CN106956004A - High stability Zn4Sb3Thermoelectric composite material and preparation method thereof - Google Patents
High stability Zn4Sb3Thermoelectric composite material and preparation method thereof Download PDFInfo
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- CN106956004A CN106956004A CN201710098786.9A CN201710098786A CN106956004A CN 106956004 A CN106956004 A CN 106956004A CN 201710098786 A CN201710098786 A CN 201710098786A CN 106956004 A CN106956004 A CN 106956004A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 229910007372 Zn4Sb3 Inorganic materials 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 27
- 239000012266 salt solution Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 description 19
- 230000005619 thermoelectricity Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910007657 ZnSb Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
-
- 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
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
A kind of Zn with high stability4Sb3The preparation method of thermoelectric composite material, including：1) by Zn4Sb3Block materials are ground；2) inorganic salt solution is prepared；3) by step 1) the middle Zn obtained4Sb3Little particle and step 2) prepare inorganic salt solution mix；4) by step 3) obtain the Zn containing inorganic salt solution4Sb3Little particle is dried；5) by step 4) the little particle sintering that obtains, obtain compact block, that is, obtain the Zn that structural stability is improved4Sb3Thermoelectric material.The present invention also provides a kind of Zn obtained by the above method4Sb3Thermoelectric composite material.
Description
Technical field
Belong to new energy materialses field the present invention relates to one kind, more particularly to a kind of high stability Zn4Sb3Compound thermoelectricity material
Material and preparation method thereof.
Background technology
In traditional energy consumption process, up to 60% energy is converted for heat, wherein substantial amounts of heat is with used heat
Form slattern.This waste not only causes greenhouse effects, and causes serious problem of environmental pollution, and research can
The environmentally friendly new energy of replacement is just causing the attention of various countries.Thermoelectric material can realize the direct mutual conversion of heat energy and electric energy,
And can be the effective means of alleviating energy crisis using low-temperature heat source in industrial waste heat, underground heat etc. come the direct generation of electricity.Its nothing
Need moving component, dependable performance long lifespan, it is easy to precise control and pollution-free, in terms of space flight, military affairs, life, industry just
Increasingly it is widely applied.Zn4Sb3It is one of most potential thermoelectric material of middle warm area, it can be with 670K or so ZT values
Reach 1.3.With other PbTe, Bi2Te3Contour performance thermoelectric material is compared, Zn4Sb3Material component Zn and Sb reserves on earth
Relative abundance and pollution-free to environment.As the thermoelectric material of excellent performance, Zn is hindered4Sb3The key of application is its high temperature
Heat endurance.Zn4Sb3When higher than 150 DEG C, simple substance Zn and ZnSb can be decomposed slowly to, so as to influence its thermoelectricity capability.Also hinder
Hinder its application in actual industrial production.
The content of the invention
In view of this, it is necessary to which a kind of high stability Zn is provided4Sb3Composite thermoelectric material and preparation method thereof.
A kind of Zn with high stability4Sb3The preparation method of thermoelectric composite material, comprises the following steps：
1) by Zn4Sb3Block materials are ground；
2) inorganic salt solution is prepared；
3) by step 1) the middle Zn obtained4Sb3Little particle and step 2) prepare inorganic salt solution mix；
4) by step 3) obtain the Zn containing inorganic salt solution4Sb3Little particle is dried；
5) by step 4) the little particle sintering that obtains, obtain compact block, that is, obtain the Zn that structural stability is improved4Sb3Heat
Electric material.
As further improved, x scope is 0 to 1.
It is used as further improved, the step 1) in, the Zn after grinding4Sb3Particle diameter is in 10nm~1mm.
As further improved, in step 1) in, the atmosphere of grinding is air atmosphere or inert gas atmosphere.
As further improved, in step 2) in, in the inorganic salt solution inorganic salts include sulfate, nitrate,
Solvent in chlorate, acetate and its mixture, the solution includes water, alcohol, ether, acetone and its mixture.
As further improved, in step 2) in, the concentration of the inorganic salt solution is 0.01mol/L~1mol/L.
As further improved, in step 3) in, it is described by Zn4Sb3Little particle and step 2) inorganic salt solution prepared
The step of mixing, includes：By Zn4Sb3In little particle immersion inorganic salt solution or to Zn4Sb3Little particle sprays inorganic salt solution.
As further improved, in step 4) in, drying course selection is dried or in inert atmosphere protection in atmosphere
Lower drying, the temperature of drying is room temperature~500 DEG C.
As further improved, in step 5) in, sintering processing selection hot pressed sintering or discharge plasma sintering.
As further improved, in step 5) in, the temperature of sintering is 300 DEG C~500 DEG C, and the pressure of sintering is
10MPa~300MPa.
The invention further relates to a kind of high stability Zn obtained according to the above method4Sb3Composite thermoelectric material.
Compared with prior art, the beneficial effects of the invention are as follows：It can not influence or influence Zn less4Sb3Conducting material thermoelectricity performance
On the premise of, it is to avoid Zn4Sb3Material at high temperature flexural deformation, improves its thermal structure stability, promotes Zn4Sb3The business of material
Change application.In addition, the present invention preparation technology also have method it is simple, it is with low cost the features such as.
Brief description of the drawings
Fig. 1 is the Zn obtained after grinding4Sb3Short grained structural representation.
Fig. 2 is dried Zn4Sb3The structural representation of powder particle.
Fig. 3 passes through the fine and close Zn after plasma activated sintering4Sb3The structural representation of thermoelectric composite material.
Main element symbol
Nothing
Embodiment
Below in conjunction with high stability Zn of the drawings and embodiments to the present invention4Sb3Composite thermoelectric material and its preparation side
Method makees specific introduce.
Fig. 1-3 are refer to, the embodiment of the present invention provides a kind of Zn with high stability4Sb3The preparation of thermoelectric composite material
Method, comprises the following steps：
1) by Zn4Sb3Block materials are ground；
2) inorganic salt solution is prepared；
3) by step 1) the middle Zn obtained4Sb3Little particle and step 2) prepare inorganic salt solution mix；
4) by step 3) obtain the Zn containing inorganic salt solution4Sb3Little particle is dried；
5) by step 4) the little particle sintering that obtains, obtain compact block, that is, obtain the Zn that structural stability is improved4Sb3Heat
Electric material.
In step 1) in, it is preferred that x scope is 0 to 1.It is furthermore preferred that x scope is 0 to 0.5.After grinding
Zn4Sb3Particle diameter is in 10nm~1mm, preferably：100nm~100 μm, more preferably：50 μm~100 μm.It is appreciated that Zn4Sb3
Particle diameter it is too small conducting material thermoelectricity performance can be caused to decline, particle can also be easily bonded together；Particle diameter is excessive to be unfavorable for improving
The stability of material, and be unfavorable for forming good contact with inorganic salts.In addition, the atmosphere of the grinding can be air atmosphere
Or inert gas atmosphere.
In step 2) in, in the inorganic salt solution inorganic salts include sulfate, nitrate, chlorate, acetate and its
Mixture.Preferably chlorate, such as iron chloride, copper chloride, zinc chloride.More preferably zinc chloride.Solvent in the solution
Including water, alcohol, ether, acetone and its mixture.In addition, the concentration of the inorganic salt solution is 0.01mol/L~1mol/L.
Experiment shows that each solvent is respectively provided with more preferred scope.When solvent is water, its concentration is about 0.05mol/L~0.2mol/
L。
In step 3) in, it is described by Zn4Sb3Little particle and step 2) inorganic salt solution prepared includes the step of mix：Will
Zn4Sb3In little particle immersion inorganic salt solution or to Zn4Sb3Little particle sprays inorganic salt solution.
In step 4) in, drying course selection drying or drying, the temperature of drying under inert atmosphere protection in atmosphere
For room temperature~500 DEG C.
In step 5) in, sintering processing selection hot pressed sintering or discharge plasma sintering.Hot pressed sintering speed is slower, electric discharge
Plasma agglomeration speed is fast, efficiency high.Therefore, preferably discharge plasma sintering.The temperature of sintering is 300 DEG C~500 DEG C, preferably
, the temperature of sintering is 400 DEG C~500 DEG C.When pressure is too small, the density of agglomerated material is relatively low, and pressure, which crosses conference, causes density
Too high its thermoelectricity capability of influence.Therefore, the pressure of sintering is 10MPa~300MPa, it is preferred that the pressure of sintering be 60MPa~
100MPa.It is furthermore preferred that the pressure of sintering is 60MPa~70MPa.The time of sintering is 5 minutes~30 minutes.After terminating
It is preferred that, 5 minutes~30 minutes are incubated under vacuum conditions, vacuum is preferably smaller than 100Pa.It is inorganic during sintering
Salt can form oxide tight in Zn4Sb3Particle surrounding, playing prevents Zn4Sb3Grains are deformed, and prevent Zn4Sb3
The effect of decomposition.
Fig. 3 is refer to, the embodiment of the present invention further relates to a kind of high stability Zn obtained according to the above method4Sb3It is compound
Thermoelectric material.
Embodiment 1
Weigh 5g Zn4Sb3Block materials, are ground using agate mortar, and grain diameter is at 50-100 μm；Prepare 0.1mol/
L ZnCl2Aqueous solution 50ml；By ground Zn4Sb3The ZnCl that powder particle immersion is prepared2In solution, and it is sufficiently mixed；
By mixed Zn4Sb3Powder is heated to 50 degrees Celsius in quartz ampoule, and argon gas atmosphere protection is lower to dry；By dried powder
In particle, the graphite jig for being fitted into a diameter of 20mm, it is put into discharge plasma sintering system and sinters.Sintering pressure 80MPa, burning
430 DEG C of junction temperature, vacuum are less than 10Pa, insulation 15 minutes.Compact block material is obtained, that is, obtains what heat endurance was improved
Zn4Sb3Thermoelectric material.
In addition, those skilled in the art can also do other changes in spirit of the invention, certainly, these are according to present invention essence
The change that god is done, should all be included in the interior of scope of the present invention.
Claims (10)
1. a kind of high stability Zn4Sb3The preparation method of composite thermoelectric material, it is characterised in that comprise the following steps：
1) by Zn4Sb3Block materials are ground；
2) inorganic salt solution is prepared；
3) by step 1) the middle Zn obtained4Sb3Little particle and step 2) prepare inorganic salt solution mix；
4) by step 3) obtain the Zn containing inorganic salt solution4Sb3Little particle is dried；
5) by step 4) the little particle sintering that obtains, obtain compact block, that is, obtain the Zn that structural stability is improved4Sb3Thermoelectricity material
Material.
2. preparation method according to claim 1, it is characterised in that the Zn after grinding4Sb3Particle diameter is in 10nm~1mm.
3. preparation method according to claim 1, it is characterised in that the step 1) in, the atmosphere of grinding is air gas
Atmosphere or inert gas atmosphere.
4. preparation method according to claim 1, it is characterised in that in step 2) in, it is inorganic in the inorganic salt solution
Salt includes sulfate, nitrate, chlorate, acetate and its mixture, the solvent in the solution include water, alcohol, ether,
Acetone and its mixture.
5. preparation method according to claim 1, it is characterised in that in step 2) in, the concentration of the inorganic salt solution
For 0.01mol/L~1mol/L.
6. preparation method according to claim 1, it is characterised in that in step 3) in, it is described by Zn4Sb3Little particle and step
The step of rapid inorganic salt solution 2) prepared is mixed includes：By Zn4Sb3In little particle immersion inorganic salt solution or to Zn4Sb3It is small
Spraying particles inorganic salt solution.
7. preparation method according to claim 1, it is characterised in that in step 4) in, drying course is selected in atmosphere
Drying is dried under inert atmosphere protection, and the temperature of drying is room temperature~500 DEG C.
8. preparation method according to claim 1, it is characterised in that in step 5) in, sintering processing selection hot pressed sintering
Or discharge plasma sintering.
9. preparation method according to claim 1, it is characterised in that in step 5) in, the temperature of sintering for 300 DEG C~
500 DEG C, the pressure of sintering is 10MPa~300MPa.
10. a kind of high stability Zn4Sb3Composite thermoelectric material, the high stability Zn4Sb3Composite thermoelectric material is by claim
Preparation method described in any one of 1-9 is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710098786.9A CN106956004B (en) | 2017-02-23 | 2017-02-23 | High stability Zn4Sb3Thermoelectric composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710098786.9A CN106956004B (en) | 2017-02-23 | 2017-02-23 | High stability Zn4Sb3Thermoelectric composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106956004A true CN106956004A (en) | 2017-07-18 |
| CN106956004B CN106956004B (en) | 2018-12-28 |
Family
ID=59481053
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| CN201710098786.9A Expired - Fee Related CN106956004B (en) | 2017-02-23 | 2017-02-23 | High stability Zn4Sb3Thermoelectric composite material and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS642380A (en) * | 1987-06-25 | 1989-01-06 | Idemitsu Petrochem Co Ltd | Manufacture of thermoelectric element |
| JP2002118299A (en) * | 2000-10-11 | 2002-04-19 | Komatsu Ltd | Manufacturing method of thermoelement |
| JP2005302954A (en) * | 2004-04-09 | 2005-10-27 | Mitsui Mining & Smelting Co Ltd | Thermoelectric conversion material and method for manufacturing the same |
| CN101723669A (en) * | 2008-10-31 | 2010-06-09 | 中国科学院上海硅酸盐研究所 | Compound capable of being used for thermoelectric material and preparation method thereof |
| CN101786862A (en) * | 2009-12-31 | 2010-07-28 | 清华大学 | Thermoelectric material and preparation method thereof |
| CN104409623A (en) * | 2014-10-21 | 2015-03-11 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
-
2017
- 2017-02-23 CN CN201710098786.9A patent/CN106956004B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS642380A (en) * | 1987-06-25 | 1989-01-06 | Idemitsu Petrochem Co Ltd | Manufacture of thermoelectric element |
| JP2002118299A (en) * | 2000-10-11 | 2002-04-19 | Komatsu Ltd | Manufacturing method of thermoelement |
| JP2005302954A (en) * | 2004-04-09 | 2005-10-27 | Mitsui Mining & Smelting Co Ltd | Thermoelectric conversion material and method for manufacturing the same |
| CN101723669A (en) * | 2008-10-31 | 2010-06-09 | 中国科学院上海硅酸盐研究所 | Compound capable of being used for thermoelectric material and preparation method thereof |
| CN101786862A (en) * | 2009-12-31 | 2010-07-28 | 清华大学 | Thermoelectric material and preparation method thereof |
| CN104409623A (en) * | 2014-10-21 | 2015-03-11 | 浙江大学 | Processing method for improving performance of N-type bismuth telluride base powder sinter block thermoelectric material |
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| Publication number | Publication date |
|---|---|
| CN106956004B (en) | 2018-12-28 |
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