CN107017331A - A kind of quick method for preparing cobalt antimony composite thermoelectric material - Google Patents
A kind of quick method for preparing cobalt antimony composite thermoelectric material Download PDFInfo
- Publication number
- CN107017331A CN107017331A CN201710226619.8A CN201710226619A CN107017331A CN 107017331 A CN107017331 A CN 107017331A CN 201710226619 A CN201710226619 A CN 201710226619A CN 107017331 A CN107017331 A CN 107017331A
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- China
- Prior art keywords
- powder
- thermoelectric material
- composite thermoelectric
- antimony composite
- cobalt antimony
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- UFIKNOKSPUOOCL-UHFFFAOYSA-N antimony;cobalt Chemical compound [Sb]#[Co] UFIKNOKSPUOOCL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 37
- 238000000227 grinding Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000013076 target substance Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000280 densification Methods 0.000 claims description 2
- 238000002360 preparation method Methods 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
- 239000000203 mixture Substances 0.000 abstract 1
- 229910018985 CoSb3 Inorganic materials 0.000 description 2
- 229910019752 Mg2Si Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005619 thermoelectricity 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
- 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
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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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 quick method for preparing cobalt antimony 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；This method directly carries out reaction in-situ using SPS sintering, and the material density of preparation is high, composition is uniform, excellent performance.
Description
Technical field
The present invention relates to thermoelectricity composite functional material field, and in particular to a kind of quickly to prepare cobalt antimony 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 quick method for preparing cobalt antimony composite thermoelectric material, and the preparation method substantially reduces preparation
In the cycle, simplify synthesis technique, reduce the dependence to equipment, with reaction speed is fast, preparation time is short, equipment is simple, work
Skill is simple, it is energy-efficient the advantages of；This method directly carries out reaction in-situ using SPS sintering, the material density of preparation is high, into
Divide uniform, excellent performance.
To achieve these goals, the invention provides a kind of quick method for preparing cobalt antimony composite thermoelectric material, the party
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, hybrid mode is ground and mixed, is obtained
Cobalt antimony composite thermoelectric material powder；
（2）Cobalt antimony composite thermoelectric material powder is fitted into graphite grinding tool and is compacted, is existed together with grinding tool<10Pa vacuum condition
Under be sintered, programming rate be 25 DEG C/min-50 DEG C/min, sintering temperature be 600-900 DEG C, pressure is 75-95MPa, burn
The knot time is 10-20h minutes, and raw material carries out reaction in-situ generation target substance during sintering, while pressurization can make again
It is densified, and finally gives the block cobalt antimony composite thermoelectric material of densification.
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, hybrid mode is ground and mixed, obtains cobalt antimony composite thermoelectric material powder.
Cobalt antimony composite thermoelectric material powder is fitted into graphite grinding tool and is compacted, is existed together with grinding tool<10Pa vacuum bar
It is sintered under part, programming rate is 25 DEG C/min, sintering temperature is 600 DEG C, pressure is 75MPa, sintering time is 10h points
Clock, raw material carries out reaction in-situ generation target substance during sintering, while pressurization can be densified it again, finally gives
Fine and close block cobalt antimony composite thermoelectric material.
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, obtains cobalt antimony composite thermoelectric material powder.
Cobalt antimony composite thermoelectric material powder is fitted into graphite grinding tool and is compacted, is existed together with grinding tool<10Pa vacuum bar
It is sintered under part, programming rate is 30 DEG C/min, sintering temperature is 700 DEG C, pressure is 80MPa, sintering time is 15h points
Clock, raw material carries out reaction in-situ generation target substance during sintering, while pressurization can be densified it again, finally gives
Fine and close block cobalt antimony composite thermoelectric material.
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, obtains cobalt antimony composite thermoelectric material powder.
Cobalt antimony composite thermoelectric material powder is fitted into graphite grinding tool and is compacted, is existed together with grinding tool<10Pa vacuum bar
It is sintered under part, programming rate is 50 DEG C/min, sintering temperature is 900 DEG C, pressure is 95MPa, sintering time is 20h points
Clock, raw material carries out reaction in-situ generation target substance during sintering, while pressurization can be densified it again, finally gives
Fine and close block cobalt antimony composite thermoelectric material.
Claims (1)
1. a kind of quick method for preparing cobalt antimony 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, hybrid mode is ground and mixed, is obtained
Cobalt antimony composite thermoelectric material powder；
（2）Cobalt antimony composite thermoelectric material powder is fitted into graphite grinding tool and is compacted, is existed together with grinding tool<10Pa vacuum condition
Under be sintered, programming rate be 25 DEG C/min-50 DEG C/min, sintering temperature be 600-900 DEG C, pressure is 75-95MPa, burn
The knot time is 10-20h minutes, and raw material carries out reaction in-situ generation target substance during sintering, while pressurization can make again
It is densified, and finally gives the block cobalt antimony composite thermoelectric material of densification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710226619.8A CN107017331A (en) | 2017-04-09 | 2017-04-09 | A kind of quick method for preparing cobalt antimony composite thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710226619.8A CN107017331A (en) | 2017-04-09 | 2017-04-09 | A kind of quick method for preparing cobalt antimony composite thermoelectric material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107017331A true CN107017331A (en) | 2017-08-04 |
Family
ID=59445593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710226619.8A Withdrawn CN107017331A (en) | 2017-04-09 | 2017-04-09 | A kind of quick method for preparing cobalt antimony composite thermoelectric material |
Country Status (1)
| Country | Link |
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| CN (1) | CN107017331A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106410023A (en) * | 2016-12-18 | 2017-02-15 | 苏州思创源博电子科技有限公司 | Method for preparing graphene composite thermoelectric material |
-
2017
- 2017-04-09 CN CN201710226619.8A patent/CN107017331A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106410023A (en) * | 2016-12-18 | 2017-02-15 | 苏州思创源博电子科技有限公司 | Method for preparing graphene composite thermoelectric material |
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Application publication date: 20170804 |