CN106129241A - Solid reaction process prepares the method for stacking faults chalcogenide thermoelectric material - Google Patents
Solid reaction process prepares the method for stacking faults chalcogenide thermoelectric material Download PDFInfo
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- CN106129241A CN106129241A CN201610743431.6A CN201610743431A CN106129241A CN 106129241 A CN106129241 A CN 106129241A CN 201610743431 A CN201610743431 A CN 201610743431A CN 106129241 A CN106129241 A CN 106129241A
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- chalcogenide
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/854—Thermoelectric active materials comprising inorganic compositions comprising only metals
Abstract
The invention belongs to Material Field, relate to a kind of method that solid reaction process prepares stacking faults chalcogenide thermoelectric material, the ratio of 1:0.04:1.96:5 in mass ratio weighs Sn powder, Cu powder or Co powder, Ti powder, S powder respectively, then ground and mixed, with putting into quartz ampoule evacuation tube sealing after the pressure tabletted of 3～5MPa, then sinter, then carry out the grinding of two-wheeled, evacuate, sinter, obtain stacking faults chalcogenide.The method that the solid reaction process that the present invention provides prepares misfit stacking faults chalcogenide, can be used for the preparation of misfit system stacking faults chalcogenide thermoelectric material, and technological operation is simple, repeatable high.The method is by the Cheng Xiangdu of process parameter control misfit compound, consistency, stacking faults such as regulation heating rate, one-tenth phase temperature, temperature retention time, sintering numbers, and controllability is strong；The characteristics such as obtained misfit lamellar compound Cheng Xiangdu is high, impurity is few, consistency is high, thermal conductivity is low and thermoelectric figure of merit is high.
Description
Technical field
The invention belongs to Material Field, relate to a kind of solid reaction process and prepare stacking faults chalcogenide thermoelectric material
Method.
Background technology
Along with being continuously increased of energy demand so that the exploitation dynamics of conventional fossil fuel is greatly improved, to environment
Cause irreversible destruction.Simultaneously with the continuous consumption of Fossil fuel, its amount of storage reduces day by day.Therefore, various newly
The energy, the exploitation of clean energy resource are brought into schedule.And solar energy, wind energy, tide energy, geothermal energy continually develop utilization, new energy
Source in energy market in occupation of increasing share.But, these numerous clean energy resourcies utilize during all the time
Cannot break away from the energy conversion machine system of primary energy mechanical energy electric energy, this greatly reduces the utilization rate of the energy.
In recent years, along with the growing progress of material science, thermoelectric material has become the new of global energy area research
Focus.Electric energy or logical is converted thermal energy into owing to thermoelectric material can directly utilize itself Seebeck (Seebeck) effect
Cross Peltier (Peltier) effect and carry out the characteristic freezed and the concern enjoying domestic and international scientific research circle.Propose in the world to utilize heat
Heat energy is directly changed into electric energy by electric material, can be greatly enhanced the utilization rate of heat energy, thus application prospect is boundless.Electricity
The proposition of sub-crystal-phonon glasses (ECPG) concept is that the research of thermoelectric material provides guiding direction especially.
Misfit chalcogenide thermoelectric material is overlapped mutually the natural superlattice structure of formation well because of its fault shape
Meet the theory of phonon glasses, there is extremely low thermal conductivity and higher thermoelectricity capability.In view of domestic temporary without this type of thermoelectricity
Relevant report prepared by compound, a lot of technology are also in the preliminary research stage.
Summary of the invention
It is an object of the invention to: provide one to be directly used in thermo-electric conversion and thermoelectricity study mechanism, preparation technology is simple,
The preparation method of the misfit stratiform chalcogenide thermoelectric material that thermal conductivity is low, thermoelectric figure of merit is higher.
Concrete technical scheme is:
Solid reaction process prepares the method for stacking faults chalcogenide thermoelectric material, comprises the following steps:
(1) ratio of 1:0.04:1.96:5 in mass ratio weighs Sn powder, Cu powder or Co powder, Ti powder, S powder altogether respectively
2g, wherein the ratio of Cu powder or Co powder is 0.04, and the ratio of Ti powder is 1.96, is the most directly mixed in agate mortar, grinds
Mill 30min, makes powder mix homogeneously.
(2) ground powder is transferred in the steel die of Φ=10mm, with 3～5MPa pressure suppress 5～
10min。
(3) sheet sample suppressed is moved in clean Φ=20mm quartz ampoule.Hydrogen-oxygen generation machine is utilized to carry out
Tube sealing；The most first with machinery pumping forevacuum, then it is evacuated to 1.5 × 10 with molecular pump-3Pa, tube sealing.
(4) last, will be equipped with the quartz ampoule of sample and be placed in batch-type furnace and be sintered.
(5) first sintering heats up: rise to 500 DEG C through 200～1200min from room temperature, is incubated 720min；Pass through again
100～500min are warming up to 800 DEG C, are incubated 2880min, natural cooling.
(6) take out fired sample in agate mortar, grind 30min, make powder full and uniform.Repeat the above steps
～(4) (2).
(7) second time sintering heats up: 200～1200min rise to 500 DEG C from room temperature, is incubated 1440min；Again through 100～
500min is warming up to 800 DEG C, is incubated 2880min, natural cooling.
(8) repeat the above steps (6), third time sintering heats up: be warming up to 350 DEG C with 200～1200min, insulation
1440min；Rise to 800 DEG C through 100～500min again, be incubated 2880min, natural cooling.
The powder that each elemental purity is 99.9%～99.99% used in the present invention.
It is preferably designed as: step (2) suppresses 5min with 5MP pressure.
Heating-up time in step (5) is respectively 1000min, 300min.
Heating-up time in step (7) is respectively 300min, 300min.
Heating-up time in step (8) is respectively 200min, 500min.
The method that the solid reaction process that the present invention provides prepares stacking faults chalcogenide thermoelectric material, can be used for
The preparation of misfit system stacking faults chalcogenide thermoelectric material, technological operation is simple, repeatable high.The method is passed through
The Cheng Xiangdu of process parameter control misfit compound, the causes such as regulation heating rate, one-tenth phase temperature, temperature retention time, sintering number
Density, stacking faults, controllability is strong；Obtained misfit lamellar compound Cheng Xiangdu is high, impurity is few, consistency is high, thermal conductance
The characteristic such as rate is low and thermoelectric figure of merit is high.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained doping Misfit chalcogenide thermoelectric material X-ray diffractogram (XRD)；
Fig. 2 is embodiment 1 gained doping Misfit chalcogenide thermoelectric material resistivity；
Fig. 3 is embodiment 1 gained Misfit chalcogenide thermoelectric material Seebeck coefficient；
Fig. 4 is embodiment 1 gained Misfit chalcogenide thermoelectric material thermal conductivity；
Fig. 5 is embodiment 1 gained Misfit chalcogenide thermoelectric material power factor (PF)；
Fig. 6 is embodiment 1 gained misfit chalcogenide thermoelectric figure of merit (zT value)；
Fig. 7 is embodiment 1 gained misfit stacking faults chalcogenide three-dimensional crystalline structure figure；
Fig. 8 is embodiment 1 gained misfit stacking faults chalcogenide two dimensional crystal structure figure.
Detailed description of the invention:
It is described in conjunction with the embodiments the detailed description of the invention of the present invention.
Embodiment 1:
(1) ratio of 1:0.04:1.96:5 in mass ratio weighs Sn powder, Cu powder or Co powder, Ti powder, S powder altogether respectively
2g, wherein the ratio of Cu powder or Co powder is 0.04, and the ratio of Ti powder is 1.96, is the most directly mixed in agate mortar, grinds
Mill 30min, makes powder mix homogeneously.
(2) ground powder is transferred in the steel die of Φ=10mm, suppresses 5min with the pressure of 5MPa.
(3) sheet sample suppressed is moved in clean Φ=20mm quartz ampoule.Hydrogen-oxygen generation machine is utilized to carry out
Tube sealing；The most first with machinery pumping forevacuum, then it is evacuated to 1.5 × 10 with molecular pump-3Pa, tube sealing.
(4) last, will be equipped with the quartz ampoule of sample and be placed in batch-type furnace and be sintered.
(5) first sintering heats up: rise to 500 DEG C through 1000min from room temperature, is incubated 720min；Again through 300min
It is warming up to 800 DEG C, is incubated 2880min, natural cooling.
(6) take out fired sample in agate mortar, grind 30min, make powder full and uniform.Repeat the above steps
～(4) (2).
(7) second time sintering heats up: rise to 500 DEG C through 300min from room temperature, is incubated 1440min；Again through 300min
It is warming up to 800 DEG C, is incubated 2880min, natural cooling.
(8) repeat the above steps (6), third time sintering heats up: rise to 350 DEG C through 200min from room temperature, insulation
1440min；It is warming up to 800 DEG C through 500min again, is incubated 2880min, natural cooling.
(9) utilize X-ray diffractometer (XRD) that misfit stratiform chalcogenide thermoelectric material is carried out material phase analysis, as
Shown in Fig. 1, wherein vertical coordinate Intensity represents that the intensity of diffraction maximum, abscissa θ represent the angle of diffraction maximum.In correspondence
There is diffraction maximum and face, the peak diffracted intensity of different crystal face in position, shows single-phase behavior, reflects stratiform chalcogenide heat
High-quality prepared by electric material.Three samples [(SnS)1+δ(TiS2)2、(SnS)1+δ(Cu0.02Ti0.98S2)2、(SnS)1+δ
(Co0.02Ti0.98S2)2, 0 δ < 0.28] miscellaneous peak does not the most occur, Cheng Xiangdu is the highest, test handling by force, repeatable high.
(10) with pyroelecthc properties evaluating apparatus (ZEM-3), misfit stratiform chalcogenide is carried out resistivity and Seebeck
Coefficient is measured, and the most as shown in Figure 2,3, wherein vertical coordinate Resistivity and Seebeck represents resistivity and Seebeck respectively
Coefficient, abscissa T represents temperature.Three samples [(SnS)1+δ(TiS2)2、(SnS)1+δ(Cu0.02Ti0.98S2)2、(SnS)1+δ
(Co0.02Ti0.98S2)2, 0 δ < 0.28] all show extraordinary metallicity behavior, Seebeck coefficient is the highest and be negative value, table
Bright electronic carrier occupies whole transport property.
(11) with laser heat conducting instrument (LFA), misfit stratiform chalcogenide is carried out thermal diffusion coefficient measurement, then change
Being counted as thermal conductivity, as shown in Figure 4, wherein vertical coordinate Thermal conductivity represents that thermal conductivity, abscissa T represent temperature
Degree.Three samples [(SnS)1+δ(TiS2)2、(SnS)1+δ(Cu0.02Ti0.98S2)2、(SnS)1+δ(Co0.02Ti0.98S2)2, 0 δ <
0.28] low-down thermal conductivity is all shown, wherein (SnS)1+δ(Cu0.02Ti0.98S2)2Thermal conductivity only have 1.1W K at 793K-1m-1。
(12) according to the test result of Fig. 2 and Fig. 3, can be converted into the power of misfit stratiform chalcogenide thermoelectric material
The factor (PF), as it is shown in figure 5, wherein vertical coordinate PF represents that power factor, abscissa T represent temperature.Three samples [(SnS)1+δ
(TiS2)2、(SnS)1+δ(Cu0.02Ti0.98S2)2、(SnS)1+δ(Co0.02Ti0.98S2)2, 0 δ < 0.28] all show the highest merit
The rate factor, shows extraordinary pyroelecthc properties.
(13) according to the test result of Fig. 2, Fig. 3, Fig. 4, can be converted into misfit stratiform chalcogenide thermoelectric material
Dimensionless thermoelectric figure of merit (zT value), as shown in Figure 6, wherein vertical coordinate zT represents that thermoelectric figure of merit, abscissa T represent temperature.Three
Sample [(SnS)1+δ(TiS2)2、(SnS)1+δ(Cu0.02Ti0.98S2)2、(SnS)1+δ(Co0.02Ti0.98S2)2, 0 δ < 0.28] all show
Go out the highest thermoelectric figure of merit, wherein (SnS)1+δ(Cu0.02Ti0.98S2)2Thermoelectric figure of merit at 793K up to 0.44, therefore have
The strongest application prospect.
(14) Fig. 7 is misfit stacking faults chalcogenide three-dimensional crystalline structure figure.Fig. 8 is corresponding two dimensional crystal knot
Composition, reflects extraordinary stacking faults and superlattices distribution characteristics, and wherein Van der Waals gap represents Fan Dewa
This gap of that.
Claims (4)
1. the method that solid reaction process prepares stacking faults chalcogenide thermoelectric material, it is characterised in that comprise the following steps:
(1) ratio of 1:0.04:1.96:5 in mass ratio weighs Sn powder, Cu powder or Co powder, Ti powder, S powder, wherein Cu respectively
The ratio of powder or Co powder is 0.04, and the ratio of Ti powder is 1.96；Then mix in agate mortar, grind 30min, make powder
Mix homogeneously；
(2) being transferred in the steel die of Φ=10mm by ground powder, the pressure with 3～5MPa continues 5～10min；
(3) sheet sample suppressed is moved in clean Φ=20mm quartz ampoule；Hydrogen-oxygen generation machine is utilized to carry out tube sealing；
First with machinery pumping forevacuum, then it is evacuated to 1.5 × 10 with molecular pump-3Pa, tube sealing；
(4) last, will be equipped with the quartz ampoule of sample and be placed in batch-type furnace and be sintered；
(5) first sintering, natural cooling；
(6) take out fired sample in agate mortar, grind 30min, make powder full and uniform；Repeat the above steps (2)
～(4)；
(7) then carry out second time to sinter, natural cooling；
(8) repeat the above steps (6), then carry out third time and sinter, natural cooling.
2. the method preparing stacking faults chalcogenide thermoelectric material according to the solid reaction process described in claim, its feature
Being, the first sintering described in step (5) heats up: rise to 500 DEG C through 200～1200min from room temperature, is incubated 720min；
It is warming up to 800 DEG C through 100～500min again, is incubated 2880min, natural cooling.
3. the method preparing stacking faults chalcogenide thermoelectric material according to the solid reaction process described in claim, its feature
Being, the second time sintering described in step (7) heats up: 200～1200min rise to 500 DEG C from room temperature, are incubated 1440min；Warp again
Cross 100～500min and be warming up to 800 DEG C, be incubated 2880min, natural cooling.
4. the method preparing stacking faults chalcogenide thermoelectric material according to the solid reaction process described in claim, its feature
Being, the third time sintering described in step (8) heats up: is warming up to 350 DEG C with 200～1200min, is incubated 1440min；Pass through again
100～500min rise to 800 DEG C, are incubated 2880min, natural cooling.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107565011A (en) * | 2017-09-19 | 2018-01-09 | 四川大学 | The method that PbTe thermoelectricity capabilities are effectively improved based on Ga element dopings |
| CN107768512A (en) * | 2017-10-16 | 2018-03-06 | 四川大学 | The method for improving SnTe thermoelectricity capabilities is adulterated by Zn |
| CN109604605A (en) * | 2018-12-29 | 2019-04-12 | 六盘水师范学院 | A kind of solid reaction process quickly prepares CoSb3Method |
| JP2019084688A (en) * | 2017-11-01 | 2019-06-06 | 国立研究開発法人産業技術総合研究所 | Laminate of two-dimensional layered material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107565011A (en) * | 2017-09-19 | 2018-01-09 | 四川大学 | The method that PbTe thermoelectricity capabilities are effectively improved based on Ga element dopings |
| CN107565011B (en) * | 2017-09-19 | 2019-08-02 | 四川大学 | The method for effectively improving PbTe thermoelectricity capability based on Ga element doping |
| CN107768512A (en) * | 2017-10-16 | 2018-03-06 | 四川大学 | The method for improving SnTe thermoelectricity capabilities is adulterated by Zn |
| CN107768512B (en) * | 2017-10-16 | 2019-09-13 | 四川大学 | The method for improving SnTe thermoelectricity capability is adulterated by Zn |
| JP2019084688A (en) * | 2017-11-01 | 2019-06-06 | 国立研究開発法人産業技術総合研究所 | Laminate of two-dimensional layered material |
| JP7012347B2 (en) | 2017-11-01 | 2022-02-14 | 国立研究開発法人産業技術総合研究所 | Laminate of two-dimensional layered material |
| CN109604605A (en) * | 2018-12-29 | 2019-04-12 | 六盘水师范学院 | A kind of solid reaction process quickly prepares CoSb3Method |
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