CN106129241B - The method that solid reaction process prepares stacking faults chalcogenide thermoelectric material - Google Patents
The method that solid reaction process prepares stacking faults chalcogenide thermoelectric material Download PDFInfo
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- CN106129241B CN106129241B CN201610743431.6A CN201610743431A CN106129241B CN 106129241 B CN106129241 B CN 106129241B CN 201610743431 A CN201610743431 A CN 201610743431A CN 106129241 B CN106129241 B CN 106129241B
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Abstract
The invention belongs to Material Fields, are related to a kind of method that solid reaction process prepares stacking faults chalcogenide thermoelectric material, in mass ratio 1:0.04:1.96:5 ratio weighs Sn powder, Cu powder or Co powder, Ti powder, S powder respectively, then ground and mixed, with the pressure of 3~5MPa it is tabletted after be put into quartz ampoule and vacuumize tube sealing, be then sintered, the grinding, evacuation, sintering of two-wheeled are carried out again, obtain stacking faults chalcogenide.The method that solid reaction process provided by the invention prepares misfit stacking faults chalcogenides, available for the preparation of misfit system stacking faults chalcogenide thermoelectric materials, technological operation is simple, and repeatability is high.For this method by adjusting heating rate, Cheng Xiangdu, consistency, stacking faults into the process parameter controls misfit compounds such as phase temperature, soaking time, sintering number, controllability is strong；Obtained misfit lamellar compounds Cheng Xiangdu high, the characteristics such as 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 Fields, are related to a kind of solid reaction process and prepare stacking faults chalcogenide thermoelectric material
Method.
Background technology
With being continuously increased for energy demand so that the utilization dynamics of conventional fossil fuel greatly improves, to environment
Cause irreversible destruction.Simultaneously with the continuous consumption of fossil fuel, amount of storage is increasingly reduced.Therefore, it is various new
The exploitation of the energy, clean energy resource has been brought into schedule.And solar energy, wind energy, tide energy, geothermal energy continually develop utilization, new energy
Source is in energy market in occupation of increasing share.However, these numerous clean energy resourcies during utilization always
The energy conversion machine system of primary energy-mechanical energy-electric energy can not be broken away from, this greatly reduces the utilization rate of the energy.
In recent years, with the growing progress of material science, thermoelectric material has become the new of global energy area research
Hot spot.Since thermoelectric material directly can convert thermal energy into electric energy using Seebeck (Seebeck) effect of itself or lead to
It crosses the characteristic that Peltier (Peltier) effect is freezed and receives the concern of domestic and international scientific research circle.It proposes to utilize heat in the world
Thermal energy is directly changed into electric energy by electric material, can greatly improve the utilization rate of thermal energy, thus application prospect is boundless.Electricity
The it is proposed of sub- crystal-phonon glasses (ECPG) concept even more provides the direction of directiveness for the research of thermoelectric material.
Misfit chalcogenides thermoelectric material is overlapped mutually the natural superlattice structure to be formed well because of its fault shape
The theory of phonon glasses is met, there is extremely low thermal conductivity and higher thermoelectricity capability.In view of the country is temporarily without such thermoelectricity
Relevant report prepared by object is closed, many technologies are also in the preliminary research stage.
Invention content
It is an object of the invention to：One kind is provided and is directly used in heat to electricity conversion and thermoelectricity mechanism study, preparation process is simple,
The preparation method of misfit stratiform chalcogenide thermoelectric materials that thermal conductivity is low, thermoelectric figure of merit is higher.
Specifically technical solution is：
The method that solid reaction process prepares stacking faults chalcogenide thermoelectric material, includes the following steps：
(1) in mass ratio 1:0.04:1.96:5 ratio weighs Sn powder, Cu powder or Co powder respectively, Ti powder, S powder are total to
2g, the wherein ratio of Cu powder or Co powder are that the ratio of 0.04, Ti powder is 1.96, are then directly mixed in agate mortar, grind
30min is ground, is uniformly mixed powder.
(2) ground powder is transferred in the steel die of Φ=10mm, with the pressure of 3~5MPa compacting 5~
10min。
(3) sheet sample suppressed is moved into clean Φ=20mm quartz ampoules.Machine occurs using hydrogen-oxygen to carry out
Tube sealing；Mechanical pumping forevacuum is first used later, then is evacuated to 1.5 × 10 with molecular pump-3Pa, tube sealing.
(4) finally, the quartz ampoule equipped with sample is placed in batch-type furnace and be sintered.
(5) first sintering heats up：500 DEG C are risen to from room temperature by 200~1200min, keeps the temperature 720min；Using
100~500min is warming up to 800 DEG C, keeps the temperature 2880min, natural cooling.
(6) it takes out and fires sample in agate mortar, grind 30min, make powder full and uniform.It repeats the above steps
(2)~(4).
(7) second of sintering heating：200~1200min rises to 500 DEG C from room temperature, keeps the temperature 1440min；Using 100~
500min is warming up to 800 DEG C, keeps the temperature 2880min, natural cooling.
(8) repeat the above steps (6), third time sintering heating：350 DEG C are warming up to 200~1200min, heat preservation
1440min；800 DEG C are risen to using 100~500min, keeps the temperature 2880min, natural cooling.
The each element purity used in the present invention is 99.9%~99.99% powder.
It is preferably designed as：With 5MP pressure compacting 5min in step (2).
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 solid reaction process provided by the invention prepares stacking faults chalcogenide thermoelectric material, can be used for
The preparation of misfit system stacking faults chalcogenide thermoelectric materials, technological operation is simple, and repeatability is high.This method passes through
Adjust heating rate, the Cheng Xiangdu into the process parameter controls misfit compounds such as phase temperature, soaking time, sintering number, cause
Density, stacking faults, controllability are strong；Obtained misfit lamellar compounds Cheng Xiangdu high, impurity is few, consistency is high, thermal conductivity
The characteristics such as rate is low and thermoelectric figure of merit is high.
Description of the drawings
Fig. 1 is 1 gained doping Misfit chalcogenide thermoelectric material X-ray diffractograms (XRD) of embodiment；
Fig. 2 is 1 gained doping Misfit chalcogenide thermoelectric material resistivity of embodiment；
Fig. 3 is 1 gained Misfit chalcogenide thermoelectric material Seebeck coefficients of embodiment；
Fig. 4 is 1 gained Misfit chalcogenide thermoelectric material thermal conductivities of embodiment；
Fig. 5 is 1 gained Misfit chalcogenide thermoelectric material power factors (PF) of embodiment；
Fig. 6 is 1 gained misfit chalcogenides thermoelectric figure of merit (zT values) of embodiment；
Fig. 7 is 1 gained misfit stacking faults chalcogenide three-dimensional crystalline structure figures of embodiment；
Fig. 8 is 1 gained misfit stacking faults chalcogenide two dimensional crystal structure figures of embodiment.
Specific embodiment：
It is described in conjunction with the embodiments the specific embodiment of the present invention.
Embodiment 1：
(1) in mass ratio 1:0.04:1.96:5 ratio weighs Sn powder, Cu powder or Co powder respectively, Ti powder, S powder are total to
2g, the wherein ratio of Cu powder or Co powder are that the ratio of 0.04, Ti powder is 1.96, are then directly mixed in agate mortar, grind
30min is ground, is uniformly mixed powder.
(2) ground powder is transferred in the steel die of Φ=10mm, 5min is suppressed with the pressure of 5MPa.
(3) sheet sample suppressed is moved into clean Φ=20mm quartz ampoules.Machine occurs using hydrogen-oxygen to carry out
Tube sealing；Mechanical pumping forevacuum is first used later, then is evacuated to 1.5 × 10 with molecular pump-3Pa, tube sealing.
(4) finally, the quartz ampoule equipped with sample is placed in batch-type furnace and be sintered.
(5) first sintering heats up：500 DEG C are risen to from room temperature by 1000min, keeps the temperature 720min；Using 300min
800 DEG C are warming up to, keeps the temperature 2880min, natural cooling.
(6) it takes out and fires sample in agate mortar, grind 30min, make powder full and uniform.It repeats the above steps
(2)~(4).
(7) second of sintering heating：500 DEG C are risen to from room temperature by 300min, keeps the temperature 1440min；Using 300min
800 DEG C are warming up to, keeps the temperature 2880min, natural cooling.
(8) repeat the above steps (6), third time sintering heating：350 DEG C are risen to from room temperature by 200min, heat preservation
1440min；800 DEG C are warming up to using 500min, keeps the temperature 2880min, natural cooling.
(9) material phase analysis is carried out to misfit stratiform chalcogenides thermoelectric material using X-ray diffractometer (XRD), such as
Shown in Fig. 1, wherein ordinate Intensity represents the intensity of diffraction maximum, and abscissa θ represents the angle of diffraction maximum.Corresponding
There is the diffraction maximum and peak face diffracted intensity of different crystal faces 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] do not occur miscellaneous peak, Cheng Xiangdu is very high, tests handling strong, repeatability height.
(10) resistivity and Seebeck are carried out to misfit stratiforms chalcogenide with pyroelecthc properties evaluating apparatus (ZEM-3)
Coefficient measures, and respectively as shown in Figure 2,3, wherein ordinate Resistivity and Seebeck represent resistivity and Seebeck respectively
Coefficient, 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] extraordinary metal sexual behaviour is shown, Seebeck coefficient is very high and is negative value, table
Bright electronic carrier occupies entire transport property.
(11) thermal diffusion coefficient measurement, Ran Houhuan are carried out to misfit stratiforms chalcogenide with laser heat conducting instrument (LFA)
Thermal conductivity is counted as, as shown in figure 4, wherein ordinate Thermal conductivity represent thermal conductivity, abscissa T represents 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 shown, wherein (SnS)1+δ(Cu0.02Ti0.98S2)2Thermal conductivity only have 1.1W K in 793K-1m-1。
(12) power of misfit stratiform chalcogenide thermoelectric materials is can be converted into the test result of Fig. 3 according to fig. 2
The factor (PF), as shown in figure 5, wherein ordinate PF represents power factor, 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] very high work(is shown
The rate factor shows extraordinary pyroelecthc properties.
(13) according to fig. 2, the test result of Fig. 3, Fig. 4, can be converted into misfit stratiform chalcogenide thermoelectric materials
Dimensionless thermoelectric figure of merit (zT values), as shown in fig. 6, wherein ordinate zT represents thermoelectric figure of merit, abscissa T represents 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] it shows
Go out very high thermoelectric figure of merit, wherein (SnS)1+δ(Cu0.02Ti0.98S2)2Thermoelectric figure of merit in 793K up to 0.44, therefore have
Very strong application prospect.
(14) Fig. 7 is misfit stacking faults chalcogenide three-dimensional crystalline structure figures.Fig. 8 is corresponding two dimensional crystal knot
Composition, reflects extraordinary stacking faults and superlattices distribution characteristics, and wherein Van der Waals gap represent Fan Dewa
This gap of that.
Claims (4)
1. the method that solid reaction process prepares stacking faults chalcogenide thermoelectric material, which is characterized in that include the following steps：
(1) in mass ratio 1:0.04:1.96:5 ratio weighs Sn powder, Cu powder or Co powder, Ti powder, wherein S powder, Cu respectively
The ratio of powder or Co powder is that the ratio of 0.04, Ti powder is 1.96；Then it is mixed in agate mortar, grinds 30min, make powder
It is uniformly mixed；
(2) ground powder is transferred in the steel die of Φ=10mm, continues 5~10min with the pressure of 3~5MPa；
(3) sheet sample suppressed is moved into clean Φ=20mm quartz ampoules；Machine occurs using hydrogen-oxygen and carries out tube sealing；
Mechanical pumping forevacuum is first used, then 1.5 × 10 are evacuated to molecular pump-3Pa, tube sealing；
(4) finally, the quartz ampoule equipped with sample is placed in batch-type furnace and be sintered；
(5) first sintering, natural cooling；
(6) sample fired is taken out in agate mortar, is ground 30min, is made powder full and uniform；It repeats the above steps (2)
~(4)；
(7) and then be sintered for the second time, natural cooling；
(8) repeat the above steps (6), then carries out third time sintering, natural cooling.
2. the method that solid reaction process according to claim 1 prepares stacking faults chalcogenide thermoelectric material, special
Sign is that the first sintering described in step (5) heats up：500 DEG C are risen to from room temperature by 200~1200min, heat preservation
720min；800 DEG C are warming up to using 100~500min, keeps the temperature 2880min, natural cooling.
3. the method that solid reaction process according to claim 1 prepares stacking faults chalcogenide thermoelectric material, special
Sign is that second of sintering described in step (7) heats up：200~1200min rises to 500 DEG C from room temperature, keeps the temperature 1440min；Again
800 DEG C are warming up to by 100~500min, keeps the temperature 2880min, natural cooling.
4. the method that solid reaction process according to claim 1 prepares stacking faults chalcogenide thermoelectric material, special
Sign is that the third time sintering described in step (8) heats up：350 DEG C are warming up to 200~1200min, keeps the temperature 1440min；It passes through again
It crosses 100~500min and rises to 800 DEG C, keep the temperature 2880min, natural cooling.
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| CN107768512B (en) * | 2017-10-16 | 2019-09-13 | 四川大学 | The method for improving SnTe thermoelectricity capability is adulterated by Zn |
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