CN106684236A - Method for preparing high-performance Cu2GeTe3 thermoelectric material - Google Patents
Method for preparing high-performance Cu2GeTe3 thermoelectric material Download PDFInfo
- Publication number
- CN106684236A CN106684236A CN201611155280.9A CN201611155280A CN106684236A CN 106684236 A CN106684236 A CN 106684236A CN 201611155280 A CN201611155280 A CN 201611155280A CN 106684236 A CN106684236 A CN 106684236A
- Authority
- CN
- China
- Prior art keywords
- thermoelectric material
- performance
- gete
- preparation
- ingot
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- H10N10/80—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
-
- 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
Abstract
The invention relates to a method for preparing a high-performance Cu2GeTe3 thermoelectric material. The method comprises the following steps: weighing raw materials Cu powder, Ge granules and Te granules according to a stoichiometric ratio of 2:1:3, and evenly mixing the raw materials to obtain a mixture; carrying out a reaction on the mixture at 900-1000 DEG C for 12-24h by using a high temperature vacuum melting method; separately performing treatments of natural cooling in the furnace, quenching and annealing after quenching to obtain an ingot, washing the ingot, drying the ingot, and grinding the ingot into fine powder in an agate mortar; and carrying out discharge plasma sintering on the obtained fine powder to obtain the high-performance Cu2GeTe3 thermoelectric material. Compared with the Cu2GeTe3 thermoelectric material prepared by the traditional method of melting and natural cooling in the furnace, the performance of the high-performance Cu2GeTe3 thermoelectric material prepared by melting and annealing is improved by 38%. The method has the advantages of simple preparation process, high controllability, low cost, good stability and the like, and is suitable for the preparation of the high-performance Cu2GeTe3 thermoelectric material.
Description
Technical field
The invention belongs to the preparing technical field of thermoelectric material, emphasis relates to a kind of high-performance Cu2GeTe3The system of thermoelectric material
Standby technique.
Background technology
Thermoelectric material is the energy and material that a kind of utilization pyroelectric effect is realized being converted between heat and electricity, and it utilizes Seebeck
Heat energy can be converted into electric energy by effect, and heat energy can be converted electrical energy into using Peltier effects.The thermoelectric material system of using
Standby thermoelectric power generating component without mechanical moving element, does not produce noise pollution when having work, does not also discharge any poisonous
Or greenhouse gases, small volume, long lifespan, high reliability.In space industry, industrial afterheat recovery and geothermal utilization etc.
Field has much potentiality, in the today's society that the energy is increasingly reduced, be badly in need of energy and material to alleviate, at the same time energy and material exist
In the modern society of energy growing tension, people progressively strengthen the efficient utilization study of the energy, and these all constantly promote people
Research and development to high performance thermoelectric material.
Be pursue higher performance thermoelectric material, the new thermoelectric material of the continuous developmental research of people, it aims at effort
While improving the electrical properties such as electrical conductivity, the Seebeck coefficient of material aspect thermal conductivity is reduced in terms of material hot property.Thermoelectricity
The performance height of material is assessed using dimensionless thermoelectric figure of merit ZT, and the expression formula of ZT is ZT=α2σ T/ κ, α is referred to as in formula
Seebeck coefficients are also thermoelectromotive force, and it refers to the electrical potential difference size of unit temperature.σ is the electrical conductivity of material, and κ is material
Thermal conductivity, T is absolute temperature.The parameter of α, σ, κ these three thermoelectricity capabilities depends on the electronic structure and carrier of material
Scattering is strong and weak, and wherein the thermal conductivity of material is divided into lattice thermal conductivity and electron thermal conductivity again, and its expression formula is κ=κL+κe, κLIt is
Refer to the lattice thermal conductivity of material, κeRefer to the electron thermal conductivity of material, want reduction κ and it is critical only that reduction κL, that is, strengthen lattice
Dot matrix is to the scattering of phonon so as to reduce lattice thermal conductivity.Theoretically analyze, the material of amorphous structure has low κ values,
Glem Slack propose that a kind of new concept material is referred to as phonon glasses electron crystal " phonon glass electron
Crystal " (PGEC), that is, a kind of can have electric conductivity and its thermal conductivity such as glass one higher as crystal
The weak material of sample.Slack thinks there is a kind of weak " rattling " atom of adhesion in crystal structure, has to heat-carrying phonon
Strong scattering process causes thermal conductivity drastically to decline, and does not have too big influence on electric conductivity.
Cu2GeTe3Thermoelectric material is a kind of thermoelectric material of diamond-like, its complicated crystal structure and relatively low
Specific heat impart the relatively low thermal conductivity of such material, at the same time possess preferable electrical property.It is referred to as phonon glasses electricity
Sub- crystal（PGEC）In a member.Current Cu2GeTe3Base thermoelectricity material is answered again by after compound or admixture and doping
The dimensionless thermoelectric figure of merit of the thermoelectric material after conjunction（ZT）All have and be obviously improved, be great in high temperature thermoelectric material
A kind of new thermoelectric materials of development potentiality.The present invention under the theoretical direction of ternary alloy phase diagram, from different preparation works
The high performance Cu of skill gain of parameter2GeTe3Thermoelectric material, either improves from means such as compound or doping at present
Cu2GeTe3Thermoelectric material, to its matrix phase Cu2GeTe3Performance and purity suffer from strict requirements, there is rule to follow,
Under having a scientific guidance principle of Zhang Kezun, for high-purity, high performance Cu2GeTe3The preparation of matrix phase has much room for improvement.From
Different preparation technology parameters prepares high-performance, the Cu of high-purity2GeTe3Thermoelectric material, is Cu2GeTe3Base thermoelectricity material
Lifting of the compound and different element dopings to the thermoelectric figure of merit of its material provides experimental basis and refers to and instruct basis.
The content of the invention
The present invention is directed to high-performance Cu2GeTe3Thermoelectric material possesses larger development potentiality, its object is to for
Cu2GeTe3The compound and doping of base thermoelectricity material provides a kind of high-performance, the Cu of high-purity2GeTe3Matrix phase.Party's legal system
Standby process is simple, controllability is high, low cost, the advantages of good stability.
The technical scheme that is proposed to achieve the above object of the present invention is：
A kind of high-performance Cu2GeTe3The preparation method of thermoelectric material, it is comprised the following steps：
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and mixed, and are existed using high-temperature vacuum fusion method
900-1000 DEG C is reacted 12-24 hours；Block is obtained after nature furnace cooling, quenching and quenching after annealing treatment is respectively adopted
Ingot, is washed to it, and drying and processing is carried out at a certain temperature, and grinding obtains Cu in agate mortar2GeTe3Fine powder.To
To fine powder carry out discharge plasma sintering, obtain high-performance Cu2GeTe3Thermoelectric material, the dimensionless thermoelectricity obtained in 700K is excellent
Value up to 0.61, compared with Cu prepared by conventional melt method2GeTe3The ZT values 0.44 of thermoelectric material are relative to improve 38%.
The beneficial effects of the invention are as follows：(1) preparation process is simple of the present invention, technological parameter are easy to control, can be used for high-volume
It is prepared by production；(2) preparation technology low cost of the present invention, controllability is high, with application value higher；(3) present invention is not using
Same preparation technology prepares high performance Cu2GeTe3Thermoelectric material.
Specific embodiment：
The present invention is illustrated below by way of instantiation.
The present invention is comprised the following steps：（1）Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and mixed
It is even.（2）Above-mentioned compound is carried out into vacuum fusion treatment using different melt temperatures, soaking time and cooldown rate.（3）It is right
Cu prepared by vacuum fusion2GeTe3After block ingot carries out washing and drying treatment, fine powder is ground to form.（4）Fine powder to obtaining is put
Electric plasma agglomeration, obtains high performance Cu2GeTe3Thermoelectric material.
Embodiment 1
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and are uniformly mixed so as to obtain three kinds of compounds of element, will
The compound for obtaining is placed in carries out Vacuum Package treatment in quartz ampoule, packaged quartz ampoule is placed in into temperature programmed control vertical tubular
In resistance furnace, 960 DEG C are warming up to the speed of 2 DEG C/min, 12h is incubated at such a temperature, then cool to room temperature with the furnace.Will be molten
Melt the block ingot of preparation, washed and ground to form fine powder.Fine powder to obtaining carries out discharge plasma sintering, and sintering pressure is
10MPa, soaking time is 6min, obtains Cu2GaTe3Thermoelectric material ZT values reach 0.45 in 700K.
Embodiment 2
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and are uniformly mixed so as to obtain three kinds of compounds of element, will
The compound for obtaining is placed in carries out Vacuum Package treatment in quartz ampoule, packaged quartz ampoule is placed in into temperature programmed control vertical tubular
In resistance furnace, 1000 DEG C are warming up to the speed of 2 DEG C/min, 12h is incubated at such a temperature, then cool to room temperature with the furnace.Will
The block ingot for preparing is melted, fine powder is washed and ground to form.Fine powder to obtaining carries out discharge plasma sintering, and sintering pressure is
10MPa, soaking time is 6min, obtains Cu2GeTe3Thermoelectric material ZT values reach 0.44 in 700K.
Embodiment 3
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and are uniformly mixed so as to obtain three kinds of compounds of element, will
The compound for obtaining is placed in carries out Vacuum Package treatment in quartz ampoule, packaged quartz ampoule is placed in into temperature programmed control vertical tubular
In resistance furnace, 1000 DEG C are warming up to the speed of 2 DEG C/min, 24h is incubated at such a temperature, then cool to room temperature with the furnace.Will
The block ingot for preparing is melted, fine powder is washed and ground to form.Fine powder to obtaining carries out discharge plasma sintering, and sintering pressure is
10MPa, soaking time is 6min, obtains Cu2GeTe3Thermoelectric material ZT values reach 0.46 in 700K.
Embodiment 4
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and are uniformly mixed so as to obtain three kinds of compounds of element, will
The compound for obtaining is placed in carries out Vacuum Package treatment in quartz ampoule, packaged quartz ampoule is placed in into temperature programmed control vertical tubular
In resistance furnace, 1000 DEG C are warming up to the speed of 2 DEG C/min, 24h is incubated at such a temperature, carry out Quenching Treatment.Melting is quenched
Block ingot prepared by fire, is washed and is ground to form fine powder.Fine powder to obtaining carries out discharge plasma sintering, and sintering pressure is
10MPa, soaking time is 6min, obtains Cu2GeTe3Thermoelectric material ZT values reach 0.52 in 700K.
Embodiment 5
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and are uniformly mixed so as to obtain three kinds of compounds of element, will
The compound for obtaining is placed in carries out Vacuum Package treatment in quartz ampoule, packaged quartz ampoule is placed in into temperature programmed control vertical tubular
In resistance furnace, 1000 DEG C are warming up to the speed of 2 DEG C/min, 24h is incubated at such a temperature, carry out Quenching Treatment.Melting is quenched
Block ingot prepared by fire, is made annealing treatment in tube furnace, and annealing temperature is 800 DEG C, and annealing time is 3 days, after annealing
Block ingot carries out being washed and being ground to form fine powder.Fine powder to obtaining carries out discharge plasma sintering, and sintering pressure is 10MPa,
Soaking time is 8min, obtains Cu2GeTe3Thermoelectric material ZT values reach 0.59 in 700K.
Embodiment 6
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and are uniformly mixed so as to obtain three kinds of compounds of element, will
The compound for obtaining is placed in carries out Vacuum Package treatment in quartz ampoule, packaged quartz ampoule is placed in into temperature programmed control vertical tubular
In resistance furnace, 1000 DEG C are warming up to the speed of 2 DEG C/min, 24h is incubated at such a temperature, carry out Quenching Treatment.Melting is quenched
Block ingot prepared by fire, is made annealing treatment in tube furnace, and annealing temperature is 760 DEG C, and annealing time is 3 days, after annealing
Block ingot carries out being washed and being ground to form fine powder.Fine powder to obtaining carries out discharge plasma sintering, and sintering pressure is 10MPa,
Soaking time is 8min, obtains Cu2GeTe3Thermoelectric material ZT values reach 0.61 in 700K.
Contrast above case obtains thermoelectric material, and it is 0.61, the heat of the relatively conventional cold preparation of melting furnace to obtain maximum ZT values
Electric material performance improves 38%.
Claims (8)
1. a kind of high-performance Cu2GeTe3The preparation method of thermoelectric material, is primarily characterized in that：
By Cu powder, Ge, Te respectively according to 2:1:3 stoichiometric proportions are weighed and mixed, and are existed using high-temperature vacuum fusion method
900-1000 DEG C is reacted 12-24 hours；Block is obtained after nature furnace cooling, quenching and quenching after annealing treatment is respectively adopted
Ingot, washs to it, drying and processing, and grinding obtains Cu in agate mortar2GeTe3Fine powder.
2. pair fine powder for obtaining carries out discharge plasma sintering, obtains high-performance Cu2GeTe3Thermoelectric material.
3. according to a kind of high-performance Cu described in claim 12GeTe3The preparation method of thermoelectric material, it is characterised in that：It is selected
Cu powder purities are that 99.99%, Ge purity is that 99.99%, Te purity is 99.999%, weigh Mass accuracy up to very much
One of.
4. according to a kind of high-performance Cu described in claim 32GeTe3The preparation method of thermoelectric material, it is characterised in that：Wherein
Cu powder, Ge and Te carries out artificial preliminary mixing in organic solvent.
5. according to a kind of high-performance Cu described in claim 42GeTe3The preparation method of thermoelectric material, it is characterised in that：Its people
The mixture that work is mixed carries out drying and processing at 100-150 DEG C.
6. according to a kind of high-performance Cu described in claim 52GeTe3The preparation method of thermoelectric material, it is characterised in that：Obtain
Mixture after drying is prepared using vacuum high-temperature fusion method, and technological parameter is：Carry out melting for 12-24 hours at 900-1000 DEG C
Melt.
7. according to a kind of high-performance Cu described in claim 62GeTe3The preparation method of thermoelectric material, it is characterised in that：Using
Furnace cooling, the different cooling rate such as quenching and quenching after annealing is prepared into Cu2GeTe3Block ingot.
8. according to a kind of high-performance Cu described in claim 72GeTe3The preparation method of thermoelectric material, it is characterised in that：Obtain
Cu2GeTe3Block ingot carries out discharge plasma sintering after grinding to form fine powder.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016110707624 | 2016-11-29 | ||
| CN201611070762 | 2016-11-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106684236A true CN106684236A (en) | 2017-05-17 |
Family
ID=58867998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611155280.9A Pending CN106684236A (en) | 2016-11-29 | 2016-12-14 | Method for preparing high-performance Cu2GeTe3 thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106684236A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950389A (en) * | 2019-03-18 | 2019-06-28 | 清华大学 | Middle warm area high performance thermoelectric material preparation method and middle warm area high performance thermoelectric material |
| CN111334685A (en) * | 2020-04-03 | 2020-06-26 | 济南大学 | Preparation method of high-density Half-Heusler thermoelectric material and obtained product |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102194989A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Method for preparing thermoelectric material of ternary diamond structure |
| US20140174494A1 (en) * | 2012-11-20 | 2014-06-26 | Samsung Electronics Co., Ltd. | Thermoelectric material, thermoelectric element and apparatus including the same, and preparation method thereof |
| CN104046876A (en) * | 2014-06-16 | 2014-09-17 | 济南大学 | Graphene/Cu2AX3 type thermoelectric composite material and preparation method thereof |
-
2016
- 2016-12-14 CN CN201611155280.9A patent/CN106684236A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102194989A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Method for preparing thermoelectric material of ternary diamond structure |
| US20140174494A1 (en) * | 2012-11-20 | 2014-06-26 | Samsung Electronics Co., Ltd. | Thermoelectric material, thermoelectric element and apparatus including the same, and preparation method thereof |
| CN104046876A (en) * | 2014-06-16 | 2014-09-17 | 济南大学 | Graphene/Cu2AX3 type thermoelectric composite material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950389A (en) * | 2019-03-18 | 2019-06-28 | 清华大学 | Middle warm area high performance thermoelectric material preparation method and middle warm area high performance thermoelectric material |
| CN111334685A (en) * | 2020-04-03 | 2020-06-26 | 济南大学 | Preparation method of high-density Half-Heusler thermoelectric material and obtained product |
| CN111334685B (en) * | 2020-04-03 | 2021-11-02 | 济南大学 | Preparation method of high-density Half-Heusler thermoelectric material and obtained product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103872237B (en) | Copper-sulfur-based high-performance thermoelectric material and preparation method thereof | |
| CN108238796B (en) | Copper seleno solid solution thermoelectric material and preparation method thereof | |
| CN102194989B (en) | Method for preparing thermoelectric material of ternary diamond structure | |
| CN107799646B (en) | Alloy thermoelectric semiconductor material and preparation method thereof | |
| CN106986315B (en) | A kind of p-type bismuth telluride thermoelectric material and preparation method suitable for low-temperature electricity-generating | |
| CN108231991A (en) | A kind of p-type bismuth telluride-base thermoelectric material to generate electricity near room temperature solid-state refrigeration and waste heat | |
| CN107887495B (en) | One-step preparation of Cu2Method for Se/BiCuSeO composite thermoelectric material | |
| CN103700759A (en) | Nanocomposite structure Mg2Si-based thermoelectric material and preparation method thereof | |
| CN102280570A (en) | Trace Cu-doped Bi2S3-based thermoelectric material | |
| CN106684236A (en) | Method for preparing high-performance Cu2GeTe3 thermoelectric material | |
| CN105990510B (en) | A kind of copper seleno high performance thermoelectric material and preparation method thereof | |
| CN108417704B (en) | High-performance europium-doped PbTe-based thermoelectric material and preparation method thereof | |
| CN108516526B (en) | High-performance PbTe-based solid solution thermoelectric material and preparation method thereof | |
| CN104004935A (en) | Method for super-rapidly preparing high-performance high-silicon-manganese thermoelectric material | |
| CN105702847A (en) | Method for increasing performance of BiTeSe-based N-type semiconductor thermoelectric material | |
| US20210074900A1 (en) | ZrNiSn-BASED HALF-HEUSLER THERMOELECTRIC MATERIAL AND PROCESS FOR MANUFACTURING SAME AND FOR REGULATING ANTISITE DEFECTS THEREIN | |
| CN107293637B (en) | Preparation method of high-performance GeSbTe-based thermoelectric material | |
| CN104022218A (en) | High-performance SbAgSeS-based thermoelectric material and preparation method thereof | |
| CN108520915B (en) | High-performance PbTe-SnTe alloy-based thermoelectric material and preparation method thereof | |
| CN103290249A (en) | Method and apparatus for producing thermoelectric conversion material, and sputtering target production method | |
| CN101857929A (en) | Zinc antimony based porous p-type thermoelectric material and preparation method thereof | |
| CN105420528B (en) | One kind prepares high-performance AgInTe2The method of thermoelectric material | |
| CN109087987A (en) | A kind of α-MgAgSb base nano composite thermoelectric materials and preparation method thereof | |
| CN101307394A (en) | Process for preparing bismuth telluride -based thermoelectric material by liquid quenching cooperated with spark plasma sintering | |
| CN104711444B (en) | A kind of method of quick preparation high-performance SiGe high temperature thermoelectric alloy materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhao Degang Inventor after: Ning Jiai Inventor after: Wu Di Inventor before: Ning Jiai Inventor before: Zhao Degang Inventor before: Wu Di |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170517 |