CN105047809A - SnSe-based thermoelectric material and preparation method thereof - Google Patents
SnSe-based thermoelectric material and preparation method thereof Download PDFInfo
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- CN105047809A CN105047809A CN201510386988.4A CN201510386988A CN105047809A CN 105047809 A CN105047809 A CN 105047809A CN 201510386988 A CN201510386988 A CN 201510386988A CN 105047809 A CN105047809 A CN 105047809A
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Abstract
The invention discloses an SnSe-based thermoelectric material and a preparation method thereof. The preparation method includes steps: S100 weighing reaction raw material according to the stoichiometric ratio of the SnSe-based thermoelectric material; S200 refining the reaction raw material through a melt-refining process to obtain SnSe-based thermoelectric material ingots; and S300 placing SnSe-based thermoelectric material ingots obtained from the S200 in a zone smelting furnace and growing polycrystalline SnSe-based thermoelectric material through a zone melting method. The SnSe-based thermoelectric material obtained through the method is preferential and has better thermoelectric performance. Compared with a method for preparing monocrystalline SnSe-based thermoelectric material, the method is simple and is short in growth period, low in cost, and suitable for mass industrial production.
Description
Technical field
The present invention relates to thermoelectric material field, particularly relate to a kind of SnSe base thermoelectricity material and preparation method thereof.
Background technology
Thermoelectric material, be utilize phonon and charge carrier transport the functional material realizing heat energy and electric energy and directly mutually change.The nondimensional thermoelectric figure of merit of general employing (ZT value) characterizes the performance of thermoelectric material, wherein, and ZT=S
2t σ/κ, S are Seebeck coefficient, and σ is conductivity, and κ is thermal conductivity, and T is temperature.Generally, ZT value is larger, and conversion efficiency of thermoelectric is higher.And the difficulty putting forward high zt be to determine this value each parameter between interrelated.At present, the main path putting forward high zt has: by introducing point defect, crystal boundary or finding the thermal conductivity that phonon glasses-electron crystal class thermoelectric material carrys out condition standing lattice; Nucleocapsid structure is utilized to improve power factor; Seebeck coefficient, being coupled between conductivity with thermal conductivity three is weakened by the low-dimensional or phase transformation etc. of material; Seek the thermoelectric material etc. that intrinsic thermal conductivity is low.
2014, the people such as Zhao Lidong have prepared lamellar single crystal SnSe by Bridgman method, it has ultralow intrinsic thermal conductivity and the power factor of medium level, thus obtains the ZT value up to 2.6 (at 650 DEG C) at b axle, obtains the thermoelectric material that performance is up to now best.But, the bad mechanical property of lamellar single crystal, and preparation time is long, energy consumption is large, is difficult to be applied to large-scale industrial production.
The people such as S.Sassi adopt vacuum fusion to prepare the polycrystalline SnS e with certain orientation in conjunction with the technique of discharge plasma sintering, its thermoelectricity capability is perpendicular to pressure direction and be parallel to pressure direction and have certain anisotropy, but the ZT difference in both direction is not obvious, maximum ZT value is only 0.5.The people such as Q.zhang utilize smelting process to prepare polycrystalline SnS e in conjunction with the mode of hot pressed sintering, there is the problem that orientation is not good equally, and maximum ZT value is only 0.82 500 DEG C time.
Summary of the invention
The invention provides and a kind ofly prepare simple, growth cycle is short, thermoelectricity capability is excellent SnSe base thermoelectricity material and preparation method thereof.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for SnSe base thermoelectricity material, comprises the following steps:
S100, takes reaction raw materials according to the stoichiometric proportion of SnSe base thermoelectricity material;
S200, utilizes smelting process to refine described reaction raw materials, obtains SnSe base thermoelectricity material ingot casting;
S300, is placed in zone melting furnace by the SnSe base thermoelectricity material ingot casting obtained in S200, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.
Wherein in an embodiment, S200 comprises the following steps:
S210, puts into the first reaction vessel by the reaction raw materials taken in S100, sealed after being vacuumized;
S220, is placed in smelting furnace by described first reaction vessel, is incubated 1h ~ 12h after being warming up to 780 DEG C ~ 1400 DEG C;
S230, namely obtains SnSe base thermoelectricity material ingot casting after described first reaction vessel is cooled to room temperature.
Wherein in an embodiment, the heating rate in S220 is 1 DEG C/min ~ 10 DEG C/min.
Wherein in an embodiment, S300 comprises the following steps:
First reaction vessel of the described SnSe of being equipped with base thermoelectricity material ingot casting is placed in the second reaction vessel, by described second reaction vessel sealed after being vacuumized, then described second reaction vessel is placed in zone melting furnace, growing by zone melting polycrystalline SnS e base thermoelectricity material.
Wherein in an embodiment, in the growth course of described polycrystalline SnS e base thermoelectricity material, the rate travel in melting zone is 1mmh
-1~ 25mmh
-1.
Wherein in an embodiment, in the growth course of described polycrystalline SnS e base thermoelectricity material, melting zone temperature is 780 DEG C ~ 1400 DEG C, and melting zone width is 30mm ~ 40mm.
Wherein in an embodiment, described smelting furnace is rocking furnace.
A kind of SnSe base thermoelectricity material, adopt above-mentioned method to be prepared, the chemical structural formula of described SnSe base thermoelectricity material is Sn
a-xm
xse
1-yr
y;
Wherein, M is at least one in Ge, Pb, Sb, Bi, Al, Ga, In, Zn, Cd, Hg, Cu, Ag, Au, Co, Mn, Fe, Na, K and Tl, R is at least one in S, Te, Cl, Br and I, and 0.8≤a≤1.2,0≤x < 1,0≤y < 1.
Wherein in an embodiment, a=1,0≤x≤0.2,0≤y≤0.2.
Wherein in an embodiment, the degree of grain alignment of described polycrystalline SnS e base thermoelectricity material is more than or equal to 0.9.
The present invention has following beneficial effect:
The present invention prepares polycrystalline SnS e base thermoelectricity material by the mode that smelting process combines with zone-melting process, first the raw material prepared is placed in smelting furnace and carries out melting, obtain SnSe base thermoelectricity material ingot casting, then the ingot casting obtained is placed in zone melting furnace, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.Owing to utilizing zone-melting process to grow in the process of polycrystalline, the movement in melting zone has certain directivity, such that crystal grain is easier to be grown along specific direction, and the polycrystalline product preferred orientation finally obtained is obvious, more levels off to monocrystalline, has preferably thermoelectricity capability; Meanwhile, compared with the preparation of monocrystalline SnSe base thermoelectricity material, the preparation method of polycrystalline SnS e base thermoelectricity material of the present invention is simple, and growth cycle is short, with low cost, can be applicable to large-scale industrial production.
Polycrystalline SnS e base thermoelectricity material provided by the invention, utilize method of the present invention to be prepared from, degree of grain alignment is higher, and preferred orientation is obvious, has excellent thermoelectricity capability, is beneficial to has broad application prospects in heat generating etc.
Accompanying drawing explanation
Fig. 1 is the SnSe powder diffraction spectrum of the powder diffraction spectrum of the sample that the embodiment of the present invention 1 obtains, block diffracting spectrum and standard;
Fig. 2 is the scanning electron microscope (SEM) photograph of the section of the sample that the embodiment of the present invention 1 obtains;
Fig. 3 is the thermoelectricity capability variation with temperature relation of the sample that the embodiment of the present invention 1 obtains.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of SnSe base thermoelectricity material, can obtain by the method the polycrystalline SnS e base thermoelectricity material that preferred orientation is obvious, thermoelectricity capability is excellent.Wherein, the SnSe base thermoelectricity material in the present invention comprises SnSe thermoelectric material, and the thermoelectric material that generating portion atom replaces on the architecture basics of SnSe, the SnSe thermoelectric material namely adulterated.
Particularly, the preparation method of SnSe base thermoelectricity material of the present invention comprises the following steps:
S100, takes reaction raw materials according to the stoichiometric proportion of SnSe base thermoelectricity material.
In the present invention, as far as possible the selection principle of reaction raw materials does not introduce irrelevant element, under normal circumstances, select compound that in the simple substance of respective element in SnSe base thermoelectricity material or SnSe base thermoelectricity material, two or more element is formed as reaction raw materials, such as, when SnSe base thermoelectricity material is SnSe
0.9br
0.1time, Sn simple substance, Se simple substance and SnBr can be selected
2compound is as reaction raw materials.As preferably, the purity of reaction raw materials is more than or equal to 99%.
S200, utilizes smelting process to refine the reaction raw materials taken in S100, obtains SnSe base thermoelectricity material ingot casting.
Preferably, as a kind of embodiment, S200 comprises the following steps:
S210, puts into the first reaction vessel by the reaction raw materials taken in S100, and by the first reaction vessel sealed after being vacuumized.
In order to prevent reaction raw materials from reacting with the oxygen in air at a higher temperature or preventing from occurring the defects such as bubble in ingot casting, need the first reaction vessel to carry out vacuumizing process and seal, preferably, the vacuum degree of the first reaction vessel is less than or equal to 10
-5pa.Wherein, the first reaction vessel adopts high temperature resistant resistance to, that chemical stability is good material to make, and is preferably quartz.In order to ensure sealing property, improving product quality, adopts oxy arc to seal quartz container.
S220, is placed in smelting furnace by the first reaction vessel, is warming up to held for some time after preset temperature.Preferably, preset temperature is 780 DEG C ~ 1400 DEG C, and temperature retention time is 1h ~ 12h.
After first reaction vessel is placed in smelting furnace, need to heat up to the first reaction vessel, wherein, in temperature-rise period, can there is solid phase reaction in reaction raw materials, generates SnSe; After temperature is increased to the fusing point of SnSe, SnSe starts to melt; After temperature is increased to preset temperature, under preset temperature, be incubated the regular hour, SnSe is melted completely as liquid.
In order to ensure the complete reaction of reaction raw materials, promote the quality of ingot casting, the heating rate in S220 is preferably 1 DEG C/min ~ 10 DEG C/min.
Preferably, the smelting furnace used in S220 is rocking furnace.In fusion process, the burner hearth waving smelting furnace can be made to swing, be beneficial to the abundant mixing of raw material, improve solid phase reaction speed and reaction mass, shorten smelting time.As preferably, the wobble frequency of rocking furnace is 5r/min ~ 15r/min, and swing angle is more than or equal to 15 ° and is less than or equal to 60 °.In this number range, the uniformity of reaction raw materials mixing can be improved further, improve reaction rate.
S230, after the first reaction vessel is cooled to room temperature, can obtain SnSe base thermoelectricity material ingot casting.
Wherein, the first reaction vessel can be cooled to the furnace room temperature; Also can cool to the first reaction vessel with the furnace certain temperature, taking-up is placed in air to naturally cool to room temperature or be placed in mixture of ice and water and is cooled to room temperature; Directly the first reaction vessel can also be taken out after melting, then be placed in air and naturally cool to room temperature or be placed in mixture of ice and water and be cooled to room temperature.
Because cooling procedure has important impact for the crystal habit of the ingot casting finally obtained and tissue defects.As preferably, after the first reaction vessel being cooled to the furnace 600 DEG C ~ 900 DEG C, then the first reaction vessel is taken out smelting furnace, be placed in air and naturally cool to room temperature.Under this condition, be conducive to obtaining the ingot casting that crystal habit is good, tissue defects is few, effectively prevent the appearance in crack in ingot casting, greatly reduce the internal stress of ingot casting, improve the physicochemical property of ingot casting, the lifting of follow-up polycrystalline SnS e base thermoelectricity material performance is laid the foundation.
S300, the SnSe base thermoelectricity material ingot casting obtained by S200 is placed in zone melting furnace, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.
As a kind of embodiment, S300 comprises the following steps:
S310, is placed in the second reaction vessel by the first reaction vessel that SnSe base thermoelectricity material ingot casting is housed, and by the second reaction vessel sealed after being vacuumized.
Owing to there is significant thermal expansion coefficient difference between SnSe base thermoelectricity material and the first reaction vessel, thus the first reaction vessel may be caused to melt in process in district burst, after first reaction vessel being placed in the second reaction vessel of Vacuum Package, effectively can avoid the oxidation of the first reaction vessel SnSe base thermoelectricity material after bursting.
S320, is placed in zone melting furnace by described second reaction vessel, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.
Zone-melting process is normally by an ingot melting Ge Zhai district, and the remainder of ingot casting keeps solid-state, then makes melting zone move along the length direction of ingot casting, makes the remainder of whole ingot casting melt post crystallization successively.
Wherein, the growth type of crystal can be regulated and controled according to the rate travel in melting zone, when the rate travel in melting zone is slower, can single crystal product article be obtained, when the rate travel in melting zone is very fast, polycrystalline product can be obtained.As preferably, in the present invention, the rate travel in melting zone is 1mmh
-1~ 25mmh
-1.Under this rate travel, polycrystalline SnS e base thermoelectricity material can be obtained, and effectively can promote the thermoelectricity capability of the polycrystalline SnS e base thermoelectricity material obtained.
Research shows, the preferred orientation of SnSe base thermoelectricity material is more obvious, its thermoelectric figure of merit is larger, thermoelectricity capability is better, but preparation SnSe monocrystalline process is loaded down with trivial details, and growth cycle is long, be unfavorable for large-scale industrial production, and the monocrystalline bad mechanical property of preparation, therefore, main purpose of the present invention is prepares preferred orientation good polycrystalline SnS e base thermoelectricity material.
Preferably, in the growth course of polycrystalline SnS e base thermoelectricity material, melting zone temperature is 780 DEG C ~ 1400 DEG C, and melting zone width is 30mm ~ 40mm.Under this parameter, the good crystal of crystalline quality can be obtained, further increase the preferred orientation of crystal grain, and then improve the thermoelectricity capability of polycrystalline SnS e base thermoelectricity material.
The present invention prepares polycrystalline SnS e base thermoelectricity material by the mode that smelting process combines with zone-melting process, first the raw material prepared is placed in smelting furnace and carries out melting, obtain SnSe base thermoelectricity material ingot casting, then the ingot casting obtained is placed in zone melting furnace, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.Owing to utilizing zone-melting process to grow in the process of polycrystalline, the movement in melting zone has certain directivity, such that crystal grain is easier to be grown along specific direction, and the polycrystalline product preferred orientation finally obtained is obvious, more levels off to monocrystalline, has preferably thermoelectricity capability; Meanwhile, compared with the preparation of monocrystalline SnSe base thermoelectricity material, the preparation method of polycrystalline SnS e base thermoelectricity material of the present invention is simple, and growth cycle is short, with low cost, can be applicable to large-scale industrial production.
In addition, present invention also offers a kind of SnSe base thermoelectricity material utilizing above-mentioned method to be prepared from, the chemical structural formula of this SnSe base thermoelectricity material is Sn
a-xm
xse
1-yr
y; Wherein, what M replaced is the case of Sn, is selected from least one in Ge, Pb, Sb, Bi, Al, Ga, In, Zn, Cd, Hg, Cu, Ag, Au, Co, Mn, Fe, Na, K and Tl; What R replaced is the case of Se, is selected from least one in S, Te, Cl, Br and I; And 0.8≤a≤1.2,0≤x < 1,0≤y < 1.
Owing to utilizing method of the present invention to be prepared, thus, SnSe base thermoelectricity material preferred orientation of the present invention is obvious, has excellent thermoelectricity capability, is beneficial to has broad application prospects in heat generating etc.; Meanwhile, part foreign atom can affect the unit cell dimension of SnSe base thermoelectricity material, thus improves its thermoelectricity capability; Meanwhile, the density of the polycrystalline SnS e base thermoelectricity material utilizing method of the present invention to prepare is more than or equal to 6.0gcm
-3, density is more than or equal to 97%, and higher density and density can improve the conductivity of thermoelectric material, thus are conducive to the lifting of thermoelectricity capability.
In order to ensure preferably thermoelectricity capability, as preferably, in above-mentioned SnSe base thermoelectricity material, 0.8≤a≤1.2,0≤x < 0.5,0≤y < 0.5.More preferably, a=1,0≤x≤0.2,0≤y≤0.2.Which improves Sn
a-xm
xse
1-yr
ysolid solubility, decrease the growing amount of impurity, be conducive to the raising of product thermoelectricity capability.
Preferably, the degree of grain alignment of polycrystalline SnS e base thermoelectricity material of the present invention is more than or equal to 0.9, is preferably more than 0.95.Compared to the degree of grain alignment (being about about 0.2) of the polycrystalline SnS e base thermoelectricity material in conventional art, the degree of grain alignment of polycrystalline SnS e base thermoelectricity material of the present invention is significantly improved, when other conditions are constant, degree of grain alignment is higher, the preferred orientation of material is more obvious, and its thermoelectricity capability is higher.
In order to understand the present invention better, below by specific embodiment, SnSe base thermoelectricity material of the present invention and preparation method thereof is further illustrated.It should be noted that, raw material selected in following examples is marketable material, and purity is all more than or equal to 99%.
Embodiment 1
(1) Sn particle and Se particle is taken as reaction raw materials according to the stoichiometric proportion of SnSe;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then utilizes oxy arc to seal the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 950 DEG C of 1 DEG C/min, then at 950 DEG C, be incubated 1h, wherein, the wobble frequency of rocking furnace is 5r/min, and swing angle is 60 °;
(4) after melting, close the power supply of rocking furnace, take out after cooling to the first reaction vessel with the furnace 800 DEG C, in air, be cooled to room temperature, obtain SnSe ingot casting;
(5) the first reaction vessel that SnSe ingot casting is housed is placed in the second reaction vessel, the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 1mmh
-1, melting zone temperature is 780 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
The sample obtained the present embodiment respectively carries out XRD (X-rayDiffraction, X-ray diffraction) test, SEM (ScanningElectronMicroscope, scanning electron microscopy) test and thermoelectricity capability test.Wherein, the SnSe powder diffraction spectrum that Fig. 1 (a) is standard, Fig. 1 (b) for Polycrystalline that the present embodiment obtains clay into power after X ray diffracting spectrum, the X ray diffracting spectrum of block on crystal growth direction of the sample that Fig. 1 (c) obtains for the present embodiment, Fig. 2 is the scanning electron microscope (SEM) photograph of the section of the sample that the present embodiment obtains, Fig. 3 is the thermoelectricity capability variation with temperature relation of the sample that the present embodiment obtains, two curves wherein in Fig. 3 (a) are respectively sample and are being parallel to the direction of growth and are falling in the conductivityσ's variation with temperature relation in the direction of growth, two curves in Fig. 3 (b) are respectively sample and are being parallel to the direction of growth and are falling in the Seebeck coefficient variation with temperature relation in the direction of growth, two curves in Fig. 3 (c) are respectively sample and are being parallel to the direction of growth and are falling in the thermal conductivity κ variation with temperature relation in the direction of growth, two curves in Fig. 3 (d) are respectively sample and are being parallel to the direction of growth and are falling in the thermoelectric figure of merit ZT variation with temperature relation in the direction of growth.
From Fig. 1 (a) and Fig. 1 (b), the sample that the present embodiment obtains be SnSe mutually, can judge that sample that the present embodiment obtains is as SnSe thus; From Fig. 1 (c), the crystal grain of sample prepared by the present embodiment has obvious preferred orientation along the direction of growth of crystal; As shown in Figure 2, the sample that prepared by the present embodiment has obvious layer structure and anisotropy; As shown in Figure 3, the conductivity of the sample that the present embodiment obtains, thermal conductivity, Seebeck coefficient, ZT value all show obvious anisotropy, and the thermoelectricity capability being parallel to the direction of growth is much better than the thermoelectricity capability perpendicular to the direction of growth, this sample is 0.92 being parallel to the ZT value in the direction of growth at 600 DEG C, is improved largely compared with the polycrystalline SnS e material utilizing discharge plasma sintering and hot pressed sintering to prepare in conventional art.
Complex chart 1 to Fig. 3 can judge the polycrystalline SnS e material that the sample that the present embodiment obtains is obvious as preferred orientation, thermoelectricity capability is excellent.Through measuring, the degree of grain alignment of this polycrystalline SnS e material is 0.95, and density is 6.04gcm
-3, density is 97%.
Embodiment 2
(1) according to Sn
1.2the stoichiometric proportion of Se takes Sn particle and Se particle as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-6pa, then utilizes oxy arc to seal the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 900 DEG C of 2 DEG C/min, then at 900 DEG C, be incubated 8h, wherein, the wobble frequency of rocking furnace is 10r/min, and swing angle is 20 °;
(4), after melting, close the power supply of rocking furnace, cool to the first reaction vessel with the furnace room temperature, obtain Sn
1.2se ingot casting;
(5) Sn will be housed
1.2first reaction vessel of Se ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-6seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 3mmh
-1, melting zone temperature is 950 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.94, be 0.91 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.0gcm
-3, density is 95%.
Embodiment 3
(1) according to Sn
0.8the stoichiometric proportion of Se takes Sn particle and Se particle as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 920 DEG C of 5 DEG C/min, then at 920 DEG C, be incubated 6h, wherein, the wobble frequency of rocking furnace is 15r/min, and swing angle is 15 °;
(4) after melting, close the power supply of rocking furnace, the first reaction vessel is taken out and is placed in mixture of ice and water, be quickly cooled to room temperature, obtain Sn
0.8se ingot casting;
(5) Sn will be housed
0.8first reaction vessel of Se ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 25mmh
-1, melting zone temperature is 980 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.92, be 0.9 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.1gcm
-3, density is 90%.
Embodiment 4
(1) according to Sn
0.5ge
0.5the stoichiometric proportion of Se takes Sn particle, Se particle and Ge block as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-6pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 780 DEG C of 4 DEG C/min, then at 780 DEG C, be incubated 12h, wherein, the wobble frequency of rocking furnace is 8r/min, and swing angle is 30 °;
(4), after melting, close the power supply of rocking furnace, the first reaction vessel is cooled to the furnace 600 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.5ge
0.5se ingot casting;
(5) Sn will be housed
0.5ge
0.5first reaction vessel of Se ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-6seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 10mmh
-1, melting zone temperature is 780 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.96, be 0.94 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.02gcm
-3, density is 94%.
Embodiment 5
(1) according to Sn
0.85mn
0.2the stoichiometric proportion of Se takes Sn particle, Se particle and Mn particle as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 1400 DEG C of 10 DEG C/min, then at 1400 DEG C, be incubated 5h, wherein, the wobble frequency of rocking furnace is 6r/min, and swing angle is 45 °;
(4), after melting, close the power supply of rocking furnace, the first reaction vessel is cooled to the furnace 900 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.85mn
0.2se ingot casting;
(5) Sn will be housed
0.85mn
0.2first reaction vessel of Se ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 15mmh
-1, melting zone temperature is 1400 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.96, be 0.93 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.05gcm
-3, density is 94%.
Embodiment 6
(1) according to SnSe
0.9br
0.1stoichiometric proportion take Sn particle, Se particle and SnBr
2as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 880 DEG C of 3 DEG C/min, then at 880 DEG C, be incubated 6h, wherein, the wobble frequency of rocking furnace is 4r/min, and swing angle is 35 °;
(4), after melting, close the power supply of rocking furnace, the first reaction vessel is cooled to the furnace 700 DEG C of taking-ups, naturally cool to room temperature, obtain SnSe
0.9br
0.1ingot casting;
(5) SnSe will be housed
0.9br
0.1first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 1mmh
-1, melting zone temperature is 920 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.97, be 0.94 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.06gcm
-3, density is 96%.
Embodiment 7
(1) according to Sn
0.9se
0.8cl
0.2stoichiometric proportion take Sn particle, Se particle and Cl
2se powder is as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 920 DEG C of 2 DEG C/min, then at 920 DEG C, be incubated 1h, wherein, the wobble frequency of rocking furnace is 3r/min, and swing angle is 45 °;
(4), after melting, close the power supply of rocking furnace, the first reaction vessel is cooled to the furnace 800 DEG C of taking-ups, be placed in mixture of ice and water and be quickly cooled to room temperature, obtain Sn
0.9se
0.8cl
0.2ingot casting;
(5) Sn will be housed
0.9se
0.8cl
0.2first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 5mmh
-1, melting zone temperature is 920 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.95, be 0.93 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.03gcm
-3, density is 92%.
Embodiment 8
(1) according to Sn
0.95cd
0.15se
0.9br
0.1stoichiometric proportion take Sn particle, Se particle, Cd block and SnBr
2powder is as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-6pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 1000 DEG C of 5 DEG C/min, then at 1000 DEG C, be incubated 4h, wherein, the wobble frequency of rocking furnace is 2r/min, and swing angle is 15 °;
(4) after melting, close the power supply of rocking furnace, the first reaction vessel taking-up is placed in mixture of ice and water and is quickly cooled to room temperature, obtain Sn
0.95cd
0.15se
0.9br
0.1ingot casting;
(5) Sn will be housed
0.95cd
0.15se
0.9br
0.1first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-6seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 20mmh
-1, melting zone temperature is 950 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.94, be 0.91 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.02gcm
-3, density is 90%.
Embodiment 9
(1) according to Sn
0.8pb
0.1sb
0.1se
0.05te
0.05s
0.9stoichiometric proportion take Sn particle, Se particle, Pb particle, Te block and S powder as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-6pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 1200 DEG C of 5 DEG C/min, then at 1200 DEG C, be incubated 3h, wherein, the wobble frequency of rocking furnace is 4r/min, and swing angle is 25 °;
(4), after melting, close the power supply of rocking furnace, the first reaction vessel is cooled to the furnace 850 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.8pb
0.1sb
0.1se
0.05te
0.05s
0.9ingot casting;
(5) Sn will be housed
0.8pb
0.1sb
0.1se
0.05te
0.05s
0.9first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-6seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 6mmh
-1, melting zone temperature is 1100 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.96, be 0.93 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.02gcm
-3, density is 92%.
Embodiment 10
(1) according to Sn
0.9bi
0.1se
0.7i
0.3stoichiometric proportion take Sn particle, Se particle, metal Bi and I particle as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in rocking furnace, with the ramp to 950 DEG C of 5 DEG C/min, then at 950 DEG C, be incubated 5h, wherein, the wobble frequency of rocking furnace is 4r/min, and swing angle is 25 °;
(4), after melting, close the power supply of rocking furnace, the first reaction vessel is cooled to the furnace 650 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.9bi
0.1se
07i
0.3ingot casting;
(5) Sn will be housed
0.9bi
0.1se
07i
0.3first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 2mmh
-1, melting zone temperature is 1000 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.9, be 0.9 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.0gcm
-3, density is 91%.
Embodiment 11
(1) according to Sn
0.05ge
0.75in
0.1zn
0.1the stoichiometric proportion of Se takes the simple substance of Sn, Se, Ge, In and Zn as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in smelting furnace, at being warming up to 950 DEG C, is incubated 12h;
(4), after melting, close the power supply of smelting furnace, the first reaction vessel is cooled to the furnace 650 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.05ge
0.75in
0.1zn
0.1se ingot casting;
(5) Sn will be housed
0.05ge
0.75in
0.1zn
0.1first reaction vessel of Se ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 2mmh
-1, melting zone temperature is 1050 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.9, be 0.9 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.01gcm
-3, density is 92%.
Embodiment 12
(1) according to Sn
0.6hg
0.2cu
0.2se
0.6br
0.4stoichiometric proportion take simple substance and the compound S nBr of Sn, Hg, Cu, Se
2as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in smelting furnace, at being warming up to 1300 DEG C, is incubated 4h;
(4), after melting, close the power supply of smelting furnace, the first reaction vessel is cooled to the furnace 650 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.6hg
0.2cu
0.2se
0.6br
0.4ingot casting;
(5) Sn will be housed
0.6hg
0.2cu
0.2se
0.6br
0.4first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 10mmh
-1, melting zone temperature is 1250 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.9, be 0.9 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.0gcm
-3, density is 90%.
Embodiment 13
(1) according to Sn
0.5ag
0.3au
0.2se
0.5cl
0.5stoichiometric proportion take simple substance and the Compound C l of Sn, Ag, Au, Se
2se is as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in smelting furnace, at being warming up to 1200 DEG C, is incubated 1h;
(4), after melting, close the power supply of smelting furnace, the first reaction vessel is cooled to the furnace 620 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.5ag
0.3au
0.2se
0.5cl
0.5ingot casting;
(5) Sn will be housed
0.5ag
0.3au
0.2se
0.5cl
0.5first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 1mmh
-1, melting zone temperature is 1100 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.92, be 0.91 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.03gcm
-3, density is 92%.
Embodiment 14
(1) according to Sn
0.85co
0.1fe
0.05se
0.8cl
0.2stoichiometric proportion take simple substance and the Compound C l of Sn, Co, Fe, Se
2se is as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in smelting furnace, at being warming up to 800 DEG C, is incubated 10h;
(4), after melting, close the power supply of smelting furnace, the first reaction vessel is cooled to the furnace 650 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.85co
0.1fe
0.05se
0.8cl
0.2ingot casting;
(5) Sn will be housed
0.85co
0.1fe
0.05se
0.8cl
0.2first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 20mmh
-1, melting zone temperature is 900 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.95, be 0.91 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.08gcm
-3, density is 94%.
Embodiment 15
(1) according to Sn
0.98na
0.01k
0.01se
0.99cl
0.01stoichiometric proportion take simple substance and the Compound C l of Sn, Na, K, Se
2se is as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in smelting furnace, at being warming up to 900 DEG C, is incubated 2h;
(4), after melting, close the power supply of smelting furnace, the first reaction vessel is cooled to the furnace 650 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.98na
0.01k
0.01se
0.99cl
0.01ingot casting;
(5) Sn will be housed
0.98na
0.01k
0.01se
0.99cl
0.01first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 2mmh
-1, melting zone temperature is 1000 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.96, be 0.91 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.04gcm
-3, density is 92%.
Embodiment 16
(1) according to Sn
0.9tl
0.1se
0.8cl
0.1br
0.1stoichiometric proportion take simple substance and the Compound C l of Sn, Tl, Se
2se and SnBr
2as reaction raw materials;
(2) reaction raw materials taken in step (1) is loaded in clean the first dry reaction vessel, the first reaction vessel is evacuated to 10
-5pa, then seals the opening of the first reaction vessel;
(3) the first reaction vessel after sealing is placed in smelting furnace, at being warming up to 950 DEG C, is incubated 8h;
(4), after melting, close the power supply of smelting furnace, the first reaction vessel is cooled to the furnace 650 DEG C of taking-ups, naturally cool to room temperature, obtain Sn
0.9tl
0.1se
0.8cl
0.1br
0.1ingot casting;
(5) Sn will be housed
0.9tl
0.1se
0.8cl
0.1br
0.1first reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction vessel is evacuated to 10
-5seal after Pa;
(6) the second reaction vessel after sealing is placed in zone melting furnace to carry out district and melt, wherein, the rate travel in melting zone is 5mmh
-1, melting zone temperature is 1000 DEG C, and melting zone width is 30mm ~ 40mm;
(7) district can obtain sample after melting.
Known after tested, the sample that the present embodiment obtains is polycrystalline SnS e base thermoelectricity material (X-ray powder diffraction pattern of the sample obtained in the present embodiment and the SnSe powder diffraction spectrum of standard match), and the preferred orientation of this sample is obvious, thermoelectricity capability is excellent, degree of grain alignment is 0.95, be 0.9 being parallel to the ZT value in the direction of growth (600 DEG C), density is 6.0gcm
-3, density is 90%.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.For the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a preparation method for SnSe base thermoelectricity material, is characterized in that, comprises the following steps:
S100, takes reaction raw materials according to the stoichiometric proportion of SnSe base thermoelectricity material;
S200, utilizes smelting process to refine described reaction raw materials, obtains SnSe base thermoelectricity material ingot casting;
S300, is placed in zone melting furnace by the SnSe base thermoelectricity material ingot casting obtained in S200, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.
2. the preparation method of SnSe base thermoelectricity material according to claim 1, it is characterized in that, S200 comprises the following steps:
S210, puts into the first reaction vessel by the reaction raw materials taken in S100, sealed after being vacuumized;
S220, is placed in smelting furnace by described first reaction vessel, is incubated 1h ~ 12h after being warming up to 780 DEG C ~ 1400 DEG C;
S230, namely obtains SnSe base thermoelectricity material ingot casting after described first reaction vessel is cooled to room temperature.
3. the preparation method of SnSe base thermoelectricity material according to claim 2, is characterized in that, the heating rate in S220 is 1 DEG C/and min ~ 10 DEG C/min.
4. the preparation method of SnSe base thermoelectricity material according to claim 2, it is characterized in that, S300 comprises the following steps:
First reaction vessel of the described SnSe of being equipped with base thermoelectricity material ingot casting is placed in the second reaction vessel, by described second reaction vessel sealed after being vacuumized, then described second reaction vessel is placed in zone melting furnace, utilizes zone-melting process to grow polycrystalline SnS e base thermoelectricity material.
5. the preparation method of the SnSe base thermoelectricity material according to any one of Claims 1 to 4, is characterized in that, in the growth course of described polycrystalline SnS e base thermoelectricity material, the rate travel in melting zone is 1mmh
-1~ 25mmh
-1.
6. the preparation method of the SnSe base thermoelectricity material according to any one of Claims 1 to 4, is characterized in that, in the growth course of described polycrystalline SnS e base thermoelectricity material, melting zone temperature is 780 DEG C ~ 1400 DEG C, and melting zone width is 30mm ~ 40mm.
7. the preparation method of the SnSe base thermoelectricity material according to any one of Claims 1 to 4, is characterized in that, described smelting furnace is rocking furnace.
8. a SnSe base thermoelectricity material, is characterized in that, adopt the method described in any one of claim 1 ~ 7 to be prepared, the chemical structural formula of described SnSe base thermoelectricity material is Sn
a-xm
xse
1-yr
y;
Wherein, M is at least one in Ge, Pb, Sb, Bi, Al, Ga, In, Zn, Cd, Hg, Cu, Ag, Au, Co, Mn, Fe, Na, K and Tl, R is at least one in S, Te, Cl, Br and I, and 0.8≤a≤1.2,0≤x < 1,0≤y < 1.
9. SnSe base thermoelectricity material according to claim 8, is characterized in that, a=1,0≤x≤0.2,0≤y≤0.2.
10. SnSe base thermoelectricity material according to claim 8, is characterized in that, the degree of grain alignment of described polycrystalline SnS e base thermoelectricity material is more than or equal to 0.9.
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