CN101723669A - Compound capable of being used for thermoelectric material and preparation method thereof - Google Patents

Compound capable of being used for thermoelectric material and preparation method thereof Download PDF

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CN101723669A
CN101723669A CN200810202065A CN200810202065A CN101723669A CN 101723669 A CN101723669 A CN 101723669A CN 200810202065 A CN200810202065 A CN 200810202065A CN 200810202065 A CN200810202065 A CN 200810202065A CN 101723669 A CN101723669 A CN 101723669A
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thermoelectric material
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黄富强
刘敏玲
陈立东
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Shanghai Institute of Ceramics of CAS
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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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/058—Mixtures of metal powder with non-metallic powder by reaction sintering (i.e. gasless reaction starting from a mixture of solid metal compounds)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • 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
    • 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

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Abstract

The invention relates to a compound (A2BCQ4) capable of being used for a thermoelectric material and a preparation method thereof, wherein A is Cu, Ag or Au; B is any one of the divalent ions such as Zn, Cd, Hg, Fe, Ni, Pd and the like, or any one of the trivalent ions such as B, Al, Ga, In and the like; C is any one of the tetravalent ions such as Si, Ge, Sn, Pb and the like or any one of the trivalent ions such as B, Al, Ga, In and the like; and Q is S, Se and Te, or N, P, As and Sb. Properly speaking, the A2BCQ4 belongs to a tetragonal system, has a deformed blende superlattice structure and is similar to chalcopyrite (CuFeS2), and only half of Fe positions is occupied by B while the other half is occupied by C. The unique structure of the compound determines that the material of the type has considerable thermoelectric properties. The compound provided by the invention can be used for the thermoelectric material, has a unique design idea, low-price and readily available raw materials, and a simple preparation process, and the material has superior electric conductivity and superior thermoelectric properties and is a perfect novel thermoelectric candidate material.

Description

One class can be used for thermoelectric material compound and preparation method
Technical field
The present invention relates to compound and preparation method that a class can be used for thermoelectric material, belong to the thermoelectric material field.
Background technology
Thermoelectric effect is the general name of the electrical effect that causes of the reversible heat effect that causes of electric current and the temperature difference.It comprises: Seebeck (Seebeck) effect, Peltier (Pa Er card) effect and Thomson (Thomson) effect.Thermoelectric material is a kind of with the functional materials of directly changing between heat energy and the electric energy, has very important application prospects in fields such as thermoelectric power generation and refrigeration, thermostatic control and temperature surveys.
Along with development of science and technology, energy problem and environmental problem become the hot issue that people more and more are concerned about.Thermoelectric material is a kind of environmentally friendly functional materials. refrigeration and the power generation system of utilizing thermoelectric material to make can effectively utilize the used heat and the waste gas direct generation of electricity that power plant, automobile etc. are emitted, and do not need media material, do not generate any waste simultaneously; But also has long service life, steady performance.Since the nineties; serious day by day along with global environmental pollution, energy dilemma; and the development of computer technology, aeronautical and space technology, superconductor technology and microelectronics; press for the refrigeration plant of small-sized, static, fixing, long lifetime and safety, so the research of thermoelectric material is subjected to common attention.Using and studying comparatively sophisticated thermoelectric material mainly is metallic compound and solid solution alloy such as PbTe, SiGe, CrSi, Bi2Te3 and derivative thereof [(1) A.Majumdar, Science, 303,2004,777; (2) L.A.Kuznetson, V.L.Kuznetsov, D.M.Rowe, J.Phys.Cgem.Solids, 61,2000,1269; (3) D.Y.Chung, T.Hogan, P.Brazis, Science, 287,2000,1024; (4) B.Wolfing, C.Kloc, J.Teubner, Phys.Rev.Lett., 86,2001,4350; (5) L.A.Kuznetsova, V.L.Kuznetsov, D.M.Rowe, Phys.Chem.Solids, 61,2000,1269.], CoSb3[K.T.Wojciechowski, J.Tobola, J.
Figure G2008102020659D0000011
J.Alloys Compd., 361,2003,19-27.] etc., but having preparation condition, these thermoelectric materials have relatively high expectations, need under certain gas shield, to carry out, be unsuitable at high temperature working and containing harmful shortcomings such as heavy metal.Early 1990s, the Japan scholar found, at room temperature, and NaCo 2O 4Have higher thermoelectric force [(1) Y.Terasaki, U.Sasag, K.Chinokura, Phys.Rev.B, 56,1997,12685-12687; (2) T.Itoh, T.Kawata, 17 ThInternational Conference on Thermaelectrics, 1998,595-597.], low resistivity and low lattice thermal conductivity are arranged simultaneously, this type of thermoelectric material can long term operation under high temperature in the oxidizing atmosphere, most of nontoxicitys, non-environmental-pollution, and preparation is simple, but during sample preparation in air direct sintering, need not to vacuumize, cost is low, thereby enjoys people's attention.At present, this type of thermoelectric material is typical case's representative with the transition metal oxide.
Though thermoelectric material has been gone through 100 years of researches, present thermoelectric material still exists the lower shortcoming of its conversion efficiency of thermoelectric (6%-11%) [Xu Guiying, the research and development direction of thermoelectric material, material Leader, 14,2000,38-41.]。Exploration and development of new thermoelectric material efficiently are of great immediate significance, and its urgency has some idea of.
Summary of the invention
The object of the invention is to provide a class to can be used for compound of thermoelectric material and preparation method thereof, and the compound general formula that a class that is provided can be used for thermoelectric material is A 2BCQ 4, A=Cu, Ag or Au in the formula; In in the divalent ions such as B=Zn, Cd, Hg, Fe, Ni and Pd any or the 3 valency ions such as B, Al, Ga and In any; In the 4 valency ions such as C=Si, Ge, Sn and Pb any or be in the 3 valency ions such as B, Al, Ga and In any; Among Q=S, Se and the Te any or be among N, P, As and the Sb any.
Design concept of the present invention is:
(1) utilizes A 2BCQ 4Belong to tetragonal system, A, B, C form tetrahedral coordination with Q respectively, are similar to the diamond network structure, make the material lattice thermal conductance reduce (as Cu 2CdSnSe 4The low 1.5Won that reaches of thermal conductivity under 200 ℃ -1k -1).
(2) B and C can be 3 valency ions (B, Al, Ga or In) simultaneously, and its structural formula can be reduced to chalcopyrite type cpd ABQ 2Or Q is negative 3 valency negatively charged ion, and in order to satisfy the valence state balance, the C position can be 4 valency positively charged ions, and A position ion can lack, and promptly chemical expression can be reduced to BCQ ' 2
(3) because the A atom is the positively charged ion that contains d orbital electron structure, approaching with the np orbital energies of Q atom, form hydridization easily, [AQ 4] tetrahedral three-dimensional net structure be beneficial to dam the son transmission, simultaneously, Q 2-With metal ion (two A +, B 2+, C 2+) form tetrahedral coordination, reduced Q 2-The local behavior of ion np electronics, the mobility of raising hole carrier has been improved the material conductivity, and the Seebeck coefficient that has improved material is (as Cu 2ZnSnSe 4Specific conductivity is up to 10 under the room temperature 2S.cm -1).
(4) can pass through to mix, thereby the plain valency of A bit is improved, increase hole concentration, the conductivity of raising material; Can pass through to mix, thereby the plain valency of C bit is reduced, increase electron density, the conductivity of raising material; And doping way and kind are various, and as introducing room or high-valency metal in the A position, or in the B position, the C position low price/high-valency metal that mixes, or the high price negatively charged ion (as negative 3 valency ions) that mixes in the Q position increase carrier concentration, thus the conductivity of raising material; The doping scope is wider, and the concentration of dopant is between 0at%-10at%.
(5) can carry out between compound multiple compound, compound as between claim 1 and claim 3 compound: (1-x) A 2BCQ 4-xA ' B ' Q ' 2(0≤x≤1).
(6) provided by the invention to can be used for the compound that thermoelectric material comprises extensive, comprises Cu, Ag or Au in the I B family; Fe, Ni or Pd in Zn among the II B, Cd or Hg and the VIII family; Si, Ge, Sn or the Pb of IV A family; The B of IIIB, Al, Ga or In.And the material formed of sulfur family element (S, Se, Te) or the element N of VA family, P, As, Sb.According to the valence state balance principle, can form the various compd A of total class 2-x xBCQ 4(0≤x≤1).
The compound that a class provided by the invention in a word can be used for thermoelectric material belongs to tetragonal system, structure and chalcopyrite (CdFeS 2) similar, can be as the zink sulphide superlattice structure that is distortion, just the Fe position of half is replaced by the B position, occupies, and second half replaces for the C position.
From the material preparation angle, the preparation that a class provided by the invention can be used for the compound of thermoelectric material be with the element simple substance of composition material or with corresponding chalkogenide by high temperature solid state reaction or high-temperature fusion or the synthetic A that obtains of high-energy ball milling 2BCQ 4And carry out behind the adulterated polycrystal powder discharge plasma sintering (Spark Plasma Sintering, SPS) or through etc. static pressure, sintering processes obtain testing block materials.
The concrete processing step of making of the present invention is:
(a) press A 2BCQ 4The chemical constitution proportioning selects for use an amount of raw material (as corresponding simple substance or chalkogenide etc.) to prepare burden;
(b) raw material is packed in the encloses container of starvations such as quartz glass tube, through vacuumizing (less than 10 -2Pa) back encapsulation.
(c) Feng Zhuan quartz glass tube carries out the solid state reaction first time under 600 ℃～700 ℃, and the reaction times is 24～96h; Grind encapsulation again behind the open pipe, carry out the solid state reaction second time, condition is with for the first time identical; Maybe the quartz glass tube with encapsulation places High Temperature Furnaces Heating Apparatus to carry out frit reaction (650 ℃～1050 ℃ are reacted 4～96h).
(d) or with the batching of step (a) be sealed in (vacuumizing or the filling with inert gas protection) ball grinder, carry out high-energy ball milling, the ball milling time is 2～24h; Or with the batching of (a) quartz glass tube of packing into; Vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing is used in the back, carries out frit reaction in 700～1000 ℃;
(e) with step (c) or (d) gained sample grinding, obtain powder, in sinter molding under certain temperature and the pressure (as carrying out the SPS sintering or the quartz glass tube of behind the 200Mpa cold isostatic compaction, packing into, through vacuumizing (less than 10 at the pressure with 40～60MPa under 650～850 ℃ -2Pa) encapsulation, in 700～900 ℃ of sintering, insulation 6～24h finally makes thermoelectric block body material.
Solid state reaction is to carry out in the closed environment of the starvation atmosphere such as Glass tubing of sealing by fusing in preparation process.The SPS sintering is at Ar or N 2Or vacuumize down to wait under the protective atmosphere and carry out.
Sample characterization and performance evaluation
(1) thing is determined mutually
Adopt the full-automatic X-ray diffractometer of Japanese Rigaku 2000V to determine the thing phase of material.
(2) test of thermal conductivity
To the block sample of the Φ 10mm for preparing,, after the oven dry of spray carbon, adopt anti-the speeding of Germany (Netzsch, LFA427) thermal conductance instrument, and use laser pulse technology (Laser flashtechnique) and under argon gas atmosphere, measure thermal diffusivity through surface finish.
(3) electric property
Gained SPS sintered sample of the present invention after anneal, is cut into test desired shape (as strip), carry out the conductivity evaluation with classical testing method such as four-terminal methods after adding loading electrode.And, on Accent HL5500 Hall instrument, carry out the test of Hall coefficient and Seebeck coefficient.
A class thermoelectric material compound provided by the invention can be applicable to thermoelectric material, the mentality of designing uniqueness, and raw material is cheap and easy to get, and preparation technology is simple, and the conductivity of material is superior, and has superior thermoelectricity capability, is the novel thermoelectric candidate material of a kind of ideal.
Description of drawings
Fig. 1 Cu 2ZnSnS 4The crystalline structure synoptic diagram.
Fig. 2 polycrystalline Cu 2ZnSnS 4Block and mix the polycrystalline XRD diffracting spectrum of Cu sample.
Fig. 3 polycrystalline Cu 2ZnSnS 4Block and mix Cu sample specific conductivity with the variation of temperature curve.
Fig. 4 polycrystalline Cu 2ZnS 4S4 block and mix the room temperature Seebeck coefficient of Cu sample.
Fig. 5 polycrystalline Cu 2ZnSnS 4Block and the room temperature thermal conductivity of mixing the Cu sample.
Fig. 6 polycrystalline Cu 2ZnSnS 4Block and mix the room temperature thermoelectric figure of merit (ZT value) of Cu sample.
Fig. 7 polycrystalline Cu 2ZnSnSe 4Block and the room temperature thermal conductivity of mixing the Cu sample.
Fig. 8 polycrystalline Cu 2CdSnSe 4Block and the room temperature thermal conductivity of mixing the Cu sample.
Embodiment
Introduce embodiments of the invention below, but the present invention only limits to embodiment absolutely not.
Embodiment 1:
Adopt Cu powder, Zn powder, Sn powder and S powder (the quality percent purity is respectively 99.7%, 99.99%, 99.9% and 99.999% time together) according to Cu 2ZnSnS 4With mix Cu sample Cu 2+xZn 1-xSnS 4The chemical formula weighing of (x=0～0.10) and the Glass tubing of packing into vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, and the Glass tubing of adorning mixture slowly is warming up to 450 ℃ and be incubated 24h, is warming up to 600 ℃～700 ℃ then and carries out the solid state reaction first time, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time, and condition is with reaction conditions and solid state reaction is identical for the first time.With resulting pure phase powder, the pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.
Polycrystalline XRD diffracting spectrum (Fig. 2) shows the polycrystalline sample that has obtained pure phase by above-mentioned prepared.Material has excellent conducting performance (Fig. 3), and Zn mixes the position the nearly 30S cm of specific conductivity under the sample room temperature of Cu 10% -1Doped samples room temperature Seebeck coefficient is not up to 460 μ V/K (Fig. 4).Fig. 5 and Fig. 6 have provided Cu respectively 2+xZn 1-xSnS 4The room temperature thermal conductivity of (x=0～0.10) and the thermoelectric figure of merit of room temperature (ZT value).
Embodiment 2:
Adopt Cu powder, Zn powder, Sn powder and S powder (purity is respectively 99.7%, 99.99%, 99.9% and 99.999%) according to Cu 2ZnSnS 4With mix Cu sample Cu 2+xZn 1-xSn SThe chemical formula weighing of 4 (x=0～0.10) and the Glass tubing of packing into vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, carries out frit reaction in 700～1000 ℃, and with resulting pure phase powder, the pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the thermoelectric block materials of testing.
Polycrystalline XRD diffracting spectrum is similar to embodiment 1, shows that we have obtained the polycrystalline sample of pure phase.The conductivity of material is similar to embodiment 1, and the thermoelectric figure of merit of Seebeck coefficient, room temperature thermal conductivity and room temperature is all suitable with embodiment 1.
Embodiment 3:
Adopt Cu powder, Zn powder, Sn powder and S powder (purity is respectively 99.7%, 99.99%, 99.9% and 99.999%) according to Cu 2ZnSnS 4With mix Cu sample Cu 2+xZn 1-xSnS 4The chemical formula weighing of (x=0～0.10) is also put into the high-energy ball milling jar, the applying argon gas protection, and sealing, ball milling 5h, with resulting pure phase powder, the pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.
Polycrystalline XRD diffracting spectrum is similar to embodiment 1, shows that we have obtained the polycrystalline sample of pure phase.The conductivity of material is similar to embodiment 1, and the thermoelectric figure of merit of Seebeck coefficient, room temperature thermal conductivity and room temperature is all suitable with embodiment 1.
Embodiment 4:
Adopt Cu powder, Zn powder, Sn powder and S powder (purity is respectively 99.7%, 99.99%, 99.9% and 99.999%) according to Cu 2ZnSnS 4With mix Cu sample Cu 2+xZn 1-xSnS 4The chemical formula weighing of (x=0～0.10) and the Glass tubing of packing into vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, carries out frit reaction in 700～1000 ℃, with resulting pure phase powder, carries out isostatic cool pressing at the pressure of 200GPa, finally makes the thermoelectric block materials of testing.
Polycrystalline XRD diffracting spectrum is similar to embodiment 1, shows that we have obtained the polycrystalline sample of pure phase.The conductivity of material is similar to embodiment 1, and the thermoelectric figure of merit of Seebeck coefficient, room temperature thermal conductivity and room temperature is all suitable with embodiment 1.
Embodiment 5:
Adopt Cu powder, Zn powder, Sn powder and Se powder (purity is respectively 99.7%, 99.99%, 99.9% and 99.999%) according to Cu 2ZnSnSe 4With mix Cu sample Cu 2+xZn 1-xSnSe 4The chemical formula weighing of (x=0～0.10) and the Glass tubing of packing into vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, and the Glass tubing of adorning mixture slowly is warming up to 450 ℃ and be incubated 24h, is warming up to 600 ℃～700 ℃ then and carries out solid state reaction, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time, condition and preceding similar.With resulting pure phase powder, the pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.
Material has the Cu of ratio 2+xZn 1-xSnS 4Excellent conducting performance more, the lower (see figure 6) of thermal conductivity.
Embodiment 6:
Adopt Cu powder, Cd powder, Sn powder and Se powder (purity is respectively 99.7%, 99.99%, 99.9% and 99.999%) according to Cu 2CdSnSe 4With mix Cu sample Cu 2+xCd 1-xSnSe 4The chemical formula weighing of (x=0～0.10) and the Glass tubing of packing into vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, and the Glass tubing of adorning mixture slowly is warming up to 450 ℃ and be incubated 24h, is warming up to 600 ℃～700 ℃ then and carries out the solid state reaction first time, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carry out the solid state reaction second time, the processing condition of the processing condition solid state reaction first time are identical, with resulting pure phase powder, pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.
Material has the Cu of ratio 2+xZn 1-xSnS 4Excellent conducting performance more, the lower (see figure 7) of thermal conductivity.
Embodiment 8:
Adopt commercially available Cu 2S, ZnS and SnS 2(the quality percent purity all＞99%) are according to Cu 2ZnSnS 4The chemical formula weighing and the Glass tubing of packing into, vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing is used in the back, according to the method for embodiment 1 or embodiment 2 or embodiment 3 or embodiment 4, finally makes the block materials of thermoelectric test.
The performance test results is substantially the same manner as Example 1.
Embodiment 9:
Adopt Cu powder, Cd powder, Sn powder, In powder and Se powder (purity is respectively 99.7%, 99.99%, 99.9%, 99.999% and 99.999%) according to Cu 2CdSnSe 4With mix In sample Cu 2CdSn 1-xIn xSe 4The chemical formula weighing of (x=0～0.10) and the Glass tubing of packing into vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, and the Glass tubing of adorning mixture slowly is warming up to 450 ℃ and be incubated 24h, is warming up to 600 ℃～700 ℃ then and carries out solid state reaction, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time, condition and preceding similar.With resulting pure phase powder, the pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.Material has superior thermoelectricity capability.
Embodiment 10:
Adopt Cu powder, In powder and Se powder (purity is respectively 99.7%, 99.999% and 99.999%) according to CuInSe 2The chemical formula weighing and the Glass tubing of packing into, vacuumize (less than 10 -2Pa) the oxyhydrogen flame sealing by fusing use in the back, and the Glass tubing of adorning mixture slowly is warming up to 450 ℃ and be incubated 24h, is warming up to 600 ℃～700 ℃ then and carries out solid state reaction, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time, condition and preceding similar.With resulting pure phase powder, the pressure with 40～60MPa under 650 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.Material has superior thermoelectricity capability.
Embodiment 11:
Adopt Zn powder, Ge powder and P powder (purity is 99.999%),, vacuumize (less than 10 according to the chemical formula weighing of ZnGeP2 and the Glass tubing of packing into -2Pa) the oxyhydrogen flame sealing by fusing use in the back, and the Glass tubing of adorning mixture slowly is warming up to 350 ℃ and be incubated 24h, is warming up to 500 ℃～800 ℃ then and carries out the solid state reaction first time, and the reaction times is 24～96h.Powder grinds encapsulation again behind the open pipe, carries out the solid state reaction second time, and the processing condition of the processing condition solid state reaction first time are identical.With resulting pure phase powder, the pressure with 40～60MPa under 500 ℃～800 ℃ carries out the SPS sintering, finally makes the block materials of thermoelectric test.Material has superior thermoelectricity capability.

Claims (10)

1. a class can be used for the compound of thermoelectric material, and the composition general formula that it is characterized in that described compound is A 2BCQ 4, A is Cu, Ag or Au in the formula; B be in Zn, Cd, Hg, Fe, Ni and the Pd divalent ion any or be in B, Al, Ga and the In trivalent ion any; C be in Si, Ge, Sn and the Pb quadrivalent ion any or be in B, Al, Ga and the In trivalent ion any; Q be among S, Se and the Te any or be among N, P, As and the Sb any.
2. can be used for the compound of thermoelectric material by the described class of claim 1, it is characterized in that described compound belongs to tetragonal system, structure is a chalcopyrite.
3. the compound that can be used for thermoelectric material by the described class of claim 2 is characterized in that the zink sulphide superstructure of the structure of described compound for distortion, and the Fe position of half replaces by the B bit is plain, and second half then replaces by the C bit is plain.
4. the compound that can be used for thermoelectric material by the described class of claim 1 is characterized in that A, B, C form tetrahedral coordination with Q respectively, are similar to the diamond network structure.
5. the compound that can be used for thermoelectric material by the described class of claim 1, when it is characterized in that B position and C position replace for trivalent ion simultaneously in the compound, structural formula is reduced to chalcopyrite type cpd ABQ 2Or Q when the C position is quadrivalent cation, satisfies the valence state balance in the negative trivalent negatively charged ion, A position ion disappearance, and structural formula is BCQ ' 2
6. the compound that can be used for thermoelectric material by the described class of claim 1 is characterized in that by mixing, and the plain valency of A bit is improved, and increases hole concentration; Or, the plain valency of C bit is reduced by mixing, and increase electron density, improve the conductivity of material; Mixing, there have between the compound of back to be multiple compound, and the compound general formula is (1-x) A 2BCQ 4-xA ' B ' Q ' 2, 0≤x in the formula≤1.
7. can be used for the compound of thermoelectric material by the described class of claim 6, the concentration that it is characterized in that described dopant is between 0at%-10at%.
8. prepare the method that a class as claimed in claim 1 can be used for the compound of thermoelectric material, it is characterized in that preparation process is:
(a) press A 2BCQ 4It is raw material that the chemical constitution proportioning is selected corresponding simple substance or chalkogenide for use, prepares burden;
(b) raw material is packed in the encloses container of quartz glass tube starvation, encapsulation after vacuumizing;
(c) Feng Zhuan quartz glass tube carries out the solid state reaction first time under 600 ℃～700 ℃, and the reaction times is 24～96h; Grind encapsulation again behind the open pipe, carry out the solid state reaction second time, condition is with for the first time identical; Maybe the quartz glass tube with encapsulation places High Temperature Furnaces Heating Apparatus to be carried out at 650 ℃～1050 ℃ frit reactions;
(d) or with the batching of step (a) be sealed in vacuumize or filling with inert gas protection ball grinder in, carry out high-energy ball milling, the ball milling time is 2～24h; Or with the batching of step (a) quartz glass tube of packing into, vacuumize the back and use the oxyhydrogen flame sealing by fusing, carry out frit reaction in 700 ℃～1000 ℃;
(e) with step (c) or (d) gained sample grinding, obtain powder, under 650 ℃～850 ℃ temperature and the pressure of 40～60Mpa, carry out the SPS sintering or the quartz glass tube of behind the 200Mpa cold isostatic compaction, packing into be packaged in 700 ℃～900 ℃ the insulation 6～24h, finally make novel thermoelectric block body material.
9. the preparation method who can be used for the compound of thermoelectric material by the described class of claim 8 is characterized in that solid state reaction is to carry out in the closed environment of the Glass tubing starvation atmosphere of sealing by fusing, the SPS sintering carries out at Ar or N2 or under vacuumizing.
10. the preparation method who can be used for the compound of thermoelectric material by the described class of claim 8 is characterized in that step (c) the frit reaction time is 4～96 hours.
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