CN103130200B - Thermoelectricity material compound and preparation method thereof - Google Patents
Thermoelectricity material compound and preparation method thereof Download PDFInfo
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- CN103130200B CN103130200B CN201110379585.9A CN201110379585A CN103130200B CN 103130200 B CN103130200 B CN 103130200B CN 201110379585 A CN201110379585 A CN 201110379585A CN 103130200 B CN103130200 B CN 103130200B
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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 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.This technology has pollution-free, machinery-free transmission, noiselessness, high reliability in application, can be widely used in the fields such as the remaining useless pick up the heat of industry, space particular power source, minisize refrigeration device.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 efficiency 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, the thermal conductivity that κ is 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 bismuth telluride-base material, 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 and in well-oxygenated environment, use etc. the widespread use that has limited thermoelectric generation technology.
The Novel hot electric material of finding and pursue high ZT value is one of most important target of scientific worker in recent years.In 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), the material with low dimensional structures comprises nano wire, superlattice, film and there is block materials of nanostructure etc., near fermi level, introduce resonance level and increase Seebeck coefficient, near the energy level that determines performance transmission, introduce complicated energy band structure, and in block materials, realize two dimensional surface electronic wave etc.The realization of these novel materials and novel method makes the ZT value of current block materials obtain obvious lifting, and its maximum value has reached more than 1.5, and effciency of energy transfer has been greater than 10%, has great application prospect.Bi-Te class thermoelectric material is the study hotspot of this type of material, for example, referring to CN101273474A.In addition, also research and develop at present polynary electrothermal alloy as 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-xin room temperature to there is a solid phase phase transformation in Se, its transformation temperature is relevant with x value between 400K, x is larger, and transformation temperature is lower.Low-temperature phase is generally designated as α phase, and high-temperature-phase is generally designated as 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.Kashida and Akai thinks the fluorite structure of the similar distortion of low temperature α after studying by X-ray, Se atom is arranged in similar face-centred cubic mode, and Cu atom is to be distributed in an orderly manner in trihedron and tetrahedral vacancy.The Cu that further model 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, Se atom occupies with face-centered cubic and arranges, 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 to fast-ionic conductor aspect at present, less to the research of electricity and heat transport performance, only in a small amount of document, report that this material has large Seebeck coefficient and low thermal conductivity.Therefore, this material likely meets 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-xin Se, have very high Cu room, it has good specific conductivity, shows p-type electric-conducting behavior, and its size increases with the value of x.And according to simple valence electron rule, to x, be 0, meet the Cu of accurate stoichiometric ratio
2se shows semi-conductor behavior, and energy gap is about 1.23eV, and its transformation temperature is in 400 K left and right.
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, preferably 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, there is good thermoelectric figure of merit ZT, have fabulous prospects for commercial application.
Thermoelectric material compound provided by the invention be semi-conductor under 800～1000K, ZT value can be more than 0.8.At room temperature, ZT value can be more than 0.1.A preferred example is that under 1000K, ZT value can arrive 1.6, and at room temperature 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 contributes to the raising of ZT value.
On the other hand, the present invention also provides a kind of method of preparing above-mentioned thermoelectric material compound, comprising: get mol ratio for (2-x): the pure metal simple substance of 1 copper and selenium also carries out Vacuum Package to it; For example, for example, in 1050～1250 ℃ (1150 ℃ of left and right) lower melting treatment 10～14 hours (about 12 hours); For example, under 700～900 ℃ (800 ℃ of left and right), anneal is 5～8 days; And at 400～450 ℃, carry out pressure sintering.
In invention, Vacuum Package preferably at rare gas element, for example, is carried out under argon shield.Vacuum Package can 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 by the direct Vacuum Package of pure metal simple substance of copper and selenium in silica tube, and without being placed in pyrolytic boron nitride crucible in advance.
In the present invention, pressure sintering can adopt 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, reproducible, is applicable to scale production.Thermoelectric material Compound C u prepared by method of the present invention
2-xse 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.
Accompanying drawing explanation
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 specific conductivity of Se;
Fig. 2 B illustrates example thermoelectric material Cu of the present invention
2the temperature variant graphic representation of Seebeck coefficient of Se;
Fig. 2 C illustrates example thermoelectric material Cu of the present invention
2the temperature variant graphic representation of 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 specific conductivity of Se;
Fig. 3 B illustrates example thermoelectric material Cu of the present invention
1.98the temperature variant graphic representation of Seebeck coefficient of Se;
Fig. 3 C illustrates example thermoelectric material Cu of the present invention
1.98the temperature variant graphic representation of 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 specific conductivity of Se;
Fig. 4 B illustrates example thermoelectric material Cu of the present invention
1.85the temperature variant graphic representation of Seebeck coefficient of Se;
Fig. 4 C illustrates example thermoelectric material Cu of the present invention
1.85the temperature variant graphic representation of 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 are only for the present invention is described, and unrestricted the present invention.
Below with preparation Cu
2-xse(0≤x≤0.15) for example describes.
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 to Vacuum Package.Vacuum Package can be under the protection of inert gas such as argon gas in glove box or outside carry out under vacuumizing, can using plasma or flame gun packaged type, during encapsulation, silica tube vacuumizes, maintenance internal pressure is 1-10000Pa.Can, by copper and the direct Vacuum Package of selenium in silica tube, also can first copper and selenium be placed in to pyrolytic boron nitride crucible (PBN), then be packaged in silica tube.
Then can enter step S2 and carry out high-temperature fusion processing, melting process can carry out in vertical melting furnace.The first temperature rise rate with 2.5～5 ℃/min is warmed up to 685 ℃, constant temperature 2 hours; With the temperature rise rate of 0.8～2 ℃/min, be warmed up to for example 1150 ℃ of left and right of 1050～1250(again), constant temperature melting 10～14 hours (for example, about 12 hours); With the speed of 15-30 ℃/h, be slow cooling to 800 ℃ of left and right afterwards, constant temperature 8～20 hours, is finally as cold as room temperature with stove and can obtains equally distributed crystal bar.
Enter step S3 and carry out anneal, anneal can complete in tubular annealing stove.The block obtaining through melting treatment is put into tubular annealing stove, and for example, in 700-900 ℃ (800 ℃ of left and right) annealing 5-8 days, then furnace cooling is to room temperature.
Finally enter 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 to insulate; Sintering temperature can be 400～450 ℃, and pressure can be 50～65MPa, the sustainable 5-10 minute of sintering time.Sintering can obtain fine and close block.By field, launch electromicroscopic photograph and show that the compound making under room temperature is shown as thickness in the sandwich laminate structure of tens nanometer left and right (20～50nm), TEM photo shows without large crystal grain existence, in material the inside, there is numerous nanocrystalline and nanometer defects, as dislocation, twin etc.Thermoelectricity capability measurement shows that, under low temperature and high temperature, this material all has very high specific conductivity and Seebeck coefficient, thereby the power factor having had.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:
Molar ratio ingredient by raw metal Cu and Se with 2:1; pack in PBN crucible, then put into silica tube, after vacuumizing, pass into argon gas and protect gas; after repeating 3 times, with plasma flame or gas flame, encapsulate, in silica tube, passing into a small amount of argon gas is that inert atmosphere is with protecting materials.By raw material melting 12 hours at 1150 ℃, then with the speed of 15 ℃/h, be slow cooling to 800 ℃, 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 with stove, be chilled to room temperature.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 transmitting electromicroscopic photograph shows the Cu making under room temperature
2se is shown as thickness in the sandwich laminate structure of 20～50 nanometer left and right, and TEM photo shows without large crystal grain existence, has numerous nanocrystalline and nanometer defects, as dislocation, twin etc. in material the inside.Referring to Fig. 2 A～2D, thermoelectricity capability measurement shows that, at low temperature and high temperature, this material all has very high specific conductivity and Seebeck coefficient, thereby the power factor having had.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(as Fig. 2 D during high temperature 1000K).
Embodiment 2
Molar ratio ingredient by raw metal Cu and Se with 1.98:1, repeats the reaction of embodiment 1, makes pure Cu
1.98se.
Field transmitting electromicroscopic photograph shows that under room temperature, it is shown as thickness in the sandwich laminate structure of 20～50 nanometers left and right, and TEM photo shows that the large crystal grain of nothing exists, and exists numerous nanocrystalline and nanometer defects in material the inside, as dislocation, twin etc.Referring to Fig. 3 A～3D, thermoelectricity capability measurement shows at low temperature and high temperature, and this material also all has very high specific conductivity and Seebeck coefficient, thereby the power factor having had.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(as Fig. 3 D during high temperature 800K).
Embodiment 3
Molar ratio ingredient by raw metal Cu and Se with 1.85:1, repeats the reaction of embodiment 1, makes pure Cu
1.85se.Field transmitting electromicroscopic photograph shows that under room temperature, it is shown as thickness in the sandwich laminate structure of 20～50 nanometers left and right, and TEM photo shows that the large crystal grain of nothing exists, and exists numerous nanocrystalline and nanometer defects in material the inside, as dislocation, twin etc.Thermoelectricity capability measurement shows at low temperature and high temperature, and this material also all has very high specific conductivity and Seebeck coefficient, thereby the power factor having had.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(as Fig. 4 D during high temperature 800K).
Embodiment 4
Molar ratio ingredient by raw metal Cu and Se with 2:1; directly pack in silica tube; after vacuumizing, pass into argon gas protection, encapsulate after repeating 3 times with plasma flame or gas flame, in silica tube, passing into a small amount of argon gas is that inert atmosphere is with protecting materials.By raw material melting 12 hours at 1150 ℃, then with the speed of 15 ℃/h, be slow cooling to 800 ℃, constant temperature 8 hours, is then as cold as room temperature with stove.Block after melting is put into tube furnace 800 ℃ of annealing 5 days, then with stove, be chilled to room temperature.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 obtaining has performance similar to Example 1, adopts the parameter in embodiment 1 to sinter into after block in this sample, and 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, the 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 applicable to scale production.
Claims (8)
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≤0.02, the pattern of described thermoelectric material compound is the sandwich laminate structure of thickness 20～50nm, and under 800～1000K, the ZT value of described thermoelectric material compound is more than 0.8, and described thermoelectric material compound is prepared by following method:
Get mol ratio for (2-x): the pure metal simple substance of 1 copper and selenium also carries out Vacuum Package to it;
At 1050～1250 ℃, melting treatment is 10～14 hours;
At 700～900 ℃, anneal is 5～8 days; And
At 400～450 ℃, carry out pressure sintering.
2. thermoelectric material compound according to claim 1, is characterized in that, the room temperature ZT value of described thermoelectric material compound is more than 0.1.
3. a method of preparing thermoelectric material compound claimed in claim 1, is characterized in that, comprising:
Get mol ratio for (2-x): the pure metal simple substance of 1 copper and selenium also carries out Vacuum Package to it;
At 1050～1250 ℃, melting treatment is 10～14 hours;
At 700～900 ℃, anneal is 5～8 days; And
At 400～450 ℃, carry out pressure sintering.
4. method according to claim 3, is characterized in that, described Vacuum Package is carried out under protection of inert gas.
5. according to the method described in claim 3 or 4, it is characterized in that described Vacuum Package using plasma or flame gun packaged type.
6. according to the method described in claim 3 or 4, it is characterized in that, by the pure metal simple substance of described copper and selenium be placed in pyrolytic boron nitride crucible again Vacuum Package in silica tube.
7. method according to claim 3, is characterized in that, described pressure sintering adopts discharge plasma sintering mode.
8. method according to claim 7, is characterized in that, the pressure of described pressure sintering is 50～65MPa, and sintering time is 5～10 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP6365951B2 (en) | 2013-09-09 | 2018-08-01 | エルジー・ケム・リミテッド | Thermoelectric material manufacturing method |
| KR101612492B1 (en) * | 2013-09-09 | 2016-04-14 | 주식회사 엘지화학 | Thermoelectric materials |
| CN104310457B (en) * | 2014-09-30 | 2016-05-18 | 中国科学院上海硅酸盐研究所 | Can suppress the thermoelectric material of Cu ion migration and suppress the method for Cu ion migration in Cu base thermoelectricity material |
| CN105990510B (en) * | 2015-02-04 | 2018-07-20 | 中国科学院上海硅酸盐研究所 | A kind of copper seleno high performance thermoelectric material and preparation method thereof |
| CN104878234B (en) * | 2015-06-17 | 2017-06-13 | 武汉理工大学 | It is a kind of to prepare Ag from homogenizing is quick2The method of Se block thermoelectric materials |
| CN109585638B (en) * | 2018-11-30 | 2020-12-08 | 武汉理工大学 | Inorganic thermoelectric device with room temperature flexibility 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 |
| CN111807333B (en) * | 2020-07-28 | 2023-06-23 | 安徽大学 | Preparation method of three-dimensional cuprous selenide nanocrystalline superlattice |
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