CN103130200A - Thermoelectricity material compound and preparation method thereof - Google Patents
Thermoelectricity material compound and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a thermoelectricity material compound and a preparation method thereof, wherein the chemical composition of the thermoelectricity material compound is Cu2-xSe, and x is more than or equal to 0 and is less than or equal to 0.15. The thermoelectricity material compound is a semiconductor, and has characteristics of simple components, low price raw materials, high conductivity, high seebeck coefficient, low thermal conductivity, excellent thermoelectric merit figure, and good industrial application prospect compared to the conventional thermoelectricity material.
Description
Technical field
The present invention relates to the thermoelectric material field, be specifically related to a kind of novel high-performance thermoelectric material, especially thermoelectric material of the chalcogenide base of p-type Cu and preparation method thereof.
Background technology
Thermoelectric generation technology is to utilize semiconductor material directly to carry out the technology that heat energy and electric energy are changed mutually, and its principle is that Sai Beike (Seebeck) effect and Pa Er note (Peltier) effect according to material realizes thermoelectric power generation and thermoelectric refrigeration.That this technology has on using is pollution-free, machinery-free transmission, noiselessness, high reliability, can be widely used in the fields such as recycling, space particular power source, minisize refrigeration device of the remaining used heat of industry.In recent years, due to day by day serious energy shortage and problem of environmental pollution, the research of thermoelectric material more and more comes into one's own.
Thermoelectric material optimum capacity efficient is relevant with material essence performance to the high low side temperature of work, and wherein the thermoelectricity capability of material is determined by nondimensional ZT value, and specific definition is: ZT=S
2σ T/ κ, wherein S represents Seebeck coefficient, and σ represents specific conductivity, and T is absolute temperature, and κ is the thermal conductivity of material.The ZT value of material is higher, and the efficiency of conversion of thermoelectric energy is also higher.Near current room temperature, the main thermoelectric material of commercial applications is the bismuth telluride-base material, the ZT value is about 1.0, effciency of energy transfer is about 5% left and right, far below traditional efficiency of heat engine, and the thermoelectricity original paper that these materials are used as thermoelectric power generation comprises some shortcomings, for example fusing point lower, easily decompose and be unsuitable for use etc. the widespread use that has limited thermoelectric generation technology in well-oxygenated environment.
The Novel hot electric material of seeking and pursue high ZT value is one of most important target of scientific worker in recent years.in the block materials system, people in succession propose and have found a series of novel materials and improve novel method and the means of current material, comprising phonon glass-electron crystal concept being applied to (Slack G. Handbook of thermoelectric in cage compound skutterudite and clathrate, London:CRC press Inc, 1995), material with low dimensional structures comprises nano wire, superlattice, film and have block materials of nanostructure etc., introduce resonance level and increase Seebeck coefficient near fermi level, introduce complicated energy band structure near the energy level that determines the performance transmission, and realize two dimensional surface electronic wave etc. in block materials.The realization of these novel materials and novel method makes the ZT value of present block materials obtain obvious lifting, and its maximum value has reached more than 1.5, and effciency of energy transfer has great application prospect greater than 10%.Bi-Te class thermoelectric material is the study hotspot of materials, for example referring to CN101273474A.In addition, also research and develop out at present polynary electrothermal alloy as the Novel hot electric material, for example CN101823702A discloses a kind of Cu
2CdSnSe
4Semiconductor nano.
Cu and chalcogenide Cu
2-xX (X=S, Se or Te) is although have extremely simple chemical formula, and their crystalline structure, atomic arrangement, phasor and microstructure are extremely complicated.For example, Cu
2-xTo there being a solid phase phase transformation between 400K, its transformation temperature is relevant with the x value in room temperature for Se, and x is larger, and transformation temperature is lower.Low-temperature phase generally is designated as the α phase, and high-temperature-phase generally is designated as the β phase.Because the structure of low temperature α phase is extremely complicated, experimentally lack good monocrystalline, thereby people it be unclear that so far to the crystalline structure of low temperature α phase, even concrete crystallographic system is all uncertain.There is research to think that the possibility of monocline, four directions and rhombic system all exists.Think the fluorite structure of the similar distortion of low temperature α after Kashida and Akai studies by X-ray, the Se atom is arranged in similar face-centred cubic mode, and the Cu atom is to be distributed in an orderly manner in trihedron and tetrahedral vacancy.Further the model Cu that proposes to be in tetrahedron arranges in the mode of √ 3 * √ 3 along (111) face, and its repeating unit is the arrangement plane that 4 Cu atoms form.High temperature β is a cubic fluorite structure mutually, the Se atom occupies with face-centered cubic and arranges, the Cu atom is randomly dispersed in trihedron, tetrahedron and the octahedron of gap digit, and it it be unclear that at every kind of locational probability that occupies, the different model that different investigators proposes.High temperature β is fast-ionic conductor mutually, and Cu can move freely in different interstitial sites, and its mobility determines by temperature, and temperature is higher, and mobility is larger.The research of such material is focused on the fast-ionic conductor aspect at present, less to the research of electricity and heat transport performance, only reporting that this material has large Seebeck coefficient and low thermal conductivity in a small amount of document.Therefore, this material might meet the concept of " phonon glass-electron crystal (PGEC) ", has fabulous thermoelectric applications DEVELOPMENT PROSPECT.
Summary of the invention
In the face of the problems referred to above that prior art exists, the inventor recognizes due to Cu
2-xHave very high Cu room in Se, it has good specific conductivity, shows the p-type electric-conducting behavior, and its size increases with the value of x.And according to simple valence electron rule, be 0 to x, satisfy the Cu of accurate stoichiometric ratio
2Se shows the semi-conductor behavior, and energy gap is about 1.23eV, and its transformation temperature is about 400 K.
A first aspect of the present invention provides a kind of thermoelectric material compound, and the chemical constitution of described thermoelectric material compound is Cu
2-
x Se, wherein, 0＜=x＜=0.15, preferred 0＜=x＜=0.02.
Thermoelectric material compound provided by the invention is semi-conductor, and than traditional thermoelectric material, this compound forms simple, raw material is cheap, has higher specific conductivity and Seebeck coefficient, and its thermal conductivity is low simultaneously, have good thermoelectric figure of merit ZT, fabulous prospects for commercial application is arranged.
Thermoelectric material compound provided by the invention be semi-conductor under 800～1000K, the ZT value can be more than 0.8.At room temperature, the ZT value can be more than 0.1.A preferred example is that under 1000K, the ZT value can arrive 1.6, and at room temperature the ZT value still can reach 0.2.
Thermoelectric material compound provided by the invention demonstrates excellent thermoelectric figure of merit ZT.
Thermoelectric material compound provided by the invention also can form the sandwich laminate structure that thickness is 20～50nm.Its low dimensional structures also helps the raising of ZT value.
On the other hand, the present invention also provides a kind of method for preparing above-mentioned thermoelectric material compound, comprising: get mol ratio and be (2-x): the pure metal simple substance of 1 copper and selenium also carries out Vacuum Package to it; In 1050～1250 ℃ (for example 1150 ℃ of left and right) lower melting treatment 10～14 hours (for example about 12 hours); Anneal is 5～8 days under 700～900 ℃ (for example 800 ℃ of left and right); And carry out pressure sintering under 400～450 ℃.
In invention, Vacuum Package is for example carried out under argon shield preferably at rare gas element.But Vacuum Package using plasma or flame gun packaged type.
In one embodiment, the pure metal simple substance of copper and selenium can be placed in pyrolytic boron nitride crucible again Vacuum Package in silica tube.In yet another embodiment, also can be with the direct Vacuum Package of pure metal simple substance of copper and selenium in silica tube, and need not to be placed in pyrolytic boron nitride crucible in advance.
In the present invention, pressure sintering can be adopted the discharge plasma sintering mode.The pressure that pressurization is burnt can be 50～65Mpa, and sintering time can be 5～10 minutes.
Preparation method's raw material of the present invention is simple, cost is low and technical process is simple, and controllability is high, and good reproducibility is fit to scale production.The thermoelectric material Compound C u of method preparation of the present invention
2-xThe Se compound has high Seebeck coefficient, high conductivity and low thermal conductivity, and its thermoelectric figure of merit reaches 1.6 when 1000K, and effciency of energy transfer can reach more than 15%.Thermoelectric material compound provided by the invention has a phase transformation between 300-400K, and be reversible transformation, its specific conductivity under high temperature (more than 400K) continues to reduce, and Seebeck coefficient continues to increase, thermal conductivity also reduces simultaneously, has fabulous application prospect.
Description of drawings
Fig. 1 illustrates the preparation flow schematic diagram of example thermoelectric material of the present invention;
Fig. 2 A illustrates example thermoelectric material Cu of the present invention
2The temperature variant graphic representation of the specific conductivity of Se;
Fig. 2 B illustrates example thermoelectric material Cu of the present invention
2The temperature variant graphic representation of the Seebeck coefficient of Se;
Fig. 2 C illustrates example thermoelectric material Cu of the present invention
2The temperature variant graphic representation of the thermal conductivity of Se;
Fig. 2 D illustrates example thermoelectric material Cu of the present invention
2The temperature variant graphic representation of thermoelectric figure of merit ZT of Se;
Fig. 3 A illustrates example thermoelectric material Cu of the present invention
1.98The temperature variant graphic representation of the specific conductivity of Se;
Fig. 3 B illustrates example thermoelectric material Cu of the present invention
1.98The temperature variant graphic representation of the Seebeck coefficient of Se;
Fig. 3 C illustrates example thermoelectric material Cu of the present invention
1.98The temperature variant graphic representation of the thermal conductivity of Se;
Fig. 3 D illustrates example thermoelectric material Cu of the present invention
1.98The temperature variant graphic representation of thermoelectric figure of merit ZT of Se;
Fig. 4 A illustrates example thermoelectric material Cu of the present invention
1.85The temperature variant graphic representation of the specific conductivity of Se;
Fig. 4 B illustrates example thermoelectric material Cu of the present invention
1.85The temperature variant graphic representation of the Seebeck coefficient of Se;
Fig. 4 C illustrates example thermoelectric material Cu of the present invention
1.85The temperature variant graphic representation of the thermal conductivity of Se;
Fig. 4 D illustrates example thermoelectric material Cu of the present invention
1.85The temperature variant graphic representation of thermoelectric figure of merit ZT of Se.
Embodiment
With reference to Figure of description, and further illustrate with the following embodiments the present invention, should be understood that Figure of description and following embodiment only are used for explanation the present invention, and unrestricted the present invention.
The below is with preparation Cu
2-xSe(0＜=x＜=0.15) describe for example.
Referring to Fig. 1, it illustrates the schematic diagram of the preparation flow of thermoelectric material of the present invention.It is starting raw material that the present invention adopts copper and selenium pure metal simple substance, and raw material sources are abundant, easy being easy to get.At step S1, mol ratio takes copper and selenium in accordance with regulations, and it is carried out Vacuum Package.Vacuum Package can under the protection of inert gas such as argon gas in glove box or the outside carry out under vacuumizing, but using plasma or flame gun packaged type, during encapsulation, silica tube vacuumizes, the maintenance internal pressure is 1-10000Pa.Can with copper and the direct Vacuum Package of selenium in silica tube, also can first copper and selenium be placed in pyrolytic boron nitride crucible (PBN), then be packaged in silica tube.
Then can enter step S2 and carry out the high-temperature fusion processing, melting process can carry out in vertical melting furnace.First temperature rise rate with 2.5～5 ℃/minute is warmed up to 685 ℃, constant temperature 2 hours; Again with the temperature rise rate of 0.8～2 ℃/min, be warmed up to 1050～1250(for example 1150 ℃ of left and right), constant temperature melting 10～14 hours (for example about 12 hours); Be slow cooling to 800 ℃ of left and right with the speed of 15-30 ℃/hour afterwards, constant temperature 8～20 hours is as cold as room temperature with stove at last and can obtains equally distributed crystal bar.
Enter step S3 and carry out anneal, anneal can be completed in the tubular annealing stove.To put into the tubular annealing stove through the block that melting treatment obtains, in 700-900 ℃ (for example 800 ℃ of left and right) annealing 5-8 days, then furnace cooling was to room temperature.
Enter at last step S4, the block after annealing is milled to powder, carry out pressure sintering.Sintering processing can be selected discharge plasma sintering, adopts the graphite jig of Φ 10mm, and spray boron nitride (BN) is with insulation; Sintering temperature can be 400～450 ℃, and pressure can be 50～65MPa, the sustainable 5-10 of sintering time minute.Sintering can obtain fine and close block.Launch electromicroscopic photograph by the field and show that the compound that makes under room temperature is shown as thickness (sandwich laminate structure of 20～50nm) about tens nanometers, the TEM photo shows without large crystal grain existence, there is numerous nanocrystalline and nanometer defectives inside material, as dislocation, twin etc.The thermoelectricity capability measurement shows that under low temperature and high temperature, this material all has very high specific conductivity and Seebeck coefficient, thereby has good power factor.This material has abnormal low lattice thermal conductivity simultaneously.
The present invention further for example following examples so that the present invention to be described better.
Embodiment 1:
With raw metal Cu and the Se molar ratio ingredient with 2:1; pack in the PBN crucible, then put into silica tube, pass into argon gas after vacuumizing and protect gas; encapsulate with plasma flame or gas flame after repeating 3 times, passing into a small amount of argon gas in silica tube is that inert atmosphere is with protecting materials.Raw material 1150 ℃ of lower meltings 12 hours, then is slow cooling to 800 ℃ with the speed of 15 ℃/hour, and constant temperature 8 hours is as cold as room temperature with stove.Block after melting is put into tube furnace 800 ℃ of annealing 5 days, then be chilled to room temperature with stove.Block after annealing is clayed into power, carry out discharge plasma sintering, sintering temperature is 400-450 ℃, and pressure is 50-65MPa, sintering time 5-10 minute, thus obtain fine and close block.Field emission electromicroscopic photograph shows the Cu that makes under room temperature
2Se is shown as the sandwich laminate structure of thickness about 20～50 nanometers, and the TEM photo shows without large crystal grain existence, has numerous nanocrystalline and nanometer defectives inside material, as dislocation, twin etc.Referring to Fig. 2 A～2D, the thermoelectricity capability measurement shows that at low temperature and high temperature, this material all has very high specific conductivity and Seebeck coefficient, thereby has good power factor.This material has abnormal low lattice thermal conductivity simultaneously.The ZT value that shows material according to the performance computation of measuring is 0.2 left and right when room temperature, reaches 1.6(such as Fig. 2 D during high temperature 1000K).
With raw metal Cu and the Se molar ratio ingredient with 1.98:1, repeat the reaction of embodiment 1, make pure Cu
1.98Se.
Field emission electromicroscopic photograph shows that under room temperature, it is shown as the sandwich laminate structure of thickness about 20～50 nanometers, and the TEM photo shows that the large crystal grain of nothing exists, and exists numerous nanocrystalline and nanometer defectives, as dislocation, twin etc. inside material.Referring to Fig. 3 A～3D, the thermoelectricity capability measurement shows at low temperature and high temperature, and this material also all has very high specific conductivity and Seebeck coefficient, thereby has good power factor.This material has abnormal low lattice thermal conductivity simultaneously.The ZT value that shows material according to the performance computation of measuring is 0.1 left and right when room temperature, reaches 0.8(such as Fig. 3 D during high temperature 800K).
Embodiment 3
With raw metal Cu and the Se molar ratio ingredient with 1.85:1, repeat the reaction of embodiment 1, make pure Cu
1.85Se.Field emission electromicroscopic photograph shows that under room temperature, it is shown as the sandwich laminate structure of thickness about 20～50 nanometers, and the TEM photo shows that the large crystal grain of nothing exists, and exists numerous nanocrystalline and nanometer defectives, as dislocation, twin etc. inside material.The thermoelectricity capability measurement shows at low temperature and high temperature, and this material also all has very high specific conductivity and Seebeck coefficient, thereby has good power factor.This material has abnormal low lattice thermal conductivity simultaneously.The ZT value that shows material according to the performance computation of measuring is 0.02 left and right when room temperature, reaches 0.43(such as Fig. 4 D during high temperature 800K).
With raw metal Cu and the Se molar ratio ingredient with 2:1; directly pack in silica tube; pass into argon gas protection after vacuumizing, encapsulate with plasma flame or gas flame after repeating 3 times, passing into a small amount of argon gas in silica tube is that inert atmosphere is with protecting materials.Raw material 1150 ℃ of lower meltings 12 hours, then is slow cooling to 800 ℃ with the speed of 15 ℃/hour, and then constant temperature 8 hours be as cold as room temperature with stove.Block after melting is put into tube furnace 800 ℃ of annealing 5 days, then be chilled to room temperature with stove.Block after annealing is clayed into power, carry out discharge plasma sintering, sintering temperature is 400-450 ℃, and pressure is 50～65MPa, sintering time 5～10 minutes, thus obtain fine and close block.The material that obtains has performance similar to Example 1, and after sintering the parameter in this sample employing embodiment 1 into block, high temperature ZT value is between 1.3～1.6.
Industrial applicability: thermoelectric material compound chemistry of the present invention forms simple, and laminate structure, ZT value with low-dimensional are high, are suitable as a kind of novel thermoelectric material and develop.Preparation is simple for method of the present invention, cost is low, be fit to scale production.
Claims (12)
1. a thermoelectric material compound, is characterized in that, the chemical constitution of described thermoelectric material compound is Cu
2-
x Se, wherein, 0＜=x＜=0.15.
2. thermoelectric material compound according to claim 1, is characterized in that, 0＜=x＜=0.02.
3. thermoelectric material compound according to claim 1 and 2, is characterized in that, under 800～1000K, the ZT value of described thermoelectric material compound is more than 0.8.
4. thermoelectric material compound according to claim 3, is characterized in that, at room temperature, the ZT value of described thermoelectric material compound is more than 0.1.
5. thermoelectric material compound according to claim 1 and 2, is characterized in that, the formation thickness of described thermoelectric material compound is the sandwich laminate structure of 20～50nm.
6. a method for preparing thermoelectric material compound claimed in claim 1, is characterized in that, comprising:
Get mol ratio and be (2-x): the pure metal simple substance of 1 copper and selenium also carries out Vacuum Package to it;
1050～1250 ℃ of lower melting treatment 10～14 hours;
700～900 ℃ of lower anneal 5～8 days; And
Carry out pressure sintering under 400～450 ℃.
7. method according to claim 6, is characterized in that, described Vacuum Package is carried out under protection of inert gas.
8. according to claim 6 or 7 described methods, is characterized in that, described Vacuum Package using plasma or flame gun packaged type.
9. according to claim 6 or 7 described methods, is characterized in that, with the pure metal simple substance of described copper and selenium be placed in pyrolytic boron nitride crucible again Vacuum Package in silica tube.
10. according to claim 6 or 7 described methods, is characterized in that, with the direct Vacuum Package of pure metal simple substance of described copper and selenium in silica tube.
11. method according to claim 6 is characterized in that, the discharge plasma sintering mode is adopted in described pressure sintering.
12. method according to claim 11 is characterized in that, the pressure that described pressurization is burnt is 50～65Mpa, and sintering time is 5～10 minutes.
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| 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 |
| CN104878234A (en) * | 2015-06-17 | 2015-09-02 | 武汉理工大学 | Method for quickly preparing Ag2Se block thermoelectric material through self-homogenization |
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| CN105990510A (en) * | 2015-02-04 | 2016-10-05 | 中国科学院上海硅酸盐研究所 | Copper-selenium based high performance thermoelectric material and preparation method of the same |
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| CN109590481A (en) * | 2019-01-30 | 2019-04-09 | 北京科技大学 | A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material |
| CN111807333A (en) * | 2020-07-28 | 2020-10-23 | 安徽大学 | Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice |
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| CN104885240A (en) * | 2013-09-09 | 2015-09-02 | 株式会社Lg化学 | Thermoelectric material |
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| US9761778B2 (en) | 2013-09-09 | 2017-09-12 | Lg Chem, Ltd. | Method for manufacturing thermoelectric materials |
| 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 |
| CN105990510A (en) * | 2015-02-04 | 2016-10-05 | 中国科学院上海硅酸盐研究所 | Copper-selenium based high performance thermoelectric material and preparation method of the same |
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| CN104878234A (en) * | 2015-06-17 | 2015-09-02 | 武汉理工大学 | Method for quickly preparing Ag2Se block thermoelectric material through self-homogenization |
| CN109585638A (en) * | 2018-11-30 | 2019-04-05 | 武汉理工大学 | One kind having room temperature inorganic thermo-electric device flexible and preparation method thereof |
| CN109590481A (en) * | 2019-01-30 | 2019-04-09 | 北京科技大学 | A kind of Cu2-xMxThe high pressure method for preparing of Se alloy series thermoelectric material |
| CN111807333A (en) * | 2020-07-28 | 2020-10-23 | 安徽大学 | Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice |
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