CN109590481A - A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material - Google Patents
A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material Download PDFInfo
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- CN109590481A CN109590481A CN201910090373.5A CN201910090373A CN109590481A CN 109590481 A CN109590481 A CN 109590481A CN 201910090373 A CN201910090373 A CN 201910090373A CN 109590481 A CN109590481 A CN 109590481A
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- powder
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- thermoelectric material
- sintering
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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
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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
- 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
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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
- 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
- B22F3/23—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces involving a self-propagating high-temperature synthesis or reaction sintering step
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
- 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
Abstract
The present invention provides a kind of Cu2‑xMxThe high pressure method for preparing of Se alloy series thermoelectric material, belongs to field of thermoelectric material technique.Cu2‑xMxSe alloy series thermoelectric material composition are as follows: Cu2‑xMxSe, wherein doped chemical M type includes Ag, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, and dopant M doping x range is 0-10%.P-type Cu is prepared using high-pressure process2‑xMxThe technique of Se alloy series thermoelectric material is using solid metallic copper powder, selenium powder and doping metals simple substance as original material, using solid reaction process, first pass around a high-pressure synthesis material requested, then after being ground into the powder of certain particle size, cold moudling is carried out, is sintered later by a sub-high pressure.The present invention has the advantages that can fast, efficiently synthesize Cu2‑xMxSe alloy pure phase, becomes the thermoelectric material of application prospect.
Description
Technical field
The invention belongs to field of thermoelectric material technique, in particular, provide a kind of Cu2-xMxSe alloy (x=0-0.1M=
Ag, Ti, Zr, V, Cr, Mn, Fe, Co, Ni) thermoelectric material high pressure method for preparing.
Background technique
With Cu2Se is that the copper selenium alloy of representative is a kind of outstanding middle warm area thermoelectricity material with high conductivity, lower thermal conductivity
Material.Cu+It can be formed in sublattice and be moved in Se, referred to as " phonon glasses-electron crystal " (PGEC).Due to the characteristic, big electricity
Stream will lead to Cu in the case where passing through+Irreversible migration causes material structure avalanche, it is therefore desirable to adulterate some metallic elements
Pinning inhibits Cu+Nocuousness it is mobile, generally use at this stage mechanical alloying method or vacuum melting method combination hot pressed sintering or
SPS synthesis.Wherein the problem is that needing to carry out carbon coating processing to quartz ampoule in Vacuum Melting, otherwise due to the steaming of selenium
Air pressure is lower, and high temperature, which volatilizees rapidly, is full of entire quartz ampoule, can lead to quartz ampoule and burst；And then there is effects for mechanical alloying
Rate is low, requires the disadvantages of high to ball grinder.Therefore, the synthetic method for finding a kind of compromise can not only reduce it and synthesize difficulty, but also
Its combined coefficient can be improved.
Summary of the invention
The purpose of the present invention is to provide a kind of Cu2-xMxSe alloy (x=0-0.1M=Ag, Ti, Zr, V, Cr, Mn, Fe,
Co, Ni) series thermoelectric material high pressure method for preparing, it may be convenient to synthesize Cu2-xMxSe alloy avoids Se in synthesis process
The loss of element greatly improves the efficiency of synthesis.Become the thermoelectric material of application prospect.
A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material, it is characterised in that with solid metallic Cu powder,
All kinds of dopant M powder and nonmetallic Se powder are raw material, and dopant M powder includes Ag, Ti, Zr, V, Cr, Mn, Fe, Co, Ni；It utilizes
Ultra-high pressure sintering directly obtains Cu twice2-xMxSe (x=0-0.1) pure phase；Specific step is as follows:
(1) high-purity Cu powder, M powder, Se powder are put into nylon mixing tank by 2-x:x:1 (x=0-0.1) in molar ratio, are used
Ball-milling method mixing 2-10 hours, to mix well；
(2) by the obtained mixture of previous step after 80-100 DEG C of drying, in 6-10MPa cold moudling, it is put into the protection of molybdenum cup
Super high pressure mould in, under the protection of molybdenum cup carry out superelevation be pressed into so that raw material sufficiently reacts sintetics；
(3) vibration-type crusher is used to be crushed to granularity as 50 μm or less the product synthesized described in step (2)；
(4) by smashed product in 6-10MPa cold moudling；
(5) molded product is put into the mold of high-pressure sinter of molybdenum cup protection, is formed under the protection of molybdenum cup
Sintering.
Further, step (2) the super-pressure synthesis condition are as follows: under 3-6GPa, 600-900 DEG C constant temperature 3-5 minutes.
Further, step (5) the forming and sintering condition is: under 3-6GPa, 600-900 DEG C sintering 3-5 minutes.
The present invention has the advantages that compared with prior art, the present invention uses the synthetic method of super-pressure, can fast make
Standby Cu out2-xMxThe pure phase of Se alloy, the alloy belong to rhombic system, have C221 (20) symmetry.Attached drawing 1 gives 300K
The lower pure Cu synthesized using this method2The XRD diagram of Se sample
Detailed description of the invention
Fig. 1 is Cu under 300K2The XRD spectra of Se
Specific embodiment
Embodiment 1:
(1) high-purity Cu, Se powder is put into nylon mixing tank by 2:1 in molar ratio, is mixed 10 hours using ball-milling method, to fill
Divide and mixes.
(2) by the obtained mixture of previous step in a vacuum 100 DEG C drying 3 hours after in 10MPa cold moudling, place into six
In the high pressure apparatus of face, under the protection of molybdenum cup, under the conditions of 3GPa, in 900 DEG C constant temperature 4 minutes so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 10MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 3GPa, in 900
DEG C sintering 4 minutes.
Embodiment 2:
(1) high-purity Cu, Ag, Se powder is put into nylon mixing tank by 1.9:0.1:1 in molar ratio, using ball-milling method mixing 6
Hour, to mix well.
(2) by the obtained mixture of previous step in a vacuum 80 DEG C drying 3 hours after in 8MPa cold moudling, place into vacuum
In furnace, under the protection of molybdenum cup, in 5GPa, 800 DEG C constant temperature 3 minutes so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 8MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 5GPa, in 800
DEG C sintering 3 minutes.
Embodiment 3:
(1) high-purity Cu, Zr, Se powder is put into nylon mixing tank by 1.95:0.05:1 in molar ratio, is mixed using ball-milling method
2 hours, to mix well.
(2) by the obtained mixture of previous step in a vacuum 80 DEG C drying 3 hours after in 6MPa cold moudling, place into vacuum
In furnace, under the protection of molybdenum cup, in 6GPa, 600 DEG C constant temperature for 5 minutes, so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 6MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 6GPa, in 600
DEG C sintering 5 minutes.
Embodiment 4:
(1) high-purity Cu, Ti, Se powder is put into nylon mixing tank by 1.99:0.01:1 in molar ratio, is mixed using ball-milling method
8 hours, to mix well.
(2) by the obtained mixture of previous step in a vacuum 100 DEG C after drying 3 hours in 8MPa cold moudling, place into true
In empty furnace, under the protection of molybdenum cup, in 6GPa, 600 DEG C constant temperature for 5 minutes, so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 8MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 6GPa, in 600
DEG C sintering 5 minutes.
Embodiment 5:
(1) high-purity Cu, Ni, Se powder is put into nylon mixing tank by 1.92:0.08:1 in molar ratio, is mixed using ball-milling method
2 hours, to mix well.
(2) by the obtained mixture of previous step in a vacuum 100 DEG C after drying 3 hours in 8MPa cold moudling, place into true
In empty furnace, under the protection of molybdenum cup, in 3GPa, 900 DEG C constant temperature for 5 minutes, so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 8MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 3GPa, in 900
DEG C sintering 5 minutes.
Embodiment 6:
(1) high-purity Cu, Mn, Se powder is put into nylon mixing tank by 1.95:0.05:1 in molar ratio, is mixed using ball-milling method
6 hours, to mix well.
(2) by the obtained mixture of previous step in a vacuum 100 DEG C after drying 3 hours in 8MPa cold moudling, place into true
In empty furnace, under the protection of molybdenum cup, in 5GPa, 600 DEG C constant temperature 4 minutes so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 8MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 5GPa, in 600
DEG C sintering 4 minutes.
Embodiment 7:
(1) high-purity Cu, Fe, Se powder is put into nylon mixing tank by 1.9:0.1:1 in molar ratio, using ball-milling method mixing 8
Hour, to mix well.
(2) by the obtained mixture of previous step in a vacuum 80 DEG C after drying 3 hours in 10MPa cold moudling, place into true
In empty furnace, under the protection of molybdenum cup, in 6GPa, 900 DEG C constant temperature 3 minutes so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 10MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 6GPa, in 900
DEG C sintering 3 minutes.
Embodiment 8:
(1) high-purity Cu, Co, Se powder is put into nylon mixing tank by 1.98:0.02:1 in molar ratio, is mixed using ball-milling method
5 hours, to mix well.
(2) by the obtained mixture of previous step in a vacuum 100 DEG C after drying 3 hours in 8MPa cold moudling, place into true
In empty furnace, under the protection of molybdenum cup, in 3GPa, 800 DEG C constant temperature 4 minutes so that raw material sufficiently reacts synthesis.
(3) using vibration-type to be crushed crusher machine in the above-mentioned sample synthesized causes granularity for 50 μm or less.
(4) by smashed product according to the size requirement of super high pressure mould, in 8MPa cold moudling.
(5) molded product is put into the mold of ultra-high pressure sintering, under molybdenum cup protective condition, at 3GPa, in 800
DEG C sintering 4 minutes.
The Cu that embodiment 1 is prepared2Se XRD spectra invests in attached drawing 1, it can be seen that the Cu synthesized by this method2Se
Sample meets relatively good, no miscellaneous peak appearance with standard PDF card (19-1011).
Claims (3)
1. a kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material, it is characterised in that with solid metallic Cu powder, all kinds of
Dopant M powder and nonmetallic Se powder are raw material, and dopant M powder includes Ag, Ti, Zr, V, Cr, Mn, Fe, Co, Ni；Using twice
Ultra-high pressure sintering directly obtains Cu2-xMxSe (x=0-0.1) pure phase；Specific step is as follows:
(1) high-purity Cu powder, M powder, Se powder are put into nylon mixing tank by 2-x: x: 1 (x=0-0.1) in molar ratio, using ball milling
Method mixes 6-10 hours, to mix well；
(2) by the obtained mixture of previous step after 80-100 DEG C of drying, in 6-10MPa cold moudling, it is put into the super of molybdenum cup protection
In Belt-type tools, superelevation is carried out under the protection of molybdenum cup and is pressed into, so that raw material sufficiently reacts sintetics；
(3) vibration-type crusher is used to be crushed to granularity as 50 μm or less the product synthesized described in step (2)；
(4) by smashed product in 6-10MPa cold moudling；
(5) molded product is put into the mold of high-pressure sinter of molybdenum cup protection, forming and sintering is carried out under the protection of molybdenum cup.
2. Cu as described in claim 12-xMxThe high pressure method for preparing of Se alloy series thermoelectric material, it is characterised in that step (2)
The super-pressure synthesis condition are as follows: under 2-6GPa, 600-900 DEG C constant temperature 3-5 minutes.
3. Cu as described in claim 12-xMxThe high pressure method for preparing of Se alloy series thermoelectric material, it is characterised in that step (5)
The forming and sintering condition is: under 2-6GPa, 600-900 DEG C sintering 3-5 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113511897A (en) * | 2021-04-25 | 2021-10-19 | 郑州大学 | Bi2S3Block thermoelectric material and high-voltage preparation method thereof |
| US20210323060A1 (en) * | 2018-07-27 | 2021-10-21 | Centre National De La Recherche Scientifique | Copper-silver composite material |
Citations (4)
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| CN103130200A (en) * | 2011-11-25 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Thermoelectricity material compound and preparation method thereof |
| CN104310457A (en) * | 2014-09-30 | 2015-01-28 | 中国科学院上海硅酸盐研究所 | Thermoelectric material capable of inhibiting Cu ion migration and method for inhibiting Cu ion migration in Cu-base thermoelectric material |
| WO2015034321A1 (en) * | 2013-09-09 | 2015-03-12 | 주식회사 엘지화학 | Method for manufacturing thermoelectric material |
| CN107324292A (en) * | 2017-02-27 | 2017-11-07 | 武汉理工大学 | A kind of supper-fast preparation high-performance Cu2The method of Se block thermoelectric materials |
-
2019
- 2019-01-30 CN CN201910090373.5A patent/CN109590481A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130200A (en) * | 2011-11-25 | 2013-06-05 | 中国科学院上海硅酸盐研究所 | Thermoelectricity material compound and preparation method thereof |
| WO2015034321A1 (en) * | 2013-09-09 | 2015-03-12 | 주식회사 엘지화학 | Method for manufacturing thermoelectric material |
| CN104310457A (en) * | 2014-09-30 | 2015-01-28 | 中国科学院上海硅酸盐研究所 | Thermoelectric material capable of inhibiting Cu ion migration and method for inhibiting Cu ion migration in Cu-base thermoelectric material |
| CN107324292A (en) * | 2017-02-27 | 2017-11-07 | 武汉理工大学 | A kind of supper-fast preparation high-performance Cu2The method of Se block thermoelectric materials |
Non-Patent Citations (1)
| Title |
|---|
| LISHA XUE ET AL.: "Thermoelectric performance of Cu2Se bulk materials by high-temperature and high-pressure synthesis", 《JOURNAL OF MATERIOMICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210323060A1 (en) * | 2018-07-27 | 2021-10-21 | Centre National De La Recherche Scientifique | Copper-silver composite material |
| CN113511897A (en) * | 2021-04-25 | 2021-10-19 | 郑州大学 | Bi2S3Block thermoelectric material and high-voltage preparation method thereof |
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