thermoelectric material manufacture method of utilizing cold-forming economic time.
[country being supported to the explanation of research and development]
This research is under the supervisor of Korean Institute of Science and Technology, be subject to the most advanced and sophisticated integration technology development project of science of education technical division (problem title: the cooling Element Technology exploitation of molecular structure control high-efficiency thermal electric material and semi-conductor, the intrinsic numbering of problem: support 1345154294) and realizing.
Background technology
Generally speaking, thermoelectric element (thermo element) is energy converslon materials, when produce electric energy in the time that material go-and-retum applies temperature head, on the contrary, in the time giving material with electric energy, produces temperature head at material go-and-retum.
The thermoelectric power generation of thermoelectric element and the cooling Peltier effect (Peltier effect) producing that moves based on the electronics, the hole that produce the Seebeck effect (Seebeck effect) of electromotive force because of temperature head and utilize electric energy to make to have heat energy.This thermoelectric element, because fault is few, maintenance management is easy, muting advantage, can usefully be applied as small-scale energy conversion system in the space limiting.
The performance of thermoelectric element directly depends on the structure of element and the thermoelectricity capability index (figure of merit) that thermoelectric material (thermoelectric materials) has.Every kind of material reaches the optimized temperature difference of performance index, and in normal temperature region, Bi-Te alloy series shows classic pyroelecthc properties, thereby uses at most in actual components.Thermoelectricity capability index (ZT) shows as α
2σ T/ κ, wherein, α represents Seebeck coefficient (α), and σ represents specific conductivity, and κ represents thermal conductivity, and T represents absolute temperature.
Aspect this thermoelectric element of making, roughly there are now two kinds of problems.
The first, above-mentioned substance, as the material of strong toxicity, needs to make environmental pollution to realize and minimizes in operation.A large amount of mechanical alloying (mechanical alloying) or powder methods (powder method) that use have larger weakness from this viewpoint now.In addition, with regard to aforesaid method, easily oxidation in operation, the possibility that impurity etc. flow into is large, and this has greatly damaged the thermoelectric property of material.
Second, maintain high thermoelectricity capability in order and to reduce fault in material for the high mechanical strength of the degree of element, be called as pressure and heat treated two kinds of operations are essential, these two kinds of operations are used a lot of element manufacturing costs, therefore, need to save production charges by new process.Particularly as discharge plasma sintering (spark plasma sintering), hot pressing (hot press), exerting pressure with hot in the situation that, installation cost and manufacturing expenses are inevitable significantly to rise simultaneously.
With regard to above two kinds of viewpoints, now thermoelectric element industry in the urgent need to be environment amenable operation method and low price type thermoelectric material (material) synthetic technology that can save production charges.
[prior art document]
[patent documentation]
No. 10-2010-0053359th, Republic of Korea's publication communique
No. 2011-0083666th, U.S.'s publication communique
No. 2010-0295202nd, U.S.'s publication communique
No. 2008-0202575th, U.S.'s publication communique
[non-patent literature]
Identifying?the?Specific?Nanostructures?Responsible?for?the?High?Thermoelectric?Performance?of(Bi,Sb)2Te3Nanocomposites,Wenjie?Xie?et?al.
High-Thermoelectric?Performance?of?Nanostructured?Bismuth?Antimony?Telluride?Bulk?Alloys,Bed?Poudel?et?al.
Summary of the invention
The present invention is for solving problem as above, object is to provide the high performance thermoelectric material manufacture method of utilizing cold-forming, by after pyroelectric ingot casting (ingot), it is carried out to cold-forming, thermal treatment, thereby be not subject to pyroelectric kind restriction and manufacture multiple thermoelectric material, and environmentally friendly economical time.
At an embodiment for reaching the object of the invention, the high performance thermoelectric material manufacture method of utilizing cold-forming is provided, wherein, comprising: ingot casting manufacturing step, makes the rear cooling ingot casting (ingot) of manufacturing of pyroelectric fusing; Cold-forming step, carries out cold-forming to the ingot casting of described manufacture and manufactures thermoelectric material; And heat treatment step, the thermoelectric material of described manufacture is heat-treated.
In exemplary embodiment, preferred described cold-forming step is implemented more than 2 times repeatedly.
In exemplary embodiment, preferred described heat treatment step carries out in the temperature range of 250 DEG C～550 DEG C.
In exemplary embodiment, preferred described pyroelectric is N-type or P-type pyroelectric.
In exemplary embodiment, preferred described pyroelectric is more than one 2 yuan of prime system materials that are selected from Bi-Te system, Sb-Te system, Pb-Te system, Pb-Se system, Si-Ge system, In-Co system, Bi-Te-Se system, Bi-Te-Sb system and In-Co-Sb system.
In exemplary embodiment, preferably, in described cold-forming step, the pressure that puts on described ingot casting is 400MPa～2000MPa.
In exemplary embodiment, preferred described heat treatment step carries out under oxygen free condition, and described oxygen free condition is vacuum state, the nonactive atmosphere of argon (Ar) or hydrogen (H
2) reducing atmosphere.
According to the high performance thermoelectric material manufacture method of utilizing cold-forming of the present invention, can not be subject to the restriction of pyroelectric kind and manufacture various thermoelectric materials.
In addition, according to the high performance thermoelectric material manufacture method of utilizing cold-forming of the present invention, can manufacture thermoelectric material with economic and environment amenable method.
Brief description of the drawings
Fig. 1 represents that material is through the microtexture of over recovery, recrystallize and crystal grain-growth phenomenon variation in the time the material of process cold plastic deformation being heat-treated according to an embodiment of the invention.
Fig. 2 is the schematic diagram that represents according to an embodiment of the invention, thermoelectric material to be applied the process of cold-forming.
Fig. 3 is the schematic diagram that represents according to an embodiment of the invention, the thermoelectric material of cold-forming to be carried out the process of low-temperature heat treatment.
Fig. 4 represents in an embodiment of the invention, the thermoelectricity physical property variation of the thermoelectric material under the different heat treatment time.
Embodiment
With reference to the accompanying drawings, the preferred embodiment of the present invention is described.The present invention is taking illustrated embodiment in accompanying drawing as with reference to being illustrated, but this just describes as an embodiment, and technological thought of the present invention and core thereof form and act on and being not limited thereto.
Particularly including claims and summary, the term " thermoelectric element (thermo element) " that this specification sheets uses is in the whole text interpreted as meaning and in the time that material go-and-retum applies temperature head, produces electric energy, and produce the energy converslon materials of temperature head during with electric energy to material at material go-and-retum, term " thermoelectric material (thermoelectric materials) " is interpreted as meaning the material for the manufacture of described thermoelectric element.
The invention provides a kind of thermoelectric material manufacture method, the recovery using in metal metallurgy smelting field (recovery), recrystallize (recrystallization) and grain growing (grain growth) phenomenon are applied to pyroelectric by it, pressure operation separates with heat treatment step, low temperature, middle temperature or high temperature thermoelectric material that can synthesized high-performance, economical time, suppress environmental pollution possibility.
Being intended to reach in an embodiment of the object of the invention, a kind of high performance thermoelectric material manufacture method of utilizing cold-forming is provided, wherein, comprising: ingot casting manufacturing step, make pyroelectric fusing rear cooling, manufacture ingot casting (ingot); Cold-forming step, carries out cold-forming to the ingot casting of described manufacture, manufactures thermoelectric material; And heat treatment step, the thermoelectric material of described manufacture is heat-treated.
Further describe thermoelectric material manufacture method of the present invention by step.
First, make, after pyroelectric fusing (melting), to make it cooling, manufacture ingot casting (ingot).
Described pyroelectric can use N-type or P-type pyroelectric, if concrete example, can be more than one 2 yuan of prime system materials that are selected from Bi-Te system, Sb-Te system, Pb-Te system, Pb-Se system, Si-Ge system, In-Co system, Bi-Te-Se system, Bi-Te-Sb system and In-Co-Sb system, in addition, can be also 3 yuan of prime system materials such as Bi-Te-Sb.
As an example, described N-type and P-type pyroelectric can be in Bi-Te system, to add selenium (Se) etc. and become N-type, or add antimony (Sb) etc. and become P-type.In addition, not only can use favourable at normal temperatures pyroelectric, also can use the material that reveals excellent pyroelecthc properties at medium and high temperature region list.
While manufacturing described ingot casting, after making pyroelectric fusing, cooling method is not particularly limited, and for example, the material of required composition is put into silica tube (quartz tube), utilize more than rocking furnace (rocking furnace) is heated to fusing point, can well blend.Now, for anti-oxidation, preferably silica tube inside is the reducing atmosphere of the nonactive atmosphere of vacuum or argon (Ar) and so on or hydrogen (H2) and so on.Then, described silica tube can be put into water cooling.Manufacture ingot casting by this process.
Then, the ingot casting of described manufacture carries out cold-forming, manufactures thermoelectric material.
Described cold-forming be to the attenuation by rolling at normal temperatures (cold rolling (cold rolling)), bending machining (clod wash (cold bending)), the general name of forging (cold forging (cold forging), cold-heading (cold heading), (cold press) colds pressing), extruding (cold extrusion (cold extrusion)) etc. and carry out the operation of moulding.
In one embodiment, the ingot casting of described manufacture is put into the casting mold (mold) of regular hexahedron form, exerts pressure from top, and the form viscous deformation of ingot casting is become to casting mold shape (with reference to Fig. 2).
Now applied pressure can be for example within the scope of 400MPa～2000MPa, but is not particularly limited, and this is that deformation extent is higher, when thermal treatment, within the faster time, improves pyroelecthc properties because of described pressure.
Described cold-forming step can be implemented more than 1 time repeatedly, according to the number of occurrence of described process and applied pressure size, can control the cold molding degree of the thermoelectric material of manufacture.In one embodiment, described cold-forming step can be implemented 10 times repeatedly.
Described cold-forming for example also can be suppressed by single shaft (uniaxial press) and realize at normal temperatures, in addition, and can also be by cold rolling (rolling), extrude the forming method such as (extrusion) and realize.
Then, the thermoelectric material of described manufacture is through heat treatment step.
Described thermal treatment, for inhibited oxidation, need be carried out under oxygen free condition,, under the reducing atmosphere of the nonactive atmosphere of vacuum state or argon (Ar) and so on or hydrogen (H2) and so on, carries out for this reason.
When described thermal treatment, temperature condition of heat treatment is not particularly limited, and is not only low temperature, also passable under middle temperature or high temperature, and this relatively determines according to the fusing point of thermoelectric material.For example, described thermal treatment temp can be 40% to 70% temperature of the fusing point of the thermoelectric material manufactured with described cold-forming.As an example, in the embodiments of the invention of following explanation, the pyroelectric that fusing point is about to 420 DEG C has carried out thermal treatment at 300 DEG C.In the temperature range not changing because of volatilization etc. at the composition of material, if described thermal treatment temp is higher, the speed that pyroelecthc properties of the final thermoelectric material of manufacturing is saturated is faster.
Described heat treatment time is not particularly limited, but as an example, can be preferably in 2 hours.Heat-treat even if exceed the described time, more than pyroelecthc properties can not brought up to set level yet, but saturated (saturation).
According to the thermoelectric material manufacture method of series of steps that comprises described explanation, do not use the high temperature-press device of high price, do not need powder operation.Therefore, the monocrystalline mother metal of high cost that need to be not required in powder manufacturing process, can realize low temperature process, and process is simplified, thereby can reduce production costs tremendously.
The effect of existence is in addition, owing to not needing powder operation, thereby the parameter minimizing of material making, in addition, can be suppressed at the dust and 2 pollution substances that in powder operation process, occur.
Embodiment
Illustrate in greater detail the present invention below by embodiment.These embodiment, only for the present invention is given an example, shall not be construed as scope of the present invention and are limited by these embodiment, this be person of ordinary skill in the field clearly.
By 22.5%Bi
2te
3-77.5%Sb
2te
3composition 30g vacuum pack silica tube (quartz tube) into, make pressure maintain 1 × 10
-5after Torr, it is carried out after melting within the scope of 700-750 DEG C cooling, make ingot casting.
Then,, according to by the casting mold for cold deformation, be processed into the processing specification of 5mm × 5mm × 12mm.The processing of described thermoelectric material can have two kinds, a kind of is in metal material processing, to utilize the general precision sizing cutting machine (diamond blade) using, another kind is that metal wire and thermoelectric material are carried out to arc-over and process, in the present embodiment, due to efficiency and yield, use the latter to process.
The ingot casting of described processing is put into casting mold, carry out cold deformation.
Cold deformation utilizes cold-extruded platen press, applies the pressure of about 1400MPa, makes ingot casting distortion.The sample of distortion is applied to energy to inside more repeatedly.In this experiment, give 10 cold deformations, make sample can accumulate sufficient energy (with reference to Fig. 2).
The sample of described 10 cold deformations under vacuum atmosphere, has carried out thermal treatment (fusing point: 420 DEG C of left and right) (with reference to Fig. 3) for inhibited oxidation at 300 DEG C.
Measure the thermoelectricity physical property under the different heat treatment time, can confirm the effect of cold deformation, this is taking the time as parameter by the sample of heat-treating as illustrated in fig. 3, measure pyroelecthc properties (Seebeck coefficient (Seebeck coefficient), specific conductivity (electrical conductivity), thermal conductivity (thermal conductivity), z(performance index (figure of merit))) (with reference to Fig. 4), can confirm to improve because Seebeck coefficient increases with electroconductibility, thermoelectricity capability index entirety improves.
Below described in detail the specific part of content of the present invention, person of ordinary skill in the field is clear, and just preferred embodiment, scope of the present invention is not defined in this in this concrete description.Therefore, essential scope of the present invention is defined by claim and Equivalent thereof.
Claims (7)
1. a high performance thermoelectric material manufacture method of utilizing cold-forming, wherein, comprising:
Ingot casting manufacturing step, makes the rear cooling ingot casting of manufacturing of pyroelectric fusing;
Cold-forming step, carries out cold-forming to the ingot casting of described manufacture and manufactures thermoelectric material; And
Heat treatment step, heat-treats the thermoelectric material of described manufacture.
2. the high performance thermoelectric material manufacture method of utilizing cold-forming according to claim 1, wherein, described cold-forming step is implemented more than 2 times repeatedly.
3. the high performance thermoelectric material manufacture method of utilizing cold-forming according to claim 1, wherein, described heat treatment step carries out in the temperature range of 250 DEG C～550 DEG C.
4. the high performance thermoelectric material manufacture method of utilizing cold-forming according to claim 1, wherein, described pyroelectric is N-type or P-type pyroelectric.
5. the high performance thermoelectric material manufacture method of utilizing cold-forming according to claim 4, wherein, described pyroelectric is more than one 2 yuan of prime system materials that are selected from Bi-Te system, Sb-Te system, Pb-Te system, Pb-Se system, Si-Ge system, In-Co system, Bi-Te-Se system, Bi-Te-Sb system and In-Co-Sb system.
6. the high performance thermoelectric material manufacture method of utilizing cold-forming according to claim 1, wherein, in described cold-forming step, the pressure that puts on described ingot casting is 400MPa～2000MPa.
7. the high performance thermoelectric material manufacture method of utilizing cold-forming according to claim 1, wherein, described heat treatment step carries out under oxygen free condition,
Described oxygen free condition is vacuum state, the nonactive atmosphere of argon or hydrogen reduction atmosphere.
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| KR10-2013-0044554 | 2013-04-23 | ||
| KR1020130044554A KR101455713B1 (en) | 2013-04-23 | 2013-04-23 | Method of preparing high performance thermoelectric materials using cold working |
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| CN104120372A true CN104120372A (en) | 2014-10-29 |
| CN104120372B CN104120372B (en) | 2016-08-24 |
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| KR101831150B1 (en) * | 2015-11-12 | 2018-02-23 | 한국과학기술연구원 | Apparatus and method for fabricating thermoelectric materials using cold deformation |
| KR101801787B1 (en) * | 2015-12-15 | 2017-11-28 | 한국과학기술연구원 | Thermoelectric materials of high efficiency and method for manufacturing the same |
| KR101848012B1 (en) | 2016-11-14 | 2018-04-11 | 한국과학기술연구원 | A method for measuring thermal conductivity and figure-of-merit of thermoelectric materials |
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| JP2004211125A (en) * | 2002-12-27 | 2004-07-29 | Yamaha Corp | Thermoelectric material and its producing method |
| CN101073831A (en) * | 2007-06-15 | 2007-11-21 | 武汉理工大学 | Method for forming ZnSb-based block thermoelectric material at ultra-high pressure and cold pressure |
| KR20100053359A (en) * | 2008-11-12 | 2010-05-20 | 세종대학교산학협력단 | METHOD FOR MANUFACTURING OF P-TYPE Bi-Sb-Te BASED THERMOELECTRIC MATERIALS |
| CN101736173A (en) * | 2010-01-08 | 2010-06-16 | 武汉理工大学 | Method for preparing AgSbTe2 thermoelectric material by combining fusant rotatable swinging and spark plasma sintering |
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| JP2556970B2 (en) * | 1986-07-30 | 1996-11-27 | 株式会社小松製作所 | Thermoelectric material manufacturing method |
| KR20020010768A (en) * | 2000-07-31 | 2002-02-06 | 병 선 천 | Method of producing thermoelectric transform materials by using the twin rolling and the hot forming process |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004211125A (en) * | 2002-12-27 | 2004-07-29 | Yamaha Corp | Thermoelectric material and its producing method |
| CN101073831A (en) * | 2007-06-15 | 2007-11-21 | 武汉理工大学 | Method for forming ZnSb-based block thermoelectric material at ultra-high pressure and cold pressure |
| KR20100053359A (en) * | 2008-11-12 | 2010-05-20 | 세종대학교산학협력단 | METHOD FOR MANUFACTURING OF P-TYPE Bi-Sb-Te BASED THERMOELECTRIC MATERIALS |
| CN101736173A (en) * | 2010-01-08 | 2010-06-16 | 武汉理工大学 | Method for preparing AgSbTe2 thermoelectric material by combining fusant rotatable swinging and spark plasma sintering |
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| CN104120372B (en) | 2016-08-24 |
| KR101455713B1 (en) | 2014-11-04 |
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