CN106981566A - A kind of preparation method of cobalt antimony base composite thermoelectric material - Google Patents
A kind of preparation method of cobalt antimony base composite thermoelectric material Download PDFInfo
- Publication number
- CN106981566A CN106981566A CN201710246409.5A CN201710246409A CN106981566A CN 106981566 A CN106981566 A CN 106981566A CN 201710246409 A CN201710246409 A CN 201710246409A CN 106981566 A CN106981566 A CN 106981566A
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- China
- Prior art keywords
- powder
- thermoelectric material
- composite thermoelectric
- cobalt antimony
- preparation
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Links
- 239000000463 material Substances 0.000 title claims abstract description 50
- UFIKNOKSPUOOCL-UHFFFAOYSA-N antimony;cobalt Chemical compound [Sb]#[Co] UFIKNOKSPUOOCL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 42
- 238000005245 sintering Methods 0.000 claims description 25
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 230000005619 thermoelectricity Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 3
- 229910018985 CoSb3 Inorganic materials 0.000 description 2
- 229910019752 Mg2Si Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910018989 CoSb Inorganic materials 0.000 description 1
- 206010009856 Cold exposure injury Diseases 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910005642 SnTe Inorganic materials 0.000 description 1
- 229910007372 Zn4Sb3 Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
Classifications
-
- 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
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a kind of preparation method of cobalt antimony base composite thermoelectric material, the preparation method substantially reduces manufacturing cycle, simplifies synthesis technique, reduces the dependence to equipment, has the advantages that reaction speed is fast, preparation time is short, equipment is simple, technique is simple, energy-efficient；The final thermoelectricity capability for causing material is greatly enhanced, with good industrialization prospect.
Description
Technical field
The present invention relates to thermoelectricity composite functional material field, and in particular to a kind of preparation side of cobalt antimony base composite thermoelectric material
Method.
Background technology
Thermoelectric material (Thermoelectric Materials) is also referred to as thermoelectric material.Thermoelectric material is mainly used in
Prepare thermoelectric cooling device and Thermoelectric Generator.Temperature gradient field heat to electricity conversion principle abbreviation thermoelectric principle
(Thermoe1ectric), its discovery can trace back to for 19th century, 1822, and ThomasAlebeck has found thermoelectromotive force effect
Answer (thermoelectric material electricity generating principle, i.e. Alebeck principles)；1834, Jean Peltier had found two difference in current loop
Effects of reduced temperature (thermoelectric material refrigeration principle, i.e. Peltier principles) at material conductor junction interface.1950s finds
Some semi-conducting materials are good thermoelectric materials.The performance of thermoelectric material depends primarily on the dimensionless thermoelectric figure of merit of material
ZT, the value is defined as：ZT=S2σ T/ κ, wherein, S is Seebeck coefficients, and σ is electrical conductivity, and κ is thermal conductivity, and T is absolute temperature.
ZT values are higher, and the generating of corresponding device and refrigerating efficiency are higher.
The more warm thermoelectric material of Recent study mainly includes：Antimonide (CoSb3And Zn4Sb3), silicide
(Mg2Si and Mn2) and tellurides (PbTe and SnTe) etc. Si.Thermoelectricity capability is high among these, it is steady to constitute nontoxic, military service performance
Fixed CoSb3And Mg2Si most commercial applications potentiality, the electrode material of its device also turns into study hotspot in recent years.But
Mg2The CoSb of Mg elements and filled type in Si3In filling element (be generally alkali metal, alkaline-earth metal and rare metal) easily
Oxidation causes synthesis technique excessively complicated, it is necessary to operated under glove box protective atmosphere.
The content of the invention
The present invention provides a kind of preparation method of cobalt antimony base composite thermoelectric material, and the preparation method substantially reduces preparation week
Phase, simplify synthesis technique, reduce the dependence to equipment, with reaction speed is fast, preparation time is short, equipment is simple, technique
Simply, energy-efficient the advantages of；The final thermoelectricity capability for causing material is greatly enhanced, with good industrialization
Prospect.
To achieve these goals, the invention provides a kind of preparation method of cobalt antimony base composite thermoelectric material, this method
Comprise the following steps：
（1）Prepare cobalt antimony composite thermoelectric material powder
By chemical formula Co4-xAlxSb12-yTeyThe stoichiometric proportion of each element carries out weighing Co powder, Al powder, Sb powder, Te powder as original
Material, wherein 0.03≤x≤0.5,0.02≤y≤0.4；Material powder is well mixed；
（2）Mixed material powder is obtained into nanometer cobalt antimony composite thermoelectric material powder after ball milling under inert gas shielding；Institute
The rotating speed for stating ball milling is 400-600rpm, and the time is 3-4h；
（3）Using discharge plasma sintering system under vacuum or inert gas shielding to gained nanometer cobalt antimony composite thermoelectric material
Powder carries out discharge plasma sintering, obtains the cobalt antimony base composite thermoelectric material；The condition of the discharge plasma sintering is：
Heating rate is 100-150 DEG C/min, and sintering temperature is 900-1050 DEG C, and sintering pressure is 60-85MPa, and soaking time is 15-
20min。
Embodiment
Embodiment one
By chemical formula Co0.397Al0.03Sb11.98Te0.02The stoichiometric proportion of each element carries out weighing Co powder, Al powder, Sb powder, Te powder
It is used as raw material；Material powder is well mixed.
Mixed material powder is obtained into nanometer cobalt antimony composite thermoelectric material powder after ball milling under inert gas shielding；Institute
The rotating speed for stating ball milling is 400rpm, and the time is 3h.
Thermoelectricity material is combined to gained nanometer cobalt antimony under vacuum or inert gas shielding using discharge plasma sintering system
Feed powder body carries out discharge plasma sintering, obtains the cobalt antimony base composite thermoelectric material；The condition of the discharge plasma sintering
For：Heating rate is 100 DEG C/min, and sintering temperature is 900 DEG C, and sintering pressure is 60MPa, and soaking time is 15min.
Embodiment two
By chemical formula Co3.9Al0.1Sb19.8Te0.2The stoichiometric proportion of each element carries out weighing Co powder, Al powder, Sb powder, Te powder work
For raw material；Material powder is well mixed, hybrid mode is ground and mixed.
Mixed material powder is obtained into nanometer cobalt antimony composite thermoelectric material powder after ball milling under inert gas shielding；Institute
The rotating speed for stating ball milling is 500rpm, and the time is 3.5h.
Thermoelectricity material is combined to gained nanometer cobalt antimony under vacuum or inert gas shielding using discharge plasma sintering system
Feed powder body carries out discharge plasma sintering, obtains the cobalt antimony base composite thermoelectric material；The condition of the discharge plasma sintering
For：Heating rate is 120 DEG C/min, and sintering temperature is 1000 DEG C, and sintering pressure is 75MPa, and soaking time is 18min.
Embodiment three
By chemical formula Co3.5Al0.5Sb11.6Te0.4The stoichiometric proportion of each element carries out weighing Co powder, Al powder, Sb powder, Te powder work
For raw material；Material powder is well mixed, hybrid mode is ground and mixed.
Mixed material powder is obtained into nanometer cobalt antimony composite thermoelectric material powder after ball milling under inert gas shielding；Institute
The rotating speed for stating ball milling is 600rpm, and the time is 4h.
Thermoelectricity material is combined to gained nanometer cobalt antimony under vacuum or inert gas shielding using discharge plasma sintering system
Feed powder body carries out discharge plasma sintering, obtains the cobalt antimony base composite thermoelectric material；The condition of the discharge plasma sintering
For：Heating rate is 150 DEG C/min, and sintering temperature is 1050 DEG C, and sintering pressure is 85MPa, and soaking time is 20min.
Claims (1)
1. a kind of preparation method of cobalt antimony base composite thermoelectric material, this method comprises the following steps：
（1）Prepare cobalt antimony composite thermoelectric material powder
By chemical formula Co4-xAlxSb12-yTeyThe stoichiometric proportion of each element carries out weighing Co powder, Al powder, Sb powder, Te powder as original
Material, wherein 0.03≤x≤0.5,0.02≤y≤0.4；Material powder is well mixed；
（2）Mixed material powder is obtained into nanometer cobalt antimony composite thermoelectric material powder after ball milling under inert gas shielding；Institute
The rotating speed for stating ball milling is 400-600rpm, and the time is 3-4h；
（3）Using discharge plasma sintering system under vacuum or inert gas shielding to gained nanometer cobalt antimony composite thermoelectric material
Powder carries out discharge plasma sintering, obtains the cobalt antimony base composite thermoelectric material；The condition of the discharge plasma sintering is：
Heating rate is 100-150 DEG C/min, and sintering temperature is 900-1050 DEG C, and sintering pressure is 60-85MPa, and soaking time is 15-
20min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710246409.5A CN106981566A (en) | 2017-04-15 | 2017-04-15 | A kind of preparation method of cobalt antimony base composite thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710246409.5A CN106981566A (en) | 2017-04-15 | 2017-04-15 | A kind of preparation method of cobalt antimony base composite thermoelectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106981566A true CN106981566A (en) | 2017-07-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710246409.5A Pending CN106981566A (en) | 2017-04-15 | 2017-04-15 | A kind of preparation method of cobalt antimony base composite thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106981566A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417358A (en) * | 2002-12-19 | 2003-05-14 | 北京工业大学 | Prepn of Co-Sb alloy as thermoelectric material |
| CN101350394A (en) * | 2008-09-11 | 2009-01-21 | 清华大学 | Pyroelectric material with quadruple skutterudite structure and preparation method thereof |
| CN105671344A (en) * | 2014-11-21 | 2016-06-15 | 武汉理工大学 | Method for preparing high-performance CoSb3-based thermoelectric materials by one step |
-
2017
- 2017-04-15 CN CN201710246409.5A patent/CN106981566A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1417358A (en) * | 2002-12-19 | 2003-05-14 | 北京工业大学 | Prepn of Co-Sb alloy as thermoelectric material |
| CN101350394A (en) * | 2008-09-11 | 2009-01-21 | 清华大学 | Pyroelectric material with quadruple skutterudite structure and preparation method thereof |
| CN105671344A (en) * | 2014-11-21 | 2016-06-15 | 武汉理工大学 | Method for preparing high-performance CoSb3-based thermoelectric materials by one step |
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Application publication date: 20170725 |
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