CN112404440A - Method and mould for rapidly preparing homogeneous thermoelectric material - Google Patents
Method and mould for rapidly preparing homogeneous thermoelectric material Download PDFInfo
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- CN112404440A CN112404440A CN202011334854.5A CN202011334854A CN112404440A CN 112404440 A CN112404440 A CN 112404440A CN 202011334854 A CN202011334854 A CN 202011334854A CN 112404440 A CN112404440 A CN 112404440A
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- 239000000463 material Substances 0.000 title claims abstract description 140
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 22
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims description 12
- 229910007372 Zn4Sb3 Inorganic materials 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 230000005679 Peltier effect Effects 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000002490 spark plasma sintering Methods 0.000 abstract description 8
- 239000004020 conductor Substances 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000004566 building material Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a method for rapidly preparing a homogeneous thermoelectric material, which comprises the following steps: firstly, the thermoelectric material cast ingot is ground to obtain thermoelectric material powder. And then putting the thermoelectric material powder into a mold. Wherein the resistivity of the mold is lower than that of the thermoelectric material powder by more than 1 order of magnitude. And finally, placing the die into a discharge plasma sintering furnace for sintering to obtain the homogeneous thermoelectric material. The method is simple to operate, rapid in sample loading and good in repeatability, the upper surface and the lower surface of the prepared homogeneous thermoelectric material are not different, the components are uniform, and the thermoelectric performance of the homogeneous thermoelectric material is improved. The invention also provides a mould for rapidly preparing the homogeneous thermoelectric material, and the material of the mould is selected from conductive materials such as metal, alloy or graphite. When the mould selected by the invention is used for spark plasma sintering, the sintering current mainly passes through the mould. Therefore, the mold can be used for preparing compact and homogeneous thermoelectric materials, is convenient to load and can be repeatedly used.
Description
Technical Field
The invention relates to the technical field of energy conversion materials, in particular to a method and a die for quickly preparing a homogeneous thermoelectric material.
Background
Thermoelectric materials are capable of directly converting thermal energy to electrical energy. The method is an effective method for solving waste heat waste when the energy conversion material is used as an energy conversion material in the field of waste heat treatment. The most common sintering method for thermoelectric materials is Spark Plasma Sintering (SPS) or Plasma Activated Sintering (PAS). The two sintering modes are technically characterized by electrifying and sintering. Referring to fig. 1, when electricity is applied to both ends of a thermoelectric material, a temperature difference is generated between upper and lower ends of the thermoelectric material due to the peltier effect, resulting in non-uniform sintering of the thermoelectric material. In addition, when current passes through some thermoelectric materials, part of atoms are carried along, thereby causing non-uniformity of the sintered thermoelectric materials.
Although there is a method of preparing a homogeneous thermoelectric material by placing a BN-sprayed graphite paper around a thermoelectric material powder to prevent a sintering current from passing through. However, this method has the following problems: on the one hand, the uniformity of BN sprayed on the graphite paper cannot be ensured during spraying. On the other hand, BN is easy to fall off from the graphite paper in the sintering and pressing process and is mixed into sample powder, and the components of the thermoelectric material are influenced. The homogeneous thermoelectric material prepared by the method has high BN spraying process requirement and poor repeatability. In addition, placing the phlogopite sheet around the sample powder is also a way to prevent the sintering current from passing. However, the method is limited by the material of the auromite sheet, and the highest tolerance temperature of the auromite sheet is not suitable for sintering preparation of the thermoelectric material in the high-temperature region. In addition, the thickness of the film has no quantitative analysis on the effect of the current isolation.
Disclosure of Invention
The invention aims to provide a method for quickly preparing a homogeneous thermoelectric material, which is simple to operate, quick to load samples and good in repeatability.
Another object of the present invention is to provide a mold for rapidly preparing a homogeneous thermoelectric material, which can be used to prepare a homogeneous thermoelectric material and improve the thermoelectric performance of the thermoelectric material.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides a method for rapidly preparing a homogeneous thermoelectric material, which comprises the following steps:
s1, grinding the thermoelectric material cast ingot to obtain thermoelectric material powder;
s2, putting the thermoelectric material powder into a mould; wherein the resistivity of the die is lower than that of the thermoelectric material powder by more than 1 order of magnitude;
and S3, placing the die into a discharge plasma sintering furnace for sintering to obtain a thermoelectric material block, wherein the thermoelectric material block is a homogeneous thermoelectric material.
The invention provides a mold for rapidly preparing a homogeneous thermoelectric material, which is used in the method for rapidly preparing the homogeneous thermoelectric material, wherein the material of the mold is selected from metal, alloy or graphite.
The method and the die for rapidly preparing the homogeneous thermoelectric material have the advantages that:
1. the method for rapidly preparing the homogeneous thermoelectric material provided by the embodiment of the invention is characterized in that the thermoelectric material is ground to obtain thermoelectric material powder, and the thermoelectric material powder is put into a mould to be subjected to discharge plasma sintering, so that the homogeneous thermoelectric material is obtained. The resistivity of the selected die is lower than that of the thermoelectric material powder by more than 1 order of magnitude. The method is simple to operate, quick to load the sample and good in repeatability. Compared with the method for preparing the homogeneous thermoelectric material by adopting graphite paper, the homogeneous thermoelectric material prepared by adopting the method has no difference on the upper surface and the lower surface, has uniform components and also has improved thermoelectric performance.
2. The resistivity of the mold for rapidly preparing the homogeneous thermoelectric material is lower than that of the thermoelectric material powder by more than 1 order of magnitude. In spark plasma sintering, the sintering current will mainly pass through the mold. Therefore, the mold can be used for preparing compact and homogeneous thermoelectric materials, is convenient to load and can be repeatedly used.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of the Peltier effect and current driven atomic migration during spark plasma sintering;
FIG. 2 is a flow chart illustrating a process for rapidly preparing a homogeneous thermoelectric material according to an embodiment of the present invention;
FIG. 3 is a graph of sintering current paths for Y4 alloy die steel of example 1 of the present invention and graphite die of comparative example 1;
FIG. 4 shows Zn prepared in example 1 of the present invention4Sb3Thermoelectric material and Zn prepared in comparative examples 1 to 24Sb3XRD patterns of the upper and lower surfaces of the thermoelectric material;
fig. 5 is a schematic view of the distribution of BN on BN-sprayed graphite paper.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the method and the mold for rapidly preparing a homogeneous thermoelectric material according to the embodiments of the present invention.
The embodiment of the invention provides a method for rapidly preparing a homogeneous thermoelectric material, which comprises the following steps:
and S1, grinding the thermoelectric material ingot to obtain thermoelectric material powder.
Further, in the preferred embodiment of the invention, the thermoelectric material ingot is a semiconductor thermoelectric material with a Zeebel effect and a Peltier effect.
Further, in the preferred embodiment of the invention, the thermoelectric material ingot is SnSe, Zn4Sb3Or Cu2And (5) Se. The thermoelectric material ingot used in the present invention can be commercially available. For example, SnSe and Zn4Sb3Available from texas, forest materials science and technology, inc. Cu2Se is available from Yongzhong building material photoelectric material Co.
Further, in a preferred embodiment of the present invention, the grinding manner is selected from agate bowl grinding, ball milling or turbo grinding, and the grinding atmosphere is air atmosphere or inert gas atmosphere. For materials that are easily oxidized, milling in an inert gas atmosphere may be selected to prevent oxidation. Optionally, the material that is not easily oxidized may be ground in air.
Further, in a preferred embodiment of the present invention, the thermoelectric material powder has a particle size ranging from 1nm to 1mm, and the powder particles are spherical or irregular.
And S2, putting the thermoelectric material powder into a mould. Wherein the resistivity of the mold is lower than that of the thermoelectric material powder by more than 1 order of magnitude. By selecting a mold having a resistivity lower than the resistivity of the thermoelectric material, the sintering current is mainly passed through the mold during sintering. The thermoelectric material prepared by the method has no difference on the upper surface and the lower surface and uniform components.
Further, in the preferred embodiment of the present invention, the thermoelectric material powder is screened by a screen before being placed in the mold. The particle size and the particle size uniformity of the thermoelectric material powder can be controlled by sieving through a screen.
And S3, placing the die into a discharge plasma sintering furnace for sintering to obtain a thermoelectric material block, wherein the thermoelectric material block is a homogeneous thermoelectric material.
Further, in the preferred embodiment of the present invention, the sintering temperature is 50 to 1500 ℃, and the sintering pressure is 10 to 1000 MPa. The sintering temperature of the invention is controlled below the melting point of the thermoelectric material, and the sintering pressure is controlledThe selected mold is below the maximum withstand pressure. For example, for Zn4Sb3The best sintering temperature of the thermoelectric material is 200-500 ℃. The optimal sintering pressure for the Y4 alloy die steel is 100MPa to 300 MPa.
Further, in a preferred embodiment of the present invention, the atmosphere for sintering is a vacuum atmosphere or an inert gas atmosphere.
The method has the advantages of simple operation, quick sample loading and good repeatability. Compared with the method for preparing the homogeneous thermoelectric material by adopting graphite paper, the homogeneous thermoelectric material prepared by adopting the mould has no difference on the upper surface and the lower surface, uniform components and improved thermoelectric performance.
Embodiments of the present invention also provide a mold for rapidly preparing a homogeneous thermoelectric material, which is used in the method for rapidly preparing a homogeneous thermoelectric material. The material of the mould is selected from conductive materials such as metal, alloy or graphite. The invention can select conductive materials such as metal, alloy or graphite to prepare the die. The resistivity of these conductive materials is lower than that of the thermoelectric material. When the thermoelectric material powder is placed in a mold for spark plasma sintering, current mainly passes through the mold due to the low resistivity of the conductive material such as metal or alloy. Therefore, the phenomenon that the sintering is uneven due to the fact that the temperature difference is generated between the upper end and the lower end of the thermoelectric material when the current passes through the thermoelectric material is avoided, and the phenomenon that the sintered thermoelectric material is uneven due to the fact that the current drives partial atoms to migrate when passing through some thermoelectric materials is avoided.
Further, in the preferred embodiment of the present invention, the die is Y4 alloy die steel.
The resistivity of the mold for rapidly preparing the homogeneous thermoelectric material is lower than that of the thermoelectric material powder by more than 1 order of magnitude. In spark plasma sintering, the sintering current will mainly pass through the mold. Therefore, the mold can be used for preparing compact and homogeneous thermoelectric materials, is convenient to load and can be repeatedly used.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Referring to fig. 2, the present embodiment provides a method for rapidly preparing a homogeneous thermoelectric material, including the steps of:
s1, weighing 5g of Zn4Sb3Ingot casting material 1, ground to Zn in a glovebox using an agate grinding bowl4Sb3And (2) powder.
S2, adding Zn4Sb3The powder 2 is sieved by a 300-mesh sieve.
S3, screening Zn4Sb3The powder 2 was placed in a Y4 alloy die 3 having a diameter of 20 mm.
S4, adding Zn into the solution4Sb3The Y4 alloy die 3 of the powder 2 was placed in a spark plasma sintering system for sintering. Wherein the sintering pressure is 300MPa, the sintering temperature is 350 ℃, the vacuum degree is less than 10Pa, and the temperature is kept for 15min to obtain homogeneous Zn4Sb3A bulk material 4.
Comparative example 1
This comparative example provides a method of preparing a homogeneous thermoelectric material, which differs from example 1 mainly in that:
the mold used in step S3 of this comparative example was a graphite mold 5.
Comparative example 2
The present comparative example provides a method of preparing a homogeneous thermoelectric material, which is mainly different from comparative example 1 in that:
before the spark plasma sintering is performed in step S4, Zn is added4Sb3And BN sprayed carbon paper is placed around the powder 2.
Referring to fig. 3, fig. 3a is a flow chart of a sintering current 6 in sintering using a graphite mold. Wherein the resistivity of the graphite mold and Zn4Sb3The resistivity of the thermoelectric material is of the same order of magnitude. Thus, the sintering current 6 will be simultaneously passed through Zn4Sb3Powder 2 and a graphite mold. Fig. 3b is a flow chart of the sintering current 6 during sintering using the Y4 alloy die 3. Because the resistivity of the Y4 alloy die 3 is far lower than that of Zn4Sb3The resistivity of the thermoelectric material 2. The sintering current 6 will therefore mainly pass through the Y4 alloy die 3.
Test example 1
XRD spectrum analysis was performed on the homogeneous thermoelectric material prepared in example 1 and the homogeneous thermoelectric materials prepared in comparative examples 1 to 2.
Referring to FIG. 4, FIG. 4 shows Zn prepared in example 14Sb3Thermoelectric material and Zn prepared by the method of comparative examples 1 to 24Sb3Top and bottom surface XRD patterns of the thermoelectric material samples. As can be seen from FIG. 4, Zn obtained by sintering with a graphite mold4Sb3Thermoelectric material and Zn sintered by graphite paper coated with BN4Sb3The thermoelectric material has different upper and lower surfaces, and Zn is present4Sb3The upper surface of the thermoelectric material is depleted of Zn and the lower surface is enriched of Zn. Zn obtained by adopting the die sintering in the invention4Sb3The upper and lower surfaces of the thermoelectric material have no difference and have uniform components.
Test example 2
And 4 groups of graphite paper are respectively sprayed with BN.
Referring to fig. 5, fig. 5 is a schematic view showing the distribution of BN on the BN-sprayed graphite paper. As can be seen from FIG. 5, 4 groups of graphite paper all have the phenomenon of uneven spraying, and the experimental process is poor in completeness. The non-uniform spray of BN can affect the discharge plasma sintering process of thermoelectric material powder, and finally affect the components of the prepared thermoelectric material and the distribution of the components.
In conclusion, the method for rapidly preparing the homogeneous thermoelectric material and the die for preparing the homogeneous thermoelectric material have the advantages of simple operation, rapid sample loading and good repeatability. Compared with the method for preparing the homogeneous thermoelectric material by adopting graphite paper, the homogeneous thermoelectric material prepared by adopting the method has no difference on the upper surface and the lower surface, has uniform components and also improves the thermoelectric performance.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A method for rapidly preparing a homogeneous thermoelectric material, comprising the steps of:
s1, grinding the thermoelectric material cast ingot to obtain thermoelectric material powder;
s2, putting the thermoelectric material powder into a mould; wherein the resistivity of the die is lower than that of the thermoelectric material powder by more than 1 order of magnitude;
and S3, placing the die into a discharge plasma sintering furnace for sintering to obtain a thermoelectric material block, wherein the thermoelectric material block is a homogeneous thermoelectric material.
2. The method for rapidly manufacturing a homogeneous thermoelectric material as set forth in claim 1, wherein the thermoelectric material ingot is a semiconductor thermoelectric material having zeebel effect and peltier effect in step S1.
3. The method for rapidly preparing a homogeneous thermoelectric material according to claim 2, wherein in the step S1, the thermoelectric material ingot is SnSe, Zn4Sb3Or Cu2Se。
4. The method for rapidly preparing a homogeneous thermoelectric material according to claim 1, wherein in step S1, the grinding manner is selected from agate bowl grinding, ball milling or turbo grinding, and the grinding atmosphere is air atmosphere or inert gas atmosphere.
5. The method of claim 1, wherein in step S1, the thermoelectric material powder has a particle size ranging from 1nm to 1mm, and the powder particles are spherical or irregular.
6. The method for rapidly manufacturing a homogeneous thermoelectric material as set forth in claim 1, wherein the thermoelectric material powder is screened before being put into the mold in step S2.
7. The method for rapidly preparing a homogeneous thermoelectric material according to claim 1, wherein the sintering temperature is 50 to 1500 ℃ and the sintering pressure is 10 to 1000MPa in step S3.
8. The method for rapidly manufacturing a homogeneous thermoelectric material according to claim 1, wherein in step S3, the atmosphere for sintering is a vacuum atmosphere or an inert gas atmosphere.
9. A mold for rapidly manufacturing a homogeneous thermoelectric material, wherein the mold is used in the method for rapidly manufacturing a homogeneous thermoelectric material according to any one of claims 1 to 8, wherein the material of the mold is selected from a metal, an alloy or graphite.
10. The die for rapidly manufacturing a homogeneous thermoelectric material according to claim 9, wherein the die is Y4 alloy die steel.
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| CN202011334854.5A CN112404440A (en) | 2020-11-25 | 2020-11-25 | Method and mould for rapidly preparing homogeneous thermoelectric material |
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| CN202011334854.5A CN112404440A (en) | 2020-11-25 | 2020-11-25 | Method and mould for rapidly preparing homogeneous thermoelectric material |
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| CN201374833Y (en) * | 2009-03-02 | 2009-12-30 | 深圳大学 | Composite electrode pressure head and spark plasma sintering device |
| CN101857928A (en) * | 2010-04-06 | 2010-10-13 | 武汉理工大学 | P-type Zn4Sb3 based thermoelectric material and preparation method thereof |
| US20110120517A1 (en) * | 2009-11-13 | 2011-05-26 | Brookhaven Science Associates, Llc | Synthesis of High-Efficiency Thermoelectric Materials |
| JP2017007172A (en) * | 2015-06-19 | 2017-01-12 | 昭和電工株式会社 | Composite of aluminum and carbon particle and method for producing the same |
| CN107794387A (en) * | 2016-09-07 | 2018-03-13 | 武汉理工大学 | A kind of supper-fast preparation β Zn4Sb3The method of base block thermoelectric material |
| US20190097115A1 (en) * | 2016-03-07 | 2019-03-28 | Furukawa Co., Ltd. | Method of manufacturing thermoelectric conversion material |
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2020
- 2020-11-25 CN CN202011334854.5A patent/CN112404440A/en active Pending
Patent Citations (8)
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|---|---|---|---|---|
| JP2007251125A (en) * | 2006-02-16 | 2007-09-27 | Nissan Motor Co Ltd | Soft magnetic alloy consolidation object and method for fabrication thereof |
| CN101358313A (en) * | 2008-05-09 | 2009-02-04 | 北京科技大学 | Method for improving Bi-S binary system thermoelectric material performance |
| CN201374833Y (en) * | 2009-03-02 | 2009-12-30 | 深圳大学 | Composite electrode pressure head and spark plasma sintering device |
| US20110120517A1 (en) * | 2009-11-13 | 2011-05-26 | Brookhaven Science Associates, Llc | Synthesis of High-Efficiency Thermoelectric Materials |
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| JP2017007172A (en) * | 2015-06-19 | 2017-01-12 | 昭和電工株式会社 | Composite of aluminum and carbon particle and method for producing the same |
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Application publication date: 20210226 |