CN104894647B - A kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof - Google Patents
A kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof Download PDFInfo
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- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 70
- 230000006698 induction Effects 0.000 claims abstract description 44
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000002073 nanorod Substances 0.000 claims description 11
- 238000001338 self-assembly Methods 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 230000005619 thermoelectricity Effects 0.000 abstract description 11
- 238000007731 hot pressing Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000002474 experimental method Methods 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
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- 239000011148 porous material Substances 0.000 description 4
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- 239000011159 matrix material Substances 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof, and preparation method includes：Bismuth nitrate and thiocarbamide are provided as raw material, bismuth nitrate and thiocarbamide is uniform to set mixed in molar ratio；Well mixed bismuth nitrate and thiocarbamide are subjected to hydro-thermal reaction；The precursor powder is placed in progress radio frequency induction hot pressed sintering in rf induction furnace.Using gentle hydro-thermal method, the regulating microstructure of bismuth sulfide crystal is realized by rational experiment condition, the microcellular structure of a large amount of Nano grades is introduced in hot pressing block, long wave phonon in can effectively scattering, the reduction thermal conductivity of material on the premise of electric property is not influenceed, and then improve the thermoelectricity capability of material；And it is rapidly heated heating using radio frequency induction hot pressed sintering, prevents crystal grain from growing up, finally given the polycrystalline bismuth sulfide material of lower thermal conductivity.The present invention directly introduces microcellular structure using the multilevel hierarchy of precursor powder in sintering process, and preparation is simple and has preferable controllability.
Description
Technical field
The invention belongs to chemical, technical field of energy material, is specifically designed a kind of lower thermal conductivity bismuth-sulfide polycrystalline heat
Electric material and preparation method thereof, it is related to the bismuth sulfide powder and radio frequency induction hot pressed sintering work of hydro-thermal method synthesis multilevel hierarchy
Skill.
Background technology
Thermoelectric material is that by the functional material of the direct conversion of electric energy and heat energy.Current fossil energy shortage,
Under the background that environmental pollution highlights, thermoelectric material because the recycling of its used heat more than the industry application prospect by people day
Benefit concern.But the low application that govern thermoelectric material always of conversion efficiency, exploitation high performance thermoelectric material is by industrial quarters
Pay much attention to.
The quality of pyroelectric material performance is weighed with dimensionless thermoelectric figure of merit ZT.ZT=S2σ T/ κ, wherein S are Sai Beike systems
Number, σ are electrical conductivity, and T is absolute temperature, and κ is thermal conductivity, S2σ is power factor.The thermoelectric material that can be got better needs high Sai Bei
Gram coefficient and electrical conductivity, low thermal conductivity.
Nano pyroelectric material has preferable thermoelectricity capability, turns into study hotspot in recent years, because fine micro-structural
Control can significantly reduce thermal conductivity, so as to improve thermoelectricity capability.
Nano-pore is introduced in block thermoelectric material matrix, phonon can be effectively scattered, substantially reduce lattice thermal conductivity.Lun Si
Yanliang Zhang of the Institute of Technology et al. are strangled in Bi2Te3Nano-pore is introduced in matrix, analysis shows nano-pore reduces thermal conductivity
Rate [ZHANG Y, MEHTA R J, BELLEY M, et al.Applied Physics effective as nanometer crystal boundary
Letters,2012,100(19):193113.]。
Wen-Yu Zhao et al. [ZHAO W-Y, LIANG Z, WEI P, et al.Acta Materialia, 2012,60
(4):1741-6.] by complexity melting quenching and two step discharge plasmas sinter (SPS) technique be prepared for loose structure
P-type zinc stibium based pyroelectric material, reduce lattice thermal conductivity, while power factor also increases, ZT values improve 46%.But
This method time consumption and energy consumption, complex process.And two crystal grain in step SPS sintering processes easily grow up, be unfavorable for reducing thermal conductivity.
Hydro-thermal method is because of the advantages that its preparation method is simple, crystal purity is high, good dispersion, morphology controllable, in nanometer material
Expect preparation field extensive application.Simply may be used by changing hydro-thermal method conditional regulatory powder micro-structural and then introducing loose structure
Control.
Radio frequency induction hot pressing and sintering technique integrates sintering and hot pressing, can be rapidly heated and be molded, and suppresses crystal grain and exists
Grown up in sintering process.
The content of the invention
The present invention is directed to deficiencies of the prior art, it is proposed that a kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material
And preparation method thereof, based on thermoelectric material microstructure design, synthesized using hydro-thermal method with the multilevel hierarchy of nanometer rods self assembly
Nanometer vulcanization bismuth meal body, in conjunction with radio frequency induction hot-pressing sintering method, flowers shape structure is maintained at hot pressing block well
In.The high density microcellular structure formed between micro- cluster can be effectively reduced bismuth-sulfide polycrystalline material thermal conductivity, improve its thermoelectricity capability.
In order to achieve the above objects and other related objects, the present invention provides a kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectricity material
Material, has microcellular structure in the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material, and the size of the microcellular structure is 50~
300nm。
As a kind of preferred scheme of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, the lower thermal conductivity vulcanization
Bismuth polycrystalline thermoelectric material is prepared using hydro-thermal method and radio frequency induction hot pressing and sintering technique.
The present invention also provides a kind of preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material, including at least following step
Suddenly：
Bismuth nitrate and thiocarbamide are provided as raw material, bismuth nitrate and thiocarbamide is uniform to set mixed in molar ratio；
Well mixed bismuth nitrate and thiocarbamide are subjected to hydro-thermal reaction, obtain the flower formed by bismuth sulfide nano-rod self assembly
The precursor powder of tufted；
The precursor powder is placed in progress radio frequency induction hot pressed sintering in rf induction furnace, obtains polycrystalline bismuth sulfide block
Body.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, the nitre
The mol ratio of sour bismuth and thiocarbamide is 1:2.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, the water
The temperature of thermal response is 140~200 DEG C, and the reaction time is 6~50 hours.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, the sulphur
Change a diameter of 200~400nm of bismuth nanometer rods, length is 3~5 μm.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, by described in
Precursor powder, which is placed in rf induction furnace, to carry out the specific method of radio frequency induction hot pressed sintering and is：
The precursor powder is loaded in a conductive induced dies, the conductive induced dies are placed in the radio frequency induction
The first temperature is heated to by room temperature in stove；
Vacuumized in the rf induction furnace and be passed through inert gas, continue to be heated to second temperature, described second
At a temperature of be quickly cooled to room temperature after the pressure heat-preserving scheduled time.
It is described lazy as a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention
Property gas is high pure nitrogen or argon gas, and air pressure is 0.05~6 atmospheric pressure in the rf induction furnace, the rf induction furnace
Supply frequency is more than 100kHz.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, described the
One temperature is 80~120 DEG C, and the second temperature is 220~400 DEG C, and sintering pressure is 70~80MPa, and the pressure heat-preserving time is
20~40 minutes.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, described the
One temperature is 100 DEG C, and the second temperature is 220~400 DEG C, sintering pressure 75MPa, and the pressure heat-preserving time is 30 minutes.
As a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention, by room temperature
The speed for being heated to the first temperature is 15~20K/min, and the speed that second temperature is heated to by the first temperature is 20K/min, is added
Room temperature is quickly cooled to after pressure insulation.
It is described more as a kind of preferred scheme of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention
There is microcellular structure in brilliant bismuth sulfide block, the size of the microcellular structure is 50~300nm.
The present invention provides a kind of having the beneficial effect that for lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof：Using
Gentle hydro-thermal method, the regulating microstructure of bismuth sulfide crystal is realized by rational experiment condition, introduced in hot pressing block
The microcellular structure of a large amount of Nano grades, long wave phonon in can effectively scattering, the drop of material on the premise of electric property is not influenceed
Lower thermal conductivity, and then improve the thermoelectricity capability of material；And it is rapidly heated heating using radio frequency induction hot pressed sintering, prevents crystal grain
Grow up, finally given the polycrystalline bismuth sulfide material of lower thermal conductivity.The present invention is directly being burnt using the multilevel hierarchy of precursor powder
Microcellular structure is introduced during knot, preparation is simple and has preferable controllability.
Brief description of the drawings
Fig. 1 is shown as the flow chart of the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention.
Fig. 2 a are shown as hydro-thermal reaction in the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention and synthesized
The flowers shape formed by bismuth sulfide nano-rod self assembly precursor powder scanning electron microscope (SEM) photograph.
Polycrystalline vulcanization prepared by the preparation method that Fig. 2 b are shown as the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention
The scanning electron microscope (SEM) photograph of bismuth block section.
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under the spirit of the present invention.
Refer to Fig. 1~Fig. 2 b.It should be noted that the diagram provided in the present embodiment only illustrates this in a schematic way
The basic conception of invention, though only showing the component relevant with the present invention in diagram rather than according to package count during actual implement
Mesh, shape and size are drawn, and kenel, quantity and the ratio of each component can be a kind of random change during its actual implementation, and its
Assembly layout kenel may also be increasingly complex.
The present invention provides a kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material, the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectricity material
There is microcellular structure in material, the size of the microcellular structure is 50~300nm.
It should be noted that the size of the microcellular structure is specially the aperture of microcellular structure；In the present invention, it is described micro-
Pore structure is irregular structure, and the microcellular structure is regarded as into circular configuration herein according to industry is conventional；The aperture is institute
State the diameter of circular configuration.
The microcellular structure of a large amount of Nano grades is introduced in the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material, can effectively be dissipated
Long wave phonon is hit, the reduction thermal conductivity of material on the premise of electric property is not influenceed, and then improve the thermoelectricity capability of material.
Specifically, the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material is using hydro-thermal method and radio frequency induction hot pressed sintering skill
Thermoelectric material is prepared in art.Using gentle hydro-thermal method, the micro- of bismuth sulfide crystal can be realized by rational experiment condition
Structure regulating is seen, is rapidly heated heating using radio frequency induction hot pressed sintering, prevention crystal grain is grown up, and has finally given lower thermal conductivity
Polycrystalline bismuth sulfide material.
The present invention prepares the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectricity using hydro-thermal method and radio frequency induction hot pressing and sintering technique
The method of material is as shown in Fig. 1 to Fig. 2 b, including at least following steps：
S1：Bismuth nitrate and thiocarbamide are provided as raw material, bismuth nitrate and thiocarbamide is uniform to set mixed in molar ratio；It is preferred that
Ground, the bismuth nitrate are five nitric hydrate bismuths, and the mol ratio of the bismuth nitrate and thiocarbamide is 1:2；
S2：Well mixed bismuth nitrate and thiocarbamide are subjected to hydro-thermal reaction, obtain being formed by bismuth sulfide nano-rod self assembly
Flowers shape precursor powder；The temperature of the hydro-thermal reaction is 140~200 DEG C, and the reaction time is 6~50 hours, is obtained
A diameter of 200~400nm of the bismuth sulfide nano-rod, length are 3~5 μm, as shown in Figure 2 a；
S3：The precursor powder is placed in progress radio frequency induction hot pressed sintering in rf induction furnace, obtains polycrystalline bismuth sulfide
Block；The precursor powder is loaded in a conductive induced dies, the conductive induced dies are placed in the rf induction furnace
The interior speed with 15~20K/min is heated to 80~120 DEG C by room temperature；Vacuumized in the rf induction furnace and be passed through inertia
Gas, continue to be heated to 220~400 DEG C with 20K/min speed, apply 70~80MPa pressure at described 220~400 DEG C
Power, and cool to room temperature with the furnace after insulation 20~40 at this pressure, there is micropore in the obtained polycrystalline bismuth sulfide block
Structure, the size of the microcellular structure is 50~300nm, as shown in Figure 2 b；In this step, the time vacuumized is removed, it is whole
The sintering time of individual sintering process is 70~120 minutes, i.e. the total time of heating, insulation and temperature-fall period is 70~120 minutes；
The inert gas is high pure nitrogen or argon gas, and air pressure is 0.05~6 atmospheric pressure in the rf induction furnace, the radio frequency sense
The supply frequency of stove is answered to be more than 100kHz.
The preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention uses gentle hydro-thermal method, by reasonable
Experiment condition realize the regulating microstructure of bismuth sulfide crystal, introduce the micropore knot of a large amount of Nano grades in hot pressing block
Structure, long wave phonon in can effectively scattering, the reduction thermal conductivity of material on the premise of electric property is not influenceed, and then improve material
Thermoelectricity capability；And it is rapidly heated heating using radio frequency induction hot pressed sintering, prevents crystal grain from growing up, finally given low-heat and led
The polycrystalline bismuth sulfide material of rate.The present invention directly introduces microcellular structure using the multilevel hierarchy of precursor powder in sintering process,
Preparation is simple and has preferable controllability.
Embodiment one
In molar ratio：Bismuth nitrate/thiocarbamide=1:2 prepare, weigh respective quality bismuth nitrate and thiocarbamide as raw material, to go
Ionized water adds bismuth nitrate and thiocarbamide in deionized water as solvent, uniform by ultrasonic mixing；The bismuth nitrate that will be mixed
It is placed in thiocarbamide in water heating kettle and carries out hydro-thermal reaction 6 hours at 140 DEG C, obtains the flowers formed by bismuth sulfide nano-rod self assembly
The precursor powder of shape；Precursor powder will be obtained to load in a conductive induced dies, the conductive induced dies are placed in described penetrate
In frequency induction furnace 100 DEG C are heated to 15~20K/min speed by room temperature；Vacuumize and be passed through in the rf induction furnace
Inert gas, continue to be heated to 220 DEG C with 20K/min speed, apply 75MPa pressure at described 220 DEG C, and in the pressure
Room temperature is cooled to the furnace after being incubated 30 minutes under power, obtains polycrystalline bismuth sulfide block.
The obtained polycrystalline bismuth sulfide block is measured, its room temperature thermal conductivity is 0.314W/mK.
Embodiment two
In molar ratio：Bismuth nitrate/thiocarbamide=1:2 prepare, weigh respective quality bismuth nitrate and thiocarbamide as raw material, to go
Ionized water adds bismuth nitrate and thiocarbamide in deionized water as solvent, uniform by ultrasonic mixing；The bismuth nitrate that will be mixed
It is placed in thiocarbamide in water heating kettle and carries out hydro-thermal reaction 6 hours at 200 DEG C, obtains the flowers formed by bismuth sulfide nano-rod self assembly
The precursor powder of shape；Precursor powder will be obtained to load in a conductive induced dies, the conductive induced dies are placed in described penetrate
In frequency induction furnace 100 DEG C are heated to 15~20K/min speed by room temperature；Vacuumize and be passed through in the rf induction furnace
Inert gas, continue to be heated to 220 DEG C with 20K/min speed, apply 75MPa pressure at described 220 DEG C, and in the pressure
Room temperature is cooled to the furnace after being incubated 30 minutes under power, obtains polycrystalline bismuth sulfide block.
The obtained polycrystalline bismuth sulfide block is measured, its room temperature thermal conductivity is 0.337W/mK.
Embodiment three
In molar ratio：Bismuth nitrate/thiocarbamide=1:2 prepare, weigh respective quality bismuth nitrate and thiocarbamide as raw material, to go
Ionized water adds bismuth nitrate and thiocarbamide in deionized water as solvent, uniform by ultrasonic mixing；The bismuth nitrate that will be mixed
It is placed in thiocarbamide in water heating kettle and carries out hydro-thermal reaction 24 hours at 200 DEG C, obtains the flower formed by bismuth sulfide nano-rod self assembly
The precursor powder of tufted；Precursor powder will be obtained to load in a conductive induced dies, the conductive induced dies will be placed in described
In rf induction furnace 100 DEG C are heated to 15~20K/min speed by room temperature；Vacuumize and lead in the rf induction furnace
Enter inert gas, continue to be heated to 220 DEG C with 20K/min speed, apply 75MPa pressure at described 220 DEG C, and at this
Room temperature is cooled to the furnace after being incubated 30 minutes under pressure, obtains polycrystalline bismuth sulfide block.
The obtained polycrystalline bismuth sulfide block is measured, its room temperature thermal conductivity is 0.380W/mK.
Example IV
In molar ratio：Bismuth nitrate/thiocarbamide=1:2 prepare, weigh respective quality bismuth nitrate and thiocarbamide as raw material, to go
Ionized water adds bismuth nitrate and thiocarbamide in deionized water as solvent, uniform by ultrasonic mixing；The bismuth nitrate that will be mixed
It is placed in thiocarbamide in water heating kettle and carries out hydro-thermal reaction 50 hours at 200 DEG C, obtains the flower formed by bismuth sulfide nano-rod self assembly
The precursor powder of tufted；Precursor powder will be obtained to load in a conductive induced dies, the conductive induced dies will be placed in described
In rf induction furnace 100 DEG C are heated to 15~20K/min speed by room temperature；Vacuumize and lead in the rf induction furnace
Enter inert gas, continue to be heated to 220 DEG C with 20K/min speed, apply 75MPa pressure at described 220 DEG C, and at this
Room temperature is cooled to the furnace after being incubated 30 minutes under pressure, obtains polycrystalline bismuth sulfide block.
The obtained polycrystalline bismuth sulfide block is measured, its room temperature thermal conductivity is 0.351W/mK.
Embodiment five
In molar ratio：Bismuth nitrate/thiocarbamide=1:2 prepare, weigh respective quality bismuth nitrate and thiocarbamide as raw material, to go
Ionized water adds bismuth nitrate and thiocarbamide in deionized water as solvent, uniform by ultrasonic mixing；The bismuth nitrate that will be mixed
It is placed in thiocarbamide in water heating kettle and carries out hydro-thermal reaction 6 hours at 200 DEG C, obtains the flowers formed by bismuth sulfide nano-rod self assembly
The precursor powder of shape；Precursor powder will be obtained to load in a conductive induced dies, the conductive induced dies are placed in described penetrate
In frequency induction furnace 100 DEG C are heated to 15~20K/min speed by room temperature；Vacuumize and be passed through in the rf induction furnace
Inert gas, continue to be heated to 400 DEG C with 20K/min speed, apply 75MPa pressure at described 400 DEG C, and in the pressure
Room temperature is cooled to the furnace after being incubated 30 minutes under power, obtains polycrystalline bismuth sulfide block.
The obtained polycrystalline bismuth sulfide block is measured, its room temperature thermal conductivity is 0.531W/mK.
As seen from the above embodiment, prepared using the preparation method of the lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material of the present invention
Bismuth-sulfide polycrystalline thermoelectric material there is relatively low room temperature thermal conductivity.
In summary, the present invention provides a kind of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material and preparation method thereof, using temperature
The hydro-thermal method of sum, the regulating microstructure of bismuth sulfide crystal is realized by rational experiment condition, introduced in hot pressing block big
Measure the microcellular structure of Nano grade, long wave phonon in can effectively scattering, the reduction of material on the premise of electric property is not influenceed
Thermal conductivity, and then improve the thermoelectricity capability of material；And it is rapidly heated heating using radio frequency induction hot pressed sintering, prevents crystal grain from growing
Greatly, the polycrystalline bismuth sulfide material of lower thermal conductivity has been finally given.The present invention is directly being sintered using the multilevel hierarchy of precursor powder
During introduce microcellular structure, preparation is simple and has preferable controllability.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (9)
1. a kind of preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material, it is characterised in that including at least following steps：
Bismuth nitrate and thiocarbamide are provided as raw material, bismuth nitrate and thiocarbamide is uniform to set mixed in molar ratio；
Well mixed bismuth nitrate and thiocarbamide are subjected to hydro-thermal reaction, obtain the flowers shape formed by bismuth sulfide nano-rod self assembly
Precursor powder；
The precursor powder is placed in progress radio frequency induction hot pressed sintering in rf induction furnace, obtains polycrystalline bismuth sulfide block；Will
The precursor powder, which is placed in rf induction furnace, to carry out the specific method of radio frequency induction hot pressed sintering and is：The precursor powder is filled
Enter in a conductive induced dies, the conductive induced dies are placed in the rf induction furnace the first temperature is heated to by room temperature
Degree；Vacuumized in the rf induction furnace and be passed through inert gas, continue to be heated to second temperature, under the second temperature
Pressure heat-preserving is quickly cooled to room temperature after the scheduled time.
2. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：It is described
The mol ratio of bismuth nitrate and thiocarbamide is 1:2.
3. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：It is described
The temperature of hydro-thermal reaction is 140~200 DEG C, and the reaction time is 6~50 hours.
4. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：It is described
A diameter of 200~400nm of bismuth sulfide nano-rod, length are 3~5 μm.
5. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：It is described
Inert gas is high pure nitrogen or argon gas, and air pressure is 0.05~6 atmospheric pressure in the rf induction furnace, the rf induction furnace
Supply frequency be more than 100kHz.
6. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：It is described
First temperature is 80~120 DEG C, and the second temperature is 220~400 DEG C, and sintering pressure is 70~80MPa, the pressure heat-preserving time
For 20~40 minutes.
7. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 6, it is characterised in that：It is described
First temperature is 100 DEG C, and the second temperature is 220~400 DEG C, sintering pressure 75MPa, and the pressure heat-preserving time is 30 points
Clock.
8. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：By room
The speed that temperature is heated to the first temperature is 15~20K/min, and the speed that second temperature is heated to by the first temperature is 20K/min,
Room temperature is quickly cooled to after pressure heat-preserving.
9. the preparation method of lower thermal conductivity bismuth-sulfide polycrystalline thermoelectric material according to claim 1, it is characterised in that：It is described
There is microcellular structure in polycrystalline bismuth sulfide block, the size of the microcellular structure is 50~300nm.
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| CN107098387B (en) * | 2017-02-24 | 2019-06-25 | 河南师范大学 | A kind of aqueous phase preparation method of near-infrared photo-thermal nano material bismuth sulfide |
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