CN105047809B - SnSe base thermoelectricity materials and preparation method thereof - Google Patents
SnSe base thermoelectricity materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of SnSe base thermoelectricity materials and preparation method thereof, wherein, the preparation method of SnSe base thermoelectricity materials comprises the following steps：S100 weighs reaction raw materials according to the stoichiometric ratio of SnSe base thermoelectricity materials；S200 refines the reaction raw materials using smelting process, obtains SnSe base thermoelectricity material ingot castings；The SnSe base thermoelectricity material ingot castings obtained in S200 are placed in zone melting furnace by S300, grow polycrystalline SnS e base thermoelectricity materials using zone-melting process.The polycrystalline SnS e base thermoelectricity material preferred orientations that the preparation method of the present invention obtains are apparent, have preferable thermoelectricity capability；Meanwhile compared with the preparation of monocrystalline SnSe base thermoelectricity materials, preparation method of the invention is simple, and growth cycle is short, of low cost, can be applied to large-scale industrial production.
Description
Technical field
The present invention relates to thermoelectric material field, more particularly to a kind of SnSe base thermoelectricity materials and preparation method thereof.
Background technology
Thermoelectric material is the function material for transporting realization thermal energy and directly mutually being converted with electric energy using phonon and carrier
Material.The performance of thermoelectric material is generally characterized using nondimensional thermoelectric figure of merit (ZT values), wherein, ZT=S2T σ/κ, S are
Seebeck coefficients, σ are electrical conductivity, and κ is thermal conductivity, and T is temperature.Under normal circumstances, ZT values are bigger, and conversion efficiency of thermoelectric is higher.
And the difficulty for putting forward high zt be to determine it is interrelated between each parameter of the value.At present, the main path for putting forward high zt has：Pass through
It introduces point defect, crystal boundary or finds the thermal conductivity that phonon glasses-electron crystal class thermoelectric material carrys out condition standing lattice；Utilize core
Shell structure improves power factor；Seebeck coefficient, electrical conductivity and thermal conductivity three are weakened by the low-dimensional of material or phase transformation etc.
Between coupling；Seek low thermoelectric material of intrinsic thermal conductivity etc..
2014, Zhao Lidong et al. was prepared for lamellar single crystal SnSe with Bridgman method, with ultralow intrinsic thermal conductivity
The power factor of rate and medium level, thus the ZT values of up to 2.6 (at 650 DEG C) are obtained in b axis, obtain property so far
The best thermoelectric material of energy.But the bad mechanical property of lamellar single crystal, and preparation time is long, energy consumption is big, is difficult to apply to advise greatly
The industrial production of mould.
The technique that S.Sassi et al. combines discharge plasma sintering using vacuum fusion has been prepared with certain orientation
Polycrystalline SnS e, thermoelectricity capability has certain anisotropy perpendicular to pressure direction and parallel to pressure direction, but two
ZT difference unobvious on a direction, maximum ZT values are only 0.5.Q.zhang et al. utilizes the side of smelting process combination hot pressed sintering
Formula prepares polycrystalline SnS e, equally exists the problem of orientation is bad, maximum ZT values are at 500 DEG C only 0.82.
The content of the invention
Present invention offer is a kind of to prepare the SnSe base thermoelectricity materials simple, growth cycle is short, thermoelectricity capability is excellent and its system
Preparation Method.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of SnSe base thermoelectricity materials, comprises the following steps：
S100 weighs reaction raw materials according to the stoichiometric ratio of SnSe base thermoelectricity materials；
S200 refines the reaction raw materials using smelting process, obtains SnSe base thermoelectricity material ingot castings；
The SnSe base thermoelectricity material ingot castings obtained in S200 are placed in zone melting furnace by S300, grow polycrystalline using zone-melting process
SnSe base thermoelectricity materials.
In one of the embodiments, S200 comprises the following steps：
The reaction raw materials weighed in S100 are put into the first reaction vessel, sealed after being vacuumized by S210；
First reaction vessel is placed in smelting furnace by S220, and 1h~12h is kept the temperature after being warming up to 780 DEG C~1400 DEG C；
S230 obtains SnSe base thermoelectricity material ingot castings after first reaction vessel is cooled to room temperature.
In one of the embodiments, the heating rate in S220 is 1 DEG C/min~10 DEG C/min.
In one of the embodiments, S300 comprises the following steps：
First reaction vessel equipped with SnSe base thermoelectricity material ingot castings is placed in the second reaction vessel, by described
Then second reaction vessel is placed in zone melting furnace by two reaction vessel sealed after being vacuumized, growing by zone melting polycrystalline SnS e bases
Thermoelectric material.
In one of the embodiments, in the growth course of the polycrystalline SnS e base thermoelectricity materials, the rate travel in melting zone
For 1mmh-1~25mmh-1。
In one of the embodiments, in the growth course of the polycrystalline SnS e base thermoelectricity materials, melting zone temperature is 780 DEG C
~1400 DEG C, melting zone width is 30mm~40mm.
In one of the embodiments, the smelting furnace is rocking furnace.
A kind of SnSe base thermoelectricity materials, adopt and are prepared with the aforedescribed process, the chemistry knot of the SnSe base thermoelectricity materials
Structure formula is Sna-xMxSe1-yRy；
Wherein, in M Ge, Pb, Sb, Bi, Al, Ga, In, Zn, Cd, Hg, Cu, Ag, Au, Co, Mn, Fe, Na, K and Tl
At least one, at least one of R S, Te, Cl, Br and I, and 0.8≤a≤1.2,0≤x ＜ 1,0≤y ＜ 1.
In one of the embodiments, a=1,0≤x≤0.2,0≤y≤0.2.
In one of the embodiments, the degree of grain alignment of the polycrystalline SnS e base thermoelectricity materials is more than or equal to 0.9.
The present invention has the advantages that：
The present invention prepares polycrystalline SnS e base thermoelectricity materials smelting process in a manner that zone-melting process is combined, and will match somebody with somebody first
The raw material made, which is placed in smelting furnace, carries out melting, obtains SnSe base thermoelectricity material ingot castings, obtained ingot casting then is placed in area
In smelting furnace, polycrystalline SnS e base thermoelectricity materials are grown using zone-melting process.During using zone-melting process growth polycrystalline, melting zone
It is mobile that there is certain directionality so that crystal grain is grown more easily along specific direction, the polycrystalline product finally obtained
Preferred orientation is apparent, more levels off to monocrystalline, has preferable thermoelectricity capability；Meanwhile with the preparation of monocrystalline SnSe base thermoelectricity materials
It compares, the preparation method of polycrystalline SnS e base thermoelectricity materials of the invention is simple, and growth cycle is short, of low cost, can be applied to big
The industrial production of scale.
Polycrystalline SnS e base thermoelectricity materials provided by the invention, using the present invention method be prepared, degree of grain alignment compared with
Height, preferred orientation is apparent, has excellent thermoelectricity capability, is beneficial to have broad application prospects in heat power generation etc..
Description of the drawings
Fig. 1 is the SnSe powder of the powder diffraction spectrum of the obtained sample of the embodiment of the present invention 1, block diffracting spectrum and standard
Last diffracting spectrum；
Fig. 2 is the scanning electron microscope (SEM) photograph of the section for the sample that the embodiment of the present invention 1 obtains；
Fig. 3 is the thermoelectricity capability variation with temperature relation for the sample that the embodiment of the present invention 1 obtains.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The present invention provides a kind of preparation methods of SnSe base thermoelectricity materials, and it is bright to can obtain preferred orientation by this method
Polycrystalline SnS e base thermoelectricity materials aobvious, thermoelectricity capability is excellent.Wherein, the SnSe base thermoelectricity materials in the present invention include SnSe thermoelectricity
Material and the thermoelectric material that part of atoms substitution occurs on the architecture basics of SnSe, that is, the SnSe thermoelectric materials adulterated.
Specifically, the preparation method of SnSe base thermoelectricity materials of the invention comprises the following steps：
S100 weighs reaction raw materials according to the stoichiometric ratio of SnSe base thermoelectricity materials.
The selection principle of reaction raw materials is to try to not introduce unrelated element in the present invention, it is generally the case that selects SnSe
The compound that two or more element is formed in the simple substance of respective element or SnSe base thermoelectricity materials in base thermoelectricity material is made
For reaction raw materials, for example, when SnSe base thermoelectricity materials are SnSe0.9Br0.1When, Sn simple substance, Se simple substance and SnBr can be selected2Chemical combination
Object is as reaction raw materials.Preferably, the purity of reaction raw materials is more than or equal to 99%.
S200 is refined the reaction raw materials weighed in S100 using smelting process, obtains SnSe base thermoelectricity material ingot castings.
It is preferred that as a kind of embodiment, S200 comprises the following steps：
The reaction raw materials weighed in S100 are put into the first reaction vessel by S210, and the first reaction vessel is vacuumized
After seal.
Reaction raw materials react or prevent occur in ingot casting with the oxygen in air at a higher temperature in order to prevent
The defects of bubble, is, it is necessary to carry out vacuumize process by the first reaction vessel and seal, it is preferred that the vacuum degree of the first reaction vessel
Less than or equal to 10-5Pa.Wherein, the first reaction vessel is made of the material that high temperature resistant is resistance to, chemical stability is good, is preferably stone
English.In order to ensure sealing performance, product quality is promoted, quartz container is sealed using oxy arc.
First reaction vessel is placed in smelting furnace by S220, is warming up to held for some time after preset temperature.It is preferred that
Preset temperature is 780 DEG C~1400 DEG C, and soaking time is 1h~12h.
, it is necessary to heat up to the first reaction vessel after first reaction vessel is placed in smelting furnace, wherein, it was heating up
Solid phase reaction can occur for Cheng Zhong, reaction raw materials, generate SnSe；After temperature is increased to the fusing point of SnSe, SnSe starts to melt；When
After temperature is increased to preset temperature, the regular hour is kept the temperature under preset temperature, SnSe is made to melt completely as liquid.
In order to ensure the complete reaction of reaction raw materials, the quality of ingot casting is promoted, the heating rate in S220 is preferably 1 DEG C/
Min~10 DEG C/min.
It is preferred that the smelting furnace used in S220 is rocking furnace.In fusion process, the burner hearth for waving smelting furnace can be made
It swings, in favor of being sufficiently mixed for raw material, improves solid phase reaction rate and reaction mass, shorten smelting time.Preferably, it shakes
The wobble frequency of stove is put as 5r/min~15r/min, swing angle is more than or equal to 15 ° and is less than or equal to 60 °.In the numberical range,
The uniformity of reaction raw materials mixing can be further improved, improves reaction rate.
S230, after the first reaction vessel is cooled to room temperature, you can obtain SnSe base thermoelectricity material ingot castings.
Wherein, the first reaction vessel can be cooled to the furnace room temperature；Also the first reaction vessel can be cooled to the furnace centainly
Temperature, taking-up is placed in air cooled to room temperature or is placed in mixture of ice and water and be cooled to room temperature；It can also be molten
Directly the first reaction vessel is taken out after refining, cooled to room temperature in air is subsequently placed in or is placed in mixture of ice and water
It is cooled to room temperature.
Since cooling procedure has important influence for the crystal habit of ingot casting and tissue defects finally obtained.As
It is preferred that after cooling to the first reaction vessel with the furnace 600 DEG C~900 DEG C, then the first reaction vessel taken out into smelting furnace, be placed in sky
Cooled to room temperature in gas.Under the conditions of being somebody's turn to do, be conducive to obtain the ingot casting that crystal habit is good, tissue defects are few, effectively prevent
The appearance in crack in ingot casting greatly reduces the internal stress of ingot casting, improves the physicochemical property of ingot casting, to follow-up polycrystalline SnS e
The promotion of base thermoelectricity material performance lays the foundation.
The SnSe base thermoelectricity material ingot castings that S200 is obtained are placed in zone melting furnace by S300, grow polycrystalline using zone-melting process
SnSe base thermoelectricity materials.
As a kind of embodiment, S300 comprises the following steps：
The first reaction vessel equipped with SnSe base thermoelectricity material ingot castings is placed in the second reaction vessel by S310, and by
Two reaction vessel sealed after being vacuumized.
Due between SnSe base thermoelectricity materials and the first reaction vessel there are significant coefficient of thermal expansion difference, thus may
The first reaction vessel is caused to be burst during being melted in area, after the first reaction vessel is placed in the second reaction vessel of Vacuum Package,
It is possible to prevente effectively from the oxidation of the first reaction vessel SnSe base thermoelectricity materials after bursting.
Second reaction vessel is placed in zone melting furnace by S320, grows polycrystalline SnS e base thermoelectricity materials using zone-melting process.
Zone-melting process be typically will ingot melting Ge Zhai areas, ingot casting rest part holding solid-state, then make melting zone along
The length direction of ingot casting is moved so that the rest part of entire ingot casting crystallizes after melting 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,
Single crystal product article is can obtain, when the rate travel in melting zone is very fast, can obtain polycrystalline product.Preferably, in the present invention, melting zone
Rate travel is 1mmh-1~25mmh-1.Under the rate travel, polycrystalline SnS e base thermoelectricity materials can be obtained, and can effectively be carried
Rise the thermoelectricity capability of obtained polycrystalline SnS e base thermoelectricity materials.
Research shows that the preferred orientation of SnSe base thermoelectricity materials is more apparent, and thermoelectric figure of merit is bigger, and thermoelectricity capability is better,
But preparation SnSe monocrystalline processes are cumbersome, growth cycle is long, is unfavorable for large-scale industrial production, and the monocrystalline machinery prepared
Poor performance, therefore, the main object of the present invention are to prepare the preferable polycrystalline SnS e base thermoelectricity materials of preferred orientation.
It is preferred that in the growth course of polycrystalline SnS e base thermoelectricity materials, melting zone temperature is 780 DEG C~1400 DEG C, and melting zone is wide
It spends for 30mm~40mm.Under the parameter, the preferable crystal of crystalline quality is can obtain, further improves the preferred orientation of crystal grain,
And then improve the thermoelectricity capability of polycrystalline SnS e base thermoelectricity materials.
The present invention prepares polycrystalline SnS e base thermoelectricity materials smelting process in a manner that zone-melting process is combined, and will match somebody with somebody first
The raw material made, which is placed in smelting furnace, carries out melting, obtains SnSe base thermoelectricity material ingot castings, obtained ingot casting then is placed in area
In smelting furnace, polycrystalline SnS e base thermoelectricity materials are grown using zone-melting process.During using zone-melting process growth polycrystalline, melting zone
It is mobile that there is certain directionality so that crystal grain is grown more easily along specific direction, the polycrystalline product finally obtained
Preferred orientation is apparent, more levels off to monocrystalline, has preferable thermoelectricity capability；Meanwhile with the preparation of monocrystalline SnSe base thermoelectricity materials
It compares, the preparation method of polycrystalline SnS e base thermoelectricity materials of the invention is simple, and growth cycle is short, of low cost, can be applied to big
The industrial production of scale.
In addition, the present invention also provides the SnSe base thermoelectricity materials that a kind of profit is prepared with the aforedescribed process, the SnSe
The chemical structural formula of base thermoelectricity material is Sna-xMxSe1-yRy；Wherein, M substitution be Sn case, selected from Ge, Pb, Sb, Bi,
At least one of Al, Ga, In, Zn, Cd, Hg, Cu, Ag, Au, Co, Mn, Fe, Na, K and Tl；What R substituted is the case of Se, is selected
From at least one of S, Te, Cl, Br and I；And 0.8≤a≤1.2,0≤x ＜ 1,0≤y ＜ 1.
Due to being prepared using the method for the present invention, thus, SnSe base thermoelectricity material preferred orientations of the invention are apparent,
With excellent thermoelectricity capability, it is beneficial to have broad application prospects in heat power generation etc.；Meanwhile part foreign atom can influence
The unit cell dimension of SnSe base thermoelectricity materials, so as to improve its thermoelectricity capability；Meanwhile the polycrystalline of the method preparation using the present invention
The density of SnSe base thermoelectricity materials is more than or equal to 6.0gcm-3, for consistency more than or equal to 97%, higher density and consistency can
The electrical conductivity of thermoelectric material is improved, so as to be conducive to the promotion of thermoelectricity capability.
In order to ensure preferably thermoelectricity capability, preferably, in above-mentioned SnSe base thermoelectricity materials, 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 Sna-xMxSe1-yRySolid solution
Degree, reduces the growing amount of impurity, is conducive to the raising of product thermoelectricity capability.
It is preferred that the present invention polycrystalline SnS e base thermoelectricity materials degree of grain alignment be more than or equal to 0.9, be preferably 0.95 with
On.Compared to the degree of grain alignment (about 0.2 or so) of the polycrystalline SnS e base thermoelectricity materials in traditional technology, polycrystalline of the invention
The degree of grain alignment of SnSe base thermoelectricity materials is significantly improved, and when other conditions are constant, degree of grain alignment is higher, material
Preferred orientation is more apparent, and thermoelectricity capability is higher.
For a better understanding of the present invention, below by specific embodiment to the present invention SnSe base thermoelectricity materials and its
Preparation method further illustrates.It should be noted that raw material selected in following embodiment is marketable material, purity is big
In equal to 99%.
Embodiment 1
(1) Sn particles and Se particles are weighed as reaction raw materials according to the stoichiometric ratio of SnSe；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel using oxy arc；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 950 DEG C with the rate of 1 DEG C/min, then
1h is kept the temperature at 950 DEG C, wherein, the wobble frequency of rocking furnace is 5r/min, and swing angle is 60 °；
(4) after melting, the power supply of rocking furnace is closed, is taken out after cooling to the first reaction vessel with the furnace 800 DEG C, in
It is cooled to room temperature in air, obtains SnSe ingot castings；
(5) the first reaction vessel equipped with SnSe ingot castings is placed in the second reaction vessel, the second reaction vessel taken out true
Sky is to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
XRD (X-ray Diffraction, X-ray diffraction) tests, SEM are carried out to the sample that the present embodiment obtains respectively
(Scanning Electron Microscope, scanning electron microscope) is tested and thermoelectricity capability test.Wherein, Fig. 1 (a) is
The SnSe powder diffraction spectrums of standard, Fig. 1 (b) are the X-ray diffractogram after the Polycrystalline that the present embodiment obtains is clayed into power
Spectrum, Fig. 1 (c) are X ray diffracting spectrum of the block for the sample that the present embodiment obtains on crystal growth direction；Fig. 2 is this reality
Apply the scanning electron microscope (SEM) photograph of the section for the sample that example obtains；Fig. 3 is the thermoelectricity capability for the sample that the present embodiment obtains with the change of temperature
Two curves in change relation, wherein Fig. 3 (a), which are respectively sample, parallel to the direction of growth and to be fallen in the electricity in the direction of growth
Conductance σ variation with temperature relations, two curves in Fig. 3 (b), which are respectively sample, parallel to the direction of growth and to be fallen in life
Seebeck coefficient variation with temperature relations on length direction, two curves in Fig. 3 (c) are respectively sample parallel to life
Length direction and two curves fallen in the thermal conductivity κ variation with temperature relations in the direction of growth, Fig. 3 (d) are respectively sample
Product are parallel to the direction of growth and falling in the thermoelectric figure of merit ZT variation with temperature relations in the direction of growth.
From Fig. 1 (a) and Fig. 1 (b), sample that the present embodiment obtains is mutually SnSe, thus can determine that the present embodiment
Obtained sample is SnSe；From Fig. 1 (c), the crystal grain of sample manufactured in the present embodiment has along the direction of growth of crystal
Apparent preferred orientation；As shown in Figure 2, sample manufactured in the present embodiment has apparent layer structure and anisotropy；By Fig. 3
It understands, electrical conductivity, thermal conductivity, Seebeck coefficients, the ZT values of the sample that the present embodiment obtains are shown significantly respectively to different
Property, and it is much better than thermoelectricity capability perpendicular to the direction of growth parallel to the thermoelectricity capability of the direction of growth, the sample is parallel to life
ZT values on length direction are to be prepared in 0.92, with traditional technology using discharge plasma sintering and hot pressed sintering at 600 DEG C
Polycrystalline SnS e materials compared to being improved largely.
Complex chart 1 can be determined that the sample that the present embodiment obtains is more for preferred orientation is apparent, thermoelectricity capability is excellent to Fig. 3
Brilliant SnSe materials.Through measurement, the degree of grain alignment of polycrystalline SnS e materials is 0.95, density 6.04gcm-3, consistency is
97%.
Embodiment 2
(1) according to Sn1.2The stoichiometric ratio of Se weighs Sn particles and Se particles as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-6Then Pa seals the opening of the first reaction vessel using oxy arc；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 900 DEG C with the rate of 2 DEG C/min, then
8h is kept the temperature at 900 DEG C, wherein, the wobble frequency of rocking furnace is 10r/min, and swing angle is 20 °；
(4) after melting, the power supply of rocking furnace is closed, the first reaction vessel is cooled to the furnace room temperature, obtains
Sn1.2Se ingot castings；
(5) Sn will be housed1.2First reaction vessel of Se ingot castings is placed in the second reaction vessel, and the second reaction vessel is taken out
Vacuum is to 10-6It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.94, is being 0.91 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.0gcm-3, consistency 95%.
Embodiment 3
(1) according to Sn0.8The stoichiometric ratio of Se weighs Sn particles and Se particles as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 920 DEG C with the rate of 5 DEG C/min, then
6h is kept the temperature at 920 DEG C, wherein, the wobble frequency of rocking furnace is 15r/min, and swing angle is 15 °；
(4) after melting, the power supply of rocking furnace is closed, the taking-up of the first reaction vessel is placed in mixture of ice and water,
Room temperature is quickly cooled to, obtains Sn0.8Se ingot castings；
(5) Sn will be housed0.8First reaction vessel of Se ingot castings is placed in the second reaction vessel, and the second reaction vessel is taken out
Vacuum is to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.92, is being 0.9 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.1gcm-3, consistency 90%.
Embodiment 4
(1) according to Sn0.5Ge0.5The stoichiometric ratio of Se weighs Sn particles, Se particles and Ge blocks as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-6Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 780 DEG C with the rate of 4 DEG C/min, then
12h is kept the temperature at 780 DEG C, wherein, the wobble frequency of rocking furnace is 8r/min, and swing angle is 30 °；
(4) after melting, the power supply of rocking furnace is closed, cools to the first reaction vessel with the furnace 600 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.5Ge0.5Se ingot castings；
(5) Sn will be housed0.5Ge0.5First reaction vessel of Se ingot castings is placed in the second reaction vessel, and the second reaction is held
Device is evacuated to 10-6It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.96, is being 0.94 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.02gcm-3, consistency 94%.
Embodiment 5
(1) according to Sn0.85Mn0.2It is former as reaction that the stoichiometric ratio of Se weighs Sn particles, Se particles and Mn particles
Material；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 1400 DEG C with the rate of 10 DEG C/min, so
After keeping the temperature 5h at 1400 DEG C, wherein, the wobble frequency of rocking furnace is 6r/min, and swing angle is 45 °；
(4) after melting, the power supply of rocking furnace is closed, cools to the first reaction vessel with the furnace 900 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.85Mn0.2Se ingot castings；
(5) Sn will be housed0.85Mn0.2First reaction vessel of Se ingot castings is placed in the second reaction vessel, and the second reaction is held
Device is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.96, is being 0.93 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.05gcm-3, consistency 94%.
Embodiment 6
(1) according to SnSe0.9Br0.1Stoichiometric ratio weigh Sn particles, Se particles and SnBr2As reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 880 DEG C with the rate of 3 DEG C/min, then
6h is kept the temperature at 880 DEG C, wherein, the wobble frequency of rocking furnace is 4r/min, and swing angle is 35 °；
(4) after melting, the power supply of rocking furnace is closed, cools to the first reaction vessel with the furnace 700 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains SnSe0.9Br0.1Ingot casting；
(5) SnSe will be housed0.9Br0.1First reaction vessel of ingot casting is placed in the second reaction vessel, and the second reaction is held
Device is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.97, is being 0.94 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.06gcm-3, consistency 96%.
Embodiment 7
(1) according to Sn0.9Se0.8Cl0.2Stoichiometric ratio weigh Sn particles, Se particles and Cl2Se powder is as reaction
Raw material；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 920 DEG C with the rate of 2 DEG C/min, then
1h is kept the temperature at 920 DEG C, wherein, the wobble frequency of rocking furnace is 3r/min, and swing angle is 45 °；
(4) after melting, the power supply of rocking furnace is closed, the first reaction vessel is cooled to the furnace 800 DEG C of taking-ups, is placed in
Room temperature is quickly cooled in mixture of ice and water, obtains Sn0.9Se0.8Cl0.2Ingot casting；
(5) Sn will be housed0.9Se0.8Cl0.2First reaction vessel of ingot casting is placed in the second reaction vessel, by the second reaction
Container vacuum-pumping is to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.95, is being 0.93 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.03gcm-3, consistency 92%.
Embodiment 8
(1) according to Sn0.95Cd0.15Se0.9Br0.1Stoichiometric ratio weigh Sn particles, Se particles, Cd blocks and SnBr2
Powder is as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-6Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 1000 DEG C with the rate of 5 DEG C/min, so
After keeping the temperature 4h at 1000 DEG C, wherein, the wobble frequency of rocking furnace is 2r/min, and swing angle is 15 °；
(4) after melting, the power supply of rocking furnace is closed, the taking-up of the first reaction vessel is placed in mixture of ice and water fast
Speed is cooled to room temperature, and obtains Sn0.95Cd0.15Se0.9Br0.1Ingot casting；
(5) Sn will be housed0.95Cd0.15Se0.9Br0.1First reaction vessel of ingot casting is placed in the second reaction vessel, by second
Reaction vessel is evacuated to 10-6It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.94, is being 0.91 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.02gcm-3, consistency 90%.
Embodiment 9
(1) according to Sn0.8Pb0.1Sb0.1Se0.05Te0.05S0.9Stoichiometric ratio weigh Sn particles, Se particles, Pb particles,
Te blocks and S powder are as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-6Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 1200 DEG C with the rate of 5 DEG C/min, so
After keeping the temperature 3h at 1200 DEG C, wherein, the wobble frequency of rocking furnace is 4r/min, and swing angle is 25 °；
(4) after melting, the power supply of rocking furnace is closed, cools to the first reaction vessel with the furnace 850 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.8Pb0.1Sb0.1Se0.05Te0.05S0.9Ingot casting；
(5) Sn will be housed0.8Pb0.1Sb0.1Se0.05Te0.05S0.9First reaction vessel of ingot casting is placed in the second reaction vessel
In, the second reaction vessel is evacuated to 10-6It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.96, is being 0.93 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.02gcm-3, consistency 92%.
Embodiment 10
(1) according to Sn0.9Bi0.1Se0.7I0.3Stoichiometric ratio weigh Sn particles, Se particles, metal Bi and I particle make
For reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in rocking furnace, is warming up to 950 DEG C with the rate of 5 DEG C/min, then
5h is kept the temperature at 950 DEG C, wherein, the wobble frequency of rocking furnace is 4r/min, and swing angle is 25 °；
(4) after melting, the power supply of rocking furnace is closed, cools to the first reaction vessel with the furnace 650 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.9Bi0.1Se07I0.3Ingot casting；
(5) Sn will be housed0.9Bi0.1Se07I0.3First reaction vessel of ingot casting is placed in the second reaction vessel, anti-by second
Container vacuum-pumping is answered to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.9, is being 0.9 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.0gcm-3, consistency 91%.
Embodiment 11
(1) according to Sn0.05Ge0.75In0.1Zn0.1The stoichiometric ratio of Se weighs the simple substance of Sn, Se, Ge, In and Zn as anti-
Answer raw material；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in smelting furnace, is warming up at 950 DEG C and keeps the temperature 12h；
(4) after melting, the power supply of smelting furnace is closed, cools to the first reaction vessel with the furnace 650 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.05Ge0.75In0.1Zn0.1Se ingot castings；
(5) Sn will be housed0.05Ge0.75In0.1Zn0.1First reaction vessel of Se ingot castings is placed in the second reaction vessel, by
Two reaction vessels are evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.9, is being 0.9 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.01gcm-3, consistency 92%.
Embodiment 12
(1) according to Sn0.6Hg0.2Cu0.2Se0.6Br0.4Stoichiometric ratio weigh the simple substance and chemical combination of Sn, Hg, Cu, Se
Object SnBr2As reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in smelting furnace, is warming up at 1300 DEG C and keeps the temperature 4h；
(4) after melting, the power supply of smelting furnace is closed, cools to the first reaction vessel with the furnace 650 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.6Hg0.2Cu0.2Se0.6Br0.4Ingot casting；
(5) Sn will be housed0.6Hg0.2Cu0.2Se0.6Br0.4First reaction vessel of ingot casting is placed in the second reaction vessel, will
Second reaction vessel is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.9, is being 0.9 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.0gcm-3, consistency 90%.
Embodiment 13
(1) according to Sn0.5Ag0.3Au0.2Se0.5Cl0.5Stoichiometric ratio weigh the simple substance and chemical combination of Sn, Ag, Au, Se
Object Cl2Se is as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in smelting furnace, is warming up at 1200 DEG C and keeps the temperature 1h；
(4) after melting, the power supply of smelting furnace is closed, cools to the first reaction vessel with the furnace 620 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.5Ag0.3Au0.2Se0.5Cl0.5Ingot casting；
(5) Sn will be housed0.5Ag0.3Au0.2Se0.5Cl0.5First reaction vessel of ingot casting is placed in the second reaction vessel, will
Second reaction vessel is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.92, is being 0.91 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.03gcm-3, consistency 92%.
Embodiment 14
(1) according to Sn0.85Co0.1Fe0.05Se0.8Cl0.2Stoichiometric ratio weigh the simple substance and chemical combination of Sn, Co, Fe, Se
Object Cl2Se is as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in smelting furnace, is warming up at 800 DEG C and keeps the temperature 10h；
(4) after melting, the power supply of smelting furnace is closed, cools to the first reaction vessel with the furnace 650 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.85Co0.1Fe0.05Se0.8Cl0.2Ingot casting；
(5) Sn will be housed0.85Co0.1Fe0.05Se0.8Cl0.2First reaction vessel of ingot casting is placed in the second reaction vessel, will
Second reaction vessel is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.95, is being 0.91 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.08gcm-3, consistency 94%.
Embodiment 15
(1) according to Sn0.98Na0.01K0.01Se0.99Cl0.01Stoichiometric ratio weigh the simple substance and chemical combination of Sn, Na, K, Se
Object Cl2Se is as reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in smelting furnace, is warming up at 900 DEG C and keeps the temperature 2h；
(4) after melting, the power supply of smelting furnace is closed, cools to the first reaction vessel with the furnace 650 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.98Na0.01K0.01Se0.99Cl0.01Ingot casting；
(5) Sn will be housed0.98Na0.01K0.01Se0.99Cl0.01First reaction vessel of ingot casting is placed in the second reaction vessel,
Second reaction vessel is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.96, is being 0.91 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.04gcm-3, consistency 92%.
Embodiment 16
(1) according to Sn0.9Tl0.1Se0.8Cl0.1Br0.1Stoichiometric ratio weigh the simple substance and compound of Sn, Tl, Se
Cl2Se and SnBr2As reaction raw materials；
(2) reaction raw materials weighed in step (1) are fitted into the first dry reaction vessel of cleaning, the first reaction is held
Device is evacuated to 10-5Then Pa seals the opening of the first reaction vessel；
(3) the first reaction vessel after sealing is placed in smelting furnace, is warming up at 950 DEG C and keeps the temperature 8h；
(4) after melting, the power supply of smelting furnace is closed, cools to the first reaction vessel with the furnace 650 DEG C of taking-ups, it is natural
It is cooled to room temperature, obtains Sn0.9Tl0.1Se0.8Cl0.1Br0.1Ingot casting；
(5) Sn will be housed0.9Tl0.1Se0.8Cl0.1Br0.1First reaction vessel of ingot casting is placed in the second reaction vessel, will
Second reaction vessel is evacuated to 10-5It is sealed after Pa；
(6) the second reaction vessel after sealing is placed in progress area in zone melting furnace to 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) it can obtain sample after area is melted.
It understands after tested, the sample that the present embodiment obtains is the polycrystalline SnS e base thermoelectricity material (samples obtained in the present embodiment
The X-ray powder diffraction pattern of product matches with the SnSe powder diffraction spectrums of standard), and the preferred orientation of the sample it is apparent,
Thermoelectricity capability is excellent, degree of grain alignment 0.95, is being 0.9 parallel to (600 DEG C) of ZT values in the direction of growth, density is
6.0gcm-3, consistency 90%.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.For those of ordinary skill in the art, do not departing from
On the premise of present inventive concept, various modifications and improvements can be made, these belong to protection scope of the present invention.Therefore,
The protection domain of patent of the present invention should be determined by the appended claims.
Claims (9)
1. a kind of preparation method of SnSe base thermoelectricity materials, which is characterized in that comprise the following steps：
S100 weighs reaction raw materials according to the stoichiometric ratio of SnSe base thermoelectricity materials；
S200 refines the reaction raw materials using smelting process, obtains SnSe base thermoelectricity material ingot castings；
The SnSe base thermoelectricity material ingot castings obtained in S200 are placed in zone melting furnace by S300, utilize zone-melting process growth polycrystalline SnS e
Base thermoelectricity material, in the growth course of the polycrystalline SnS e base thermoelectricity materials, the rate travel in melting zone is 1mmh-1~15mmh-1。
2. the preparation method of SnSe base thermoelectricity materials according to claim 1, which is characterized in that S200 includes following step
Suddenly：
The reaction raw materials weighed in S100 are put into the first reaction vessel, sealed after being vacuumized by S210；
First reaction vessel is placed in smelting furnace by S220, and 1h~12h is kept the temperature after being warming up to 780 DEG C~1400 DEG C；
S230 obtains SnSe base thermoelectricity material ingot castings after first reaction vessel is cooled to room temperature.
3. the preparation method of SnSe base thermoelectricity materials according to claim 2, which is characterized in that the heating rate in S220
For 1 DEG C/min~10 DEG C/min.
4. the preparation method of SnSe base thermoelectricity materials according to claim 2, which is characterized in that S300 includes following step
Suddenly：
First reaction vessel equipped with SnSe base thermoelectricity material ingot castings is placed in the second reaction vessel, it is anti-by described second
It seals after answering container vacuum-pumping, then second reaction vessel is placed in zone melting furnace, utilize zone-melting process growth polycrystalline SnS e
Base thermoelectricity material.
5. according to the preparation method of Claims 1 to 4 any one of them SnSe base thermoelectricity materials, which is characterized in that described more
In the growth course of brilliant SnSe base thermoelectricity materials, melting zone temperature is 780 DEG C~1400 DEG C, and melting zone width is 30mm~40mm.
6. according to the preparation method of Claims 1 to 4 any one of them SnSe base thermoelectricity materials, which is characterized in that described molten
Furnace is rocking furnace.
7. a kind of SnSe base thermoelectricity materials, which is characterized in that it is prepared using claim 1~6 any one of them method,
The chemical structural formula of the SnSe base thermoelectricity materials is Sna-xMxSe1-yRy；
Wherein, in M Ge, Pb, Sb, Bi, Al, Ga, In, Zn, Cd, Hg, Cu, Ag, Au, Co, Mn, Fe, Na, K and Tl at least
One kind, at least one of R S, Te, Cl, Br and I, and 0.8≤a≤1.2,0≤x ＜ 1,0≤y ＜ 1.
8. SnSe base thermoelectricity materials according to claim 7, which is characterized in that a=1,0≤x≤0.2,0≤y≤0.2.
9. SnSe base thermoelectricity materials according to claim 7, which is characterized in that the crystalline substance of the polycrystalline SnS e base thermoelectricity materials
The grain degree of orientation is more than or equal to 0.9.
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| CN111490148B (en) * | 2019-01-27 | 2022-09-23 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polycrystalline SnSe-based thermoelectric material |
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| CN113113531B (en) * | 2021-03-16 | 2023-09-08 | 西北工业大学 | Preparation method of high ZT value pure SnSe polycrystal block thermoelectric material |
| CN113270534A (en) * | 2021-06-04 | 2021-08-17 | 北京航空航天大学 | P-type SnSe crystal for thermoelectric refrigeration material and preparation method thereof |
| CN113956042B (en) * | 2021-09-18 | 2023-02-03 | 深圳大学 | Rhombohedral phase GeSe-based thermoelectric material and preparation method thereof |
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| "Studies on Thermoelectric Properties of n-type Polycrystalline SnSe1-xSx by Iodine Doping";Qian Zhang等;《Advanced Energy Materials》;20150422;第5卷(第12期);第1500360-1页第2栏第3段至第1500360-8页第1栏第2段 * |
| "Thermoelectric properties of p-type polycrystalline SnSe doped with Ag";Cheng-Lung Chen等;《J. Mater. Chem. A》;20140502;第2卷;全文 * |
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