Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of polycrystalline of K hole doping
SnSe and preparation method thereof, the polycrystalline SnS e of K hole doping of the invention had not only had excellent electric property, but also had low heat
Conductance and good thermoelectricity capability, the peak power factor may be up to 350 μ W/mK2, thermal conductivity can be down to 0.20W/ in 773K
MK, thermoelectric figure of merit ZT may be up to 1.08, realize the collaboration optimization of electrical property and hot property.
In a first aspect, the present invention is provided in the polycrystalline SnS e, the polycrystalline SnS e of the K hole doping of a kind of K hole doping,
The atomic ratio of Sn, K and Se are Sn:K:Se=1-x:x:1, the value of 0 < x≤0.1, x, may be, for example, 0.0001,0.0005,
0.001,0.015,0.02,0.03,0.05,0.06,0.07,0.08,0.09 or 0.1 etc..
Preferably, in the polycrystalline SnS e of the K hole doping, the atomic ratio of Sn, K and Se are Sn:K:Se=1-x:x:1,
0.01≤x≤0.03。
In the present invention, if x is greater than 0.1, the generation of the second phase will lead to, K element residual aoxidizes.
The polycrystalline SnS e of K hole doping of the invention, space group Pnma, potassium is as p-type element, and doping is into SnSe's
Lattice, reduces thermal conductivity, and thermal conductivity can improve carrier concentration, it is excellent to improve thermoelectricity in 773K down to 0.20W/mK
Value ZT, reaching highest thermoelectric figure of merit ZT value in 773K is 1.08, this has far-reaching meaning to application of the SnSe on thermo-electric device
Justice.
Second aspect, the present invention provides the preparation method of the polycrystalline SnS e of K hole doping as described in relation to the first aspect, described
Method the following steps are included:
(1) Sn, K and Se simple substance are put into ball grinder, are passed through inert gas, dry grinded, obtain feed powder;
(2) discharge plasma sintering method is used, the feed powder that sintering step (1) obtains prepares the polycrystalline of K hole doping
SnSe。
The purpose that inert gas is passed through in the step of the method for the invention (1) is prevented in mechanical alloying
Raw material K simple substance etc. aoxidizes during (Mechanical Alloying, MA).
Below as the optimal technical scheme of the method for the invention, but not as to technical solution provided by the invention
Limitation, by following optimal technical scheme, can preferably reach and realize technical purpose and beneficial effect of the invention.
Preferably, the purity for stating Sn, K and Se simple substance is all larger than 99.999%.
Preferably, the total moles score of the Sn simple substance and K simple substance is equal with the molar fraction of Se simple substance.
Preferably, it is 90%~100% and without 100% that Sn simple substance, which accounts for the molar percentage of Se simple substance, be may be, for example,
90%, 91%, 92%, 95%, 96%, 97%, 99%, 99.5% or 99.9% etc., preferably 97%~99%.
Preferably, it is 0%~10% and without 0% that the K simple substance, which accounts for the molar percentage of Se simple substance, be may be, for example,
0.01%, 0.05%, 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5% or 3% etc., preferably 1%~3%.
Preferably, the inert gas be nitrogen, helium, neon, argon gas, Krypton or xenon in any one or at least
Two kinds of mixed gas, the mixed gas but non-limiting example has: the mixed gas of nitrogen and helium, nitrogen and argon gas
The mixed gas of mixed gas, neon and argon gas, nitrogen, argon gas and mixed gas of xenon etc..
Preferably, the ball milling is dry ball milling.
Preferably, the revolving speed of the ball milling is 100rpm~500rpm, if revolving speed can not synthesize SnSe lower than 100rpm
Phase;If revolving speed is higher than 500rpm, the polycrystalline SnS e of the K hole doping synthesized is readily adsorbed on stainless steel, reduces yield.Institute
Stating revolving speed may be, for example, 100rpm, 200rpm, 240rpm, 280rpm, 320rpm, 365rpm, 400rpm, 450rpm or 500rpm
Deng preferably 450rpm.
Preferably, the time of the ball milling can not close SnSe if the time of ball milling is shorter than 15min for 15min~96h
Phase;If the time of ball milling is longer than 96h, the polycrystalline SnS e of the K hole doping of synthesis is caused to be readily adsorbed on stainless steel, reduced
Yield.The time of the ball milling may be, for example, 15min, 30min, 1h, 5h, 8h, 10h, 12h, 15h, 20h, 23h, 25h, 28h,
30h, 36h, 40h, 45h, 50h, 53h, 56h, 60h, 65h, 70h, 75h, 80h, 85h, 90h or 96h etc., preferably 1h~12h,
Further preferably 8h.
Preferably, in the step (2), sintering temperature is 200 DEG C~500 DEG C, if sintering temperature is lower than 200 DEG C, sample
The consistency of product is too low, is unable to complete sintering process;If sintering temperature is higher than 500 DEG C, it is be easy to cause the volatilization of Se element, is made
Sample nonstoichiometry ratio, reduces the performance of material.The sintering temperature may be, for example, 200 DEG C, 230 DEG C, 260 DEG C, 280
DEG C, 300 DEG C, 325 DEG C, 350 DEG C, 380 DEG C, 400 DEG C, 450 DEG C or 500 DEG C etc., preferably 500 DEG C.
Preferably, in the step (2), being warming up to the heating rate during sintering temperature is 40 DEG C/min~180
DEG C/min, it may be, for example, 40 DEG C/min, 60 DEG C/min, 80 DEG C/min, 100 DEG C/min, 125 DEG C/min, 150 DEG C/min or 180
DEG C/min etc..
Preferably, in the step (2), the soaking time of sintering is 2min~8min, may be, for example, 2min, 3min,
5min, 6min, 7min or 8min etc..
Preferably, in the step (2), the vacuum degree of sintering is 2Pa~7Pa, may be, for example, 2Pa, 3Pa, 4Pa, 5Pa,
6Pa or 7Pa etc..
Preferably, in the step (2), the pressure of sintering is 30MPa~60MPa, may be, for example, 30MPa, 35MPa,
40MPa, 45MPa, 50MPa or 60MPa etc., preferably 50MPa.
Preferably, using the method for discharge plasma sintering, when the feed powder that sintering step (1) obtains, which is packed into
In graphite jig, it is then placed in discharge plasma sintering furnace and is sintered.
There is no restriction for size of the present invention to graphite jig, and those skilled in the art can according to need the choosing for carrying out size
It selects, it is Ф 10mm~20mm that diameter, which can be used for example, is highly sintered for the graphite jig of 2mm~6mm, correspondingly, obtains
To the diameters of block materials be about Ф 10mm~20mm, height is about 2mm~6mm, other diameters and height also can be used
Graphite jig be sintered.
Preferably, the method also includes step (1) ' is carried out before step (1): being full of N2In the glove box of atmosphere
The step of weighing Sn, K and Se simple substance, it is therefore an objective to prevent K simple substance etc. from aoxidizing.
Then method of the invention is by carrying out plasma discharging for Sn, K and Se simple substance ball milling under inert gas conditions
The method for being sintered (Spark Plasma Sintering, SPS) adjusts the technique ginseng of ball milling and discharge plasma sintering step
Number, can be realized the Effective Doping of potassium element, and potassium element is as p-type doping element, the preparation K hole doping that can reduce
Polycrystalline SnS e thermal conductivity, improve its thermoelectric figure of merit, 773K reach highest thermoelectric figure of merit ZT value be 1.08, moreover, this
The method of invention has the advantages that preparation process is simple, generated time is short, at low cost and practical, has wide application
Prospect.
As the optimal technical scheme of the method for the invention, a kind of preparation method of the polycrystalline SnS e of K hole doping, institute
State method the following steps are included:
(1) ': being full of N2Sn, K and Se simple substance that purity is greater than 99.999% are weighed in the glove box of atmosphere;
(1) Sn, K and Se simple substance that step (1) ' weighs are put into ball grinder, inert gas are passed through, with the revolving speed of 450rpm
Dry grind 8h, obtains feed powder;
(2) feed powder that step (1) obtains is fitted into graphite jig, is put into discharge plasma sintering furnace control vacuum degree
In 2Pa~7Pa, pressure is sintered in 500 DEG C of heat preservation 2min~8min in 50MPa, prepares the polycrystalline SnS e of K hole doping.
Herein under preferred technical solution, potassium is easier the lattice for being used as p-type doping element to enter SnSe, is prepared
The polycrystalline SnS e of K hole doping has better electric property and a photoelectric properties, thermal conductivity at 773K 0.6W/mK with
Under, highest thermoelectric figure of merit ZT is 1.0 or more.
Compared with the prior art, the invention has the following advantages that
(1) then method of the invention is by discharging etc. by Sn, K and Se simple substance ball milling under inert gas conditions
The method of ion sintering, adjusts the technological parameter of ball milling and discharge plasma sintering step, realizes the Effective Doping of potassium element,
The polycrystalline SnS e of K hole doping is prepared, preparation process is simple, generated time is short, cost moreover, method of the invention has
Low and practical advantage.
(2) in the polycrystalline SnS e of K hole doping of the invention, potassium element can be reduced as p-type doping element
The thermal conductivity of the polycrystalline SnS e of K hole doping is prepared, carrier concentration is improved, improves electric property.K hole doping of the invention
Polycrystalline SnS e have extraordinary comprehensive performance, while with very high power factor, but have low-down thermal conductivity
Rate and very high thermoelectric figure of merit ZT, the peak power factor can reach 350 μ W/mK in 623K2, thermal conductivity can be down in 773K
0.20W/mK, highest thermoelectric figure of merit ZT value reach 1.08 in 773K.
Embodiment 1-11
Firstly, preparing SnSe base forerunner's attritive powder with improved Mechanical Alloying, this method is by high-purity Sn, K
It according to the molar percentage that Sn simple substance accounts for Se simple substance is 90%~100% and not with Se elemental powders (purity be greater than 99.999%)
It is 0%~10% and without 0% that the simple substance containing 100%, K, which accounts for the molar percentage of Se simple substance, and guarantees the total of Sn simple substance and K simple substance
Quality is equal with the molar fraction of Se simple substance, is there is N2It is weighed in glove box under atmosphere and is put into ball grinder, be put into planetary height
In energy ball mill, it is passed through N2With the mixed gas of Ar composition, sealing carries out mechanical alloying, and dry ball milling obtains mixing K's
Then SnSe base attritive powder is sintered the SnSe based powders for mixing K with discharge plasma sintering (SPS), block is prepared
The polycrystalline SnS e of body material K hole doping, wherein sintering temperature is 200 DEG C~500 DEG C, the soaking time of sintering be 2min~
8min, the pressure of sintering are 20MPa~60MPa, and the vacuum degree of sintering is 2Pa~7Pa.
Test the polycrystalline SnS e of obtained K hole doping: the block materials K obtained with sand paper to each embodiment is empty
The polycrystalline SnS e of cave doping carries out surface grinding process, then test resistance rate (ρ), Seebeck coefficient (S) and thermal conductivity (κ) etc.
Parameter.With power factor PF=α2Electric property, the dimensionless thermoelectric figure of merit ZT=(α of/ρ evaluation material2/ ρ κ) T evaluation material
Thermoelectricity capability.
Table 1 gives starting material composition, improved MA technological parameter, SPS technological parameter and the heat of each embodiment
Electrical property characterization result.
Table 1
Comparative example 1-5
Firstly, prepare SnSe base forerunner's attritive powder with improved Mechanical Alloying, this method be by high-purity Sn and
Sn elemental powders (purity is greater than 99.999%) are 1:1 according to the molar ratio of Sn simple substance and Se simple substance, are there is N2Hand under atmosphere
It is weighed in casing and is put into ball grinder, be put into planetary high-energy ball mill, be passed through N2With the mixed gas of Ar composition, seal, into
Row mechanical alloying, dry ball milling obtain SnSe base attritive powder, then, with discharge plasma sintering (SPS) to SnSe original washing powder
End is sintered, and the polycrystalline SnS e of block materials is prepared, wherein sintering temperature is 200 DEG C~500 DEG C, the heat preservation of sintering
Time is 2min~8min, and the pressure of sintering is 20MPa~60MPa, and the vacuum degree of sintering is 2Pa~7Pa.
Obtained polycrystalline SnS e is tested: table being carried out to the block materials polycrystalline SnS e that each embodiment obtains with sand paper
Face grinding process, then parameters such as test resistance rate (ρ), Seebeck coefficient (S) and thermal conductivity (κ).With power factor PF=α2/
Electric property, the dimensionless thermoelectric figure of merit ZT=(α of ρ evaluation material2/ ρ κ) T evaluation material thermoelectricity capability.
Table 2 gives starting material composition, improved MA technological parameter, SPS technological parameter and the heat of each comparative example
Electrical property characterization result.
Table 2
Comparative example 6
Except not being passed through N in improved ma process2Outside the mixed gas of Ar composition, other preparation methods
It is same as Example 4 with condition.
The product obtained to the comparative example detects, and occurs miscellaneous phase SnO in product2, reduce the electrical property of product
Energy and thermoelectricity capability, illustrate that preparation process protective atmosphere is very important.
Fig. 1 shows the K that comparative example the 3-5 SnSe being prepared and embodiment 2-4 are prepared0.01Sn0.99The X of Se is penetrated
Ray diffraction diagram, as can be seen from the figure under different Ball-milling Times (5 hours, 8 hours and 12 hours), all block materials are main
X-ray diffraction peak be SnSe characteristic peak.When Ball-milling Time extends to 12h from 5h, the peak position of diffraction maximum is inclined to low-angle
Move, show the extension with Ball-milling Time, volatile Se element can the loss of energy and cause the variation of peak position, in addition, mixing the sample of K
Product (the K that embodiment 2-4 is prepared0.01Sn0.99Se) compared with undoped sample (SnSe that comparative example 3-5 is prepared),
The position of diffraction maximum is deviated to high angle, and the chanza for showing K makes lattice change.
Fig. 2 a and Fig. 2 b indicate what the SnSe that comparative example 3-5 is prepared and embodiment 2-4 were prepared
K0.01Sn0.99The power factor variation with temperature figure of Se.As seen from the figure, under identical temperature and pressure technological parameter, K is mixed
The sample (K that embodiment 2-4 is prepared0.01Sn0.99Se (comparative example 3-5 is prepared the sample not being doped) and
SnSe it) compares, the promotion that the highest power factor value of material is greatly improved compares under identical Ball-milling Time (8 hours), doping
Before and after K, the peak power factor is increased to up to 350 μ W/mK2(623K)。
Fig. 3 a and Fig. 3 b indicate what the SnSe that comparative example 3-5 is prepared and embodiment 2-4 were prepared
K0.01Sn0.99The thermal conductivity variation with temperature figure of Se, it can be seen that doping K reduces thermal conductivity significantly, in the room temperature of 300K
0.96W/mK or more of the thermal conductivity before mixing K, being reduced to can be down to 0.5W/mK.Thermal conductivity reduces as the temperature increases,
After tested, the thermal conductivity of 773K can be down to 0.2W/mK.K after mixing K0.01Sn0.99The thermal conductivity of Se is close with monocrystalline.
Fig. 4 a and Fig. 4 b indicate what the SnSe that comparative example 3-5 is prepared and embodiment 2-4 were prepared
K0.01Sn0.99The thermoelectric figure of merit ZT variation with temperature figure of Se, as seen from the figure, doping K improve thermoelectric figure of merit ZT significantly, most
High thermoelectric figure of merit ZT before mixing K 0.7 hereinafter, being increased to up to 1.08, the percentage of raising may be up to 67%.
In conclusion then the present invention is by discharging etc. Sn, K and Se simple substance ball milling under inert gas conditions
The method of ion sintering, adjusts the technological parameter of ball milling and discharge plasma sintering step, realizes effective hole of potassium element
Doping, is prepared the polycrystalline SnS e of K hole doping, with low thermal conductivity, high power factor and ZT value, thermal conductivity exist
773K can be up to respectively 350 μ W/mK down to 0.2W/mK, the peak power factor and highest thermoelectric figure of merit ZT2With 1.08, have non-
Often good comprehensive performance while with very high power factor, and has low-down thermal conductivity and very high thermoelectricity excellent
Value ZT shows excellent electric property and thermoelectricity capability.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.