CN106676322B - A kind of environmentally friendly sulfur family stannide thermoelectric material and preparation method thereof - Google Patents
A kind of environmentally friendly sulfur family stannide thermoelectric material and preparation method thereof Download PDFInfo
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- CN106676322B CN106676322B CN201710019860.3A CN201710019860A CN106676322B CN 106676322 B CN106676322 B CN 106676322B CN 201710019860 A CN201710019860 A CN 201710019860A CN 106676322 B CN106676322 B CN 106676322B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
Abstract
The present invention relates to a kind of high-performance environment-friendly type sulfur family stannide thermoelectric material and preparation method thereof, the chemical general formula of the thermoelectric material is Sn1.03‑yMgyTe(Cu2Te)x(0 ＜ x≤0.05,0 ＜ y≤0.12)；Preparation method is using the metal simple-substance of purity ＞ 99% as raw material, by chemical formula Sn1.03‑yMgyTe(Cu2Te)xStoichiometric ratio carry out dispensing, after Vacuum Package, high-temperature fusion, annealing heat-treats, grind into powder carries out vacuum heating-press sintering, obtains the novel sulfur family stannide thermoelectric material that flaky material is target components after slow cooling.Present invention design realizes that the collaboration of electronic transport performance and thermotransport performance optimizes to promote its thermoelectricity capability in telluride tin (SnTe) material.Compared with prior art, the present invention develops a kind of environmentally friendly Sn with high performance1.03‑yMgyTe(Cu2Te)xNew thermoelectric materials, zT values have reached 1.4 in 900K, are a kind of environmentally friendly high performance thermoelectric materials with the traditional p-type telluride lead material of potentiality substitution.
Description
Technical field
The invention belongs to novel energy resource material technology field, more particularly, to a kind of sulfur family stannide thermoelectric material and its preparation
Method.
Background technology
Expanding economy not only increases demand for energy, while also exacerbates environmental pollution so that for renewable clear
The research of the clean energy attracts attention.Based on Sai Er Bakes effect, thermoelectricity energy and material is realized by the carrier transport in material
The mutual conversion of two kinds of form energy of thermal energy and electric energy.Thermoelectric energy conversion device has noiseless, pollution-free, environmental-friendly etc.
Feature is a kind of sustainable clean energy resource.In space flight and aviation power supply, industrial afterheat recovery, automobile exhaust heat utilize
Certain application is obtained.The extensive use of thermoelectricity energy and material can not only solve the problems, such as part energy demand, can also slow down
Environmental pollution.
The bottleneck of its large-scale application is currently limited when the transfer efficiency of thermoelectric material is relatively low, performance usually uses dimensionless
Thermoelectric figure of merit zT is weighed, zT=S2σ T/ κ, wherein：T is absolute temperature, and S is Seebeck coefficient, and σ is conductivity, and κ is thermal conductivity
Rate, by electron thermal conductivity κEWith lattice thermal conductivity κLTwo parts form.Due to Seebeck coefficient S, conductivityσ, electron thermal conductivity κE
The strong effect of intercoupling between three parameters, the single a certain parameter of optimization can not improve whole thermoelectric figure of merit.Currently
The method that can be achieved effectively to promote conducting material thermoelectricity performance has：Band engineering improves the power factor S of material2σ and nanosizing or
Alloying reduces the independent parameter lattice thermal conductivity κ of materialL。
Lead telluride (PbTe) is played as conventional thermoelectric materials, Thermoelectric Generator in aerospace and military aspect
Effect.Last decade significantly improves the thermoelectricity capability of the material by the means such as band engineering and introducing nano-second-phase.By
There is toxicity in its component Pb, limit large-scale application of the thermoelectric material in each field.Telluride tin (SnTe) material
It is a kind of environmentally friendly thermoelectricity material for being expected to substitution PbTe with the crystal structure identical with PbTe and similar band structure
Material.Since the energy difference between two valence band of SnTe materials is relatively large, lead to the electronic transport poor-performing of the material, therefore its heat
Electrical property needs to be further improved.Be currently based on the material research focus primarily upon by with MnTe (Journal of
Materiomics 2015,1,307)、HgTe(Energy&Environment Science 2015,8,267)、CdTe
(Journal of the American Chemical Society 2014,136,7006)、MgTe(Chemistry of
Materials 2015,27,581), the compounds such as CaTe (Chemistry of Materials 2015,28,376) formed it is solid
Solution realizes that energy band degeneracy (it is poor to reduce the energy between two valence band) promotes its electronic transport performance.Additionally due to its lattice thermal conductivity compared with
Height, part research introduces nano-second-phase while energy band degeneracy reduces lattice thermal conductivity (the Journal of the of material
American Chemical Society 2014,136,7006), more means optimizations make the thermoelectricity capability of material reach 1.4.Closely
Phase we by with cuprous telluride (Cu2Te) formation solid solution can introduce clearance C u atom and effectively scatter phonon, make SnTe base materials
The lattice thermal conductivity of material is reduced to 0.5W/m-K, close to theoretical minimum (Advanced Electronic Materials
2016,2,1600019).Due to containing the toxic elements such as Cd/Hg in the component of current high performance telluride tin-based material, have with
Environmentally friendly problem identical PbTe.
Invention content
The purpose of the present invention is regulate and control while realize energy band merger promotion electronic transport performance by ingredient and introduce gap original
Sub- defects scattering phonon reduces lattice thermal conductivity, and the final collaboration optimization for realizing electrical property and hot property significantly carries
The thermoelectricity capability of material is risen, develops environmentally friendly sulfur family stannide thermoelectric material with high performance.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of environmentally friendly sulfur family stannide thermoelectric material, chemical formula Sn1.03-yMgyTe(Cu2Te)x(0 ＜ x≤
0.05,0 ＜ y≤0.12), it is semi-conductor thermoelectric material.
Preferably, x=0~0.05 and y=0~0.12, but be not 0.
It is further preferred that x=0.03~0.05, material has preferably electrical property；The y=0.1~
0.12, material has relatively low lattice thermal conductivity.
Still further preferably, during x=0.05 and y=0.12, material has optimal electric property and minimum simultaneously
Lattice thermal conductivity, i.e. the sulfur family stannide thermoelectric material dimensionless thermoelectric figure of merit highest.
A kind of preparation method of environmentally friendly sulfur family stannide thermoelectric material, includes the following steps：
(1) Vacuum Package：Chemical formula Sn is pressed with simple substance element S n, Mg, Cu, the Te of purity more than 99.99%1.03-yMgyTe
(Cu2Te)xStoichiometric ratio in (0 ＜ x≤0.05,0 ＜ y≤0.12) carries out dispensing, and Vacuum Package is in quartz ampoule；
(2) melting quenching：Quartz ampoule equipped with raw material is put into shaft furnace and is slowly heated, makes raw material in the molten state
It is fully reacted, then quenches, obtain ingot casting；
(3) annealing quenching：By gained ingot casting in (2) again Vacuum Package in quartz ampoule, and it is put into shaft furnace slowly
Heating carries out high annealing, then quenches, obtain ingot casting；
(4) hot pressed sintering：The ingot casting grind into powder that will be obtained in (3) with agate mortar, is positioned in graphite jig, into
Row vacuum heating-press sintering, the sheet block materials that subsequent slow cooling obtains are the sulfur family stannide thermoelectricity material of target components
Material.
Preferably, in step (2) with 150~200 DEG C per hour of rate by quartz ampoule from room temperature to 850~900
DEG C and keep the temperature 6 hours, raw material is made adequately to be reacted in the molten state.
It is further preferred that in step (2), by quartz ampoule with 200 DEG C per hour from room temperature to 850 DEG C.
Preferably, in step (3) with 150~200 DEG C per hour of rate by quartz ampoule from room temperature to 650~700
DEG C and keep the temperature 2~4 days, be heat-treated.
It is further preferred that in step (3), by quartz ampoule with 200 DEG C per hour from room temperature to 677 DEG C, and 3 are kept the temperature
My god, it anneals.
Preferably, in step (4), ingot casting grind into powder is placed in graphite jig, using sensing heating, with every point
The rate that 100~300 DEG C of clock is warming up to 650~750 DEG C, and adjusting pressure is 60~80MPa, and constant temperature and pressure is handled 30 minutes,
Vacuum heating-press sintering is carried out, room temperature is then down to 50 DEG C per minute of rate Slow cooling, you can the sulphur of target components is made
Race's stannide thermoelectric material.
It is further preferred that in step (4), the temperature of sintering is 677 DEG C, and pressure used in sintering is 70MPa.
Preferably, the Absolute truth reciprocal of duty cycle of the vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
The present invention is based on early period and telluride magnesium (MgTe) formed solid solution realize energy band degeneracy promotion electronic transport performance and with
Cuprous telluride (Cu2Te the Research foundation that solid solution introduces clearance C u atom scattering phonon reduction lattice thermal conductivity) is formed,
MgTe and Cu are dissolved in SnTe materials simultaneously2The electrical property and hot property of Te materials collaboration optimization material.By being dissolved telluride magnesium
(MgTe) reduce the energy difference between two valence band and realize energy band convergence optimization electrical property；By being dissolved cuprous telluride (Cu2Te it) introduces
Lattice thermal conductivity (~0.5W/m-K) is greatly lowered in interstitial atom scattering phonon realization.The invention resulting materials not only form member
Element is environmentally friendly, and with higher thermoelectricity capability.The Sn with high performance obtained based on the invention1.03- yMgyTe(Cu2Te)xNew thermoelectric materials, zT values have reached 1.4 in 900K, are that one kind is hopeful to replace traditional p-type lead telluride
Material realizes the environmentally friendly new thermoelectric materials of large-scale commercial application.
Compared with existing telluride tinbase thermoelectric material, the invention has the advantages that：
(1) present invention significantly improves the pyroelectricity of SnTe sills by the collaboration optimization of electronic transport and thermotransport
Can, zT values have reached 1.4 in 900K, can significantly promote conversion efficiency of thermoelectric and the output of the thermo-electric device being made of the material
Power.
(2) compared with currently introducing nano-second-phase and reducing the technology of SnTe material lattice thermal conductivities to a certain degree, this hair
A kind of bright interstitial atom defect sturcture of thermodynamics stable state of introducing effectively scatters phonon, considerably reduces the crystalline substance of SnTe sills
Lattice thermal conductivity close to theoretical boundary, provides safeguard for thermoelectricity capability stability of the material under thermal cycle use condition.
(3) in component, compared with currently having high thermoelectricity capability SnTe sills, the invention avoids cadmium, mercury etc. to have
The introducing of malicious element obtains the environmentally friendly sulfur family stannide thermoelectricity material with high thermoelectricity capability by simple vacuum fusion
Material, has great importance to the extensive commercial application of the system material.
Description of the drawings
Fig. 1 is Sn1.03-yMgyTe(Cu2Te)0.05The Hall coefficient of (0 ＜ y≤0.12) and the relationship of mobility and temperature
Figure；
Fig. 2 is Sn1.03-yMgyTe(Cu2Te)0.05The Seebeck coefficients of (0 ＜ y≤0.12) and the pass of resistivity and temperature
System's figure；
Fig. 3 is Sn1.03-yMgyTe(Cu2Te)0.05(0 ＜ y≤0.12) total thermal conductivity and the relationship of lattice thermal conductivity and temperature
Figure；
Fig. 4 is Sn1.03-yMgyTe(Cu2Te)0.05The zT values of (0 ＜ y≤0.12) and the relational graph of temperature.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of high-performance environment-friendly type sulfur family stannide thermoelectric material, chemical formula Sn1.03-yMgyTe(Cu2Te)x(0
＜ x≤0.05,0 ＜ y≤0.12), by taking x=0.05 and y=0.05,0.08,0.1 and 0.12 in the present embodiment, under
Preparation method is stated, obtains the Sn of different Mg concentration1.03-yMgyTe(Cu2Te)0.05Block materials：
(1) different y values are taken, by chemical formula Sn1.03-yMgyTe(Cu2Te)0.05The stoichiometric ratio of (0 ＜ y≤0.12) weighs
Simple substance raw material tin Sn of the purity more than 99.99%, magnesium Mg, copper Cu, tellurium Te, raw material are positioned in quartz ampoule, and under vacuum
Encapsulate quartz ampoule.
(2) quartz ampoule for placing raw material is hung in shaft furnace, 850 DEG C is to slowly warm up to the rate of 200K/h, and
6h is kept the temperature, rapid quenching cools down to obtain the first ingot casting later；
(3) quenched first ingot casting of high-temperature fusion that step (2) obtains is heat-treated, is delayed with the rate of 200K/h
It is slow to be warming up to 677 DEG C, 3 days are kept the temperature, rapid quenching cools down to obtain the second ingot casting later；
(4) by the obtained second ingot casting grind into powder of step (3), powder is placed in graphite jig, using sensing
Heating is warming up to 677 DEG C with the rate of 200K/min, and adjustings pressure is 70MPa, and constant temperature 30 minutes, and it is hot to carry out vacuum high-temperature
Pressure sintering, is then slowly cooled to room temperature with the rate of 50K/min, obtains Sn1.03-yMgyTe(Cu2Te)0.05Flaky material, i.e.,
For target components sulfur family stannide thermoelectric material；
The Absolute truth reciprocal of duty cycle of vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
X=0.05 is set, when y=0.05,0.08,0.1,0.12, as shown in Figure 1a, peak RH/RH,300Corresponding temperature
Degree reduces with the increase of y, it was confirmed that poor can reduce with the increase of y between two valence band of the material.It can from Fig. 1 b
To find out, hall mobility variation with temperature trend is μ~T-1.5, announcement transports performance mechanism by based on acoustic phonon scattering
It leads, the thermoelectric material haveing excellent performance generally all meets phonon acoustic scattering mechanism.
The Sn of different y values1.03-yMgyTe(Cu2Te)0.05Seebeck coefficients and the relationship of resistivity and temperature such as Fig. 2 institutes
Show；As can be seen from the figure due to the reduction for waiting energy poor between two valence band, Seebeck coefficients are in 300-900K warm areas with y's
Increase and increase.It can be seen that most samples are degeneracy semiconductor material from Seebeck coefficients and resistivity.
The Sn of different y values1.03-yMgyTe(Cu2Te)0.05Total thermal conductivity and the relationship of lattice thermal conductivity and temperature such as Fig. 3
It is shown；As can be seen from the figure the total thermal conductivity of material and lattice thermal conductivity all reduce with the increase of y and temperature, 900K's
When minimum lattice thermal conductivity be 0.5W/m-K, close to the theoretical minimum of the material.
The Sn of different y values1.03-yMnyTe(Cu2Te)0.05ZT values and temperature relationship it is as shown in Figure 4；It can from figure
Go out the zT values of material increases with the increase of y and temperature, and zT values reach 1.4 in 900K, the peak for the material.
Embodiment 2
A kind of environmentally friendly sulfur family stannide thermoelectric material, chemical formula Sn1.03-yMgyTe(Cu2Te)x(x=
0.03, y=0.05), it is semi-conductor thermoelectric material.
A kind of preparation method of environmentally friendly sulfur family stannide thermoelectric material, includes the following steps：
(1) Vacuum Package：Chemical formula Sn is pressed with simple substance element S n, Mg, Cu, the Te of purity more than 99.99%1.03-yMgyTe
(Cu2Te)xStoichiometric ratio in (x=0.03, y=0.05) carries out dispensing, and Vacuum Package is in quartz ampoule；
(2) melting quenching：Quartz ampoule equipped with raw material is put into shaft furnace, it will be quartzy with 150 DEG C per hour of rate
Pipe is from room temperature to 850 DEG C and keeps the temperature 6 hours, and slow heating makes raw material fully be reacted in the molten state, then quenches
Fire obtains ingot casting；
(3) annealing quenching：It by gained ingot casting in (2) again Vacuum Package in quartz ampoule, and is put into shaft furnace, with every
Quartz ampoule from room temperature to 650 DEG C and is kept the temperature 2 days by the rate of 150 DEG C of hour, is carried out high annealing, is then quenched, obtain
Ingot casting；
(4) hot pressed sintering：The ingot casting grind into powder that will be obtained in (3) with agate mortar, is positioned in graphite jig, profit
With sensing heating, 650 DEG C are warming up to 100 DEG C per minute of rate, adjusting pressure is 60MPa, and constant temperature and pressure handles 30 points
Clock carries out vacuum heating-press sintering, is then down to room temperature with 50 DEG C per minute of rate Slow cooling, you can target components are made
Sulfur family stannide thermoelectric material.
Wherein, the Absolute truth reciprocal of duty cycle of the vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
Embodiment 3
A kind of environmentally friendly sulfur family stannide thermoelectric material, chemical formula Sn1.03-yMgyTe(Cu2Te)x(x=
0.05, y=0.12), it is semi-conductor thermoelectric material.
A kind of preparation method of environmentally friendly sulfur family stannide thermoelectric material, includes the following steps：
(1) Vacuum Package：Chemical formula Sn is pressed with simple substance element S n, Mg, Cu, the Te of purity more than 99.99%1.03-yMgyTe
(Cu2Te)xStoichiometric ratio in (x=0.05, y=0.12) carries out dispensing, and Vacuum Package is in quartz ampoule；
(2) melting quenching：Quartz ampoule equipped with raw material is put into shaft furnace, it will be quartzy with 200 DEG C per hour of rate
Pipe is from room temperature to 900 DEG C and keeps the temperature 6 hours, and slow heating makes raw material fully be reacted in the molten state, then quenches
Fire obtains ingot casting；
(3) annealing quenching：It by gained ingot casting in (2) again Vacuum Package in quartz ampoule, and is put into shaft furnace, with every
Quartz ampoule from room temperature to 700 DEG C and is kept the temperature 2 days by the rate of 200 DEG C of hour, is carried out high annealing, is then quenched, obtain
Ingot casting；
(4) hot pressed sintering：The ingot casting grind into powder that will be obtained in (3) with agate mortar, is positioned in graphite jig, profit
With sensing heating, 750 DEG C are warming up to 300 DEG C per minute of rate, adjusting pressure is 80MPa, and constant temperature and pressure handles 30 points
Clock carries out vacuum heating-press sintering, is then down to room temperature with 50 DEG C per minute of rate Slow cooling, you can target components are made
Sulfur family stannide thermoelectric material.
Wherein, the Absolute truth reciprocal of duty cycle of the vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
Embodiment 4
A kind of environmentally friendly sulfur family stannide thermoelectric material, chemical formula Sn1.03-yMgyTe(Cu2Te)x(x=
0.04, y=0.1), it is semi-conductor thermoelectric material.
A kind of preparation method of environmentally friendly sulfur family stannide thermoelectric material, includes the following steps：
(1) Vacuum Package：Chemical formula Sn is pressed with simple substance element S n, Mg, Cu, the Te of purity more than 99.99%1.03-yMgyTe
(Cu2Te)xStoichiometric ratio in (x=0.04, y=0.1) carries out dispensing, and Vacuum Package is in quartz ampoule；
(2) melting quenching：Quartz ampoule equipped with raw material is put into shaft furnace, it will be quartzy with 180 DEG C per hour of rate
Pipe is from room temperature to 880 DEG C and keeps the temperature 6 hours, and slow heating makes raw material fully be reacted in the molten state, then quenches
Fire obtains ingot casting；
(3) annealing quenching：It by gained ingot casting in (2) again Vacuum Package in quartz ampoule, and is put into shaft furnace, with every
Quartz ampoule from room temperature to 680 DEG C and is kept the temperature 3 days by the rate of 180 DEG C of hour, is carried out high annealing, is then quenched, obtain
Ingot casting；
(4) hot pressed sintering：The ingot casting grind into powder that will be obtained in (3) with agate mortar, is positioned in graphite jig, profit
With sensing heating, 700 DEG C are warming up to 200 DEG C per minute of rate, adjusting pressure is 70MPa, and constant temperature and pressure handles 30 points
Clock carries out vacuum heating-press sintering, is then down to room temperature with 50 DEG C per minute of rate Slow cooling, you can target components are made
Sulfur family stannide thermoelectric material.
Wherein, the Absolute truth reciprocal of duty cycle of the vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
Embodiment 5
A kind of environmentally friendly sulfur family stannide thermoelectric material, chemical formula Sn1.03-yMgyTe(Cu2Te)x(x=
0.05, y=0.12), it is semi-conductor thermoelectric material.
A kind of preparation method of environmentally friendly sulfur family stannide thermoelectric material, includes the following steps：
(1) Vacuum Package：Chemical formula Sn is pressed with simple substance element S n, Mg, Cu, the Te of purity more than 99.99%1.03-yMgyTe
(Cu2Te)xStoichiometric ratio in (x=0.05, y=0.12) carries out dispensing, and Vacuum Package is in quartz ampoule；
(2) melting quenching：Quartz ampoule equipped with raw material is put into shaft furnace, it will be quartzy with 200 DEG C per hour of rate
Pipe is from room temperature to 850 DEG C and keeps the temperature 6 hours, and slow heating makes raw material fully be reacted in the molten state, then quenches
Fire obtains ingot casting；
(3) annealing quenching：It by gained ingot casting in (2) again Vacuum Package in quartz ampoule, and is put into shaft furnace, with every
Quartz ampoule from room temperature to 677 DEG C and is kept the temperature 3 days by the rate of 200 DEG C of hour, is carried out high annealing, is then quenched, obtain
Ingot casting；
(4) hot pressed sintering：The ingot casting grind into powder that will be obtained in (3) with agate mortar, is positioned in graphite jig, profit
With sensing heating, 677 DEG C are warming up to 200 DEG C per minute of rate, adjusting pressure is 70MPa, and constant temperature and pressure handles 30 points
Clock carries out vacuum heating-press sintering, is then down to room temperature with 50 DEG C per minute of rate Slow cooling, you can target components are made
Sulfur family stannide thermoelectric material.
Wherein, the Absolute truth reciprocal of duty cycle of the vacuum described in step (1), step (3) and step (4) is no more than 10-1Pa。
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously can easily make these embodiments various modifications, and described herein general
Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to above-described embodiment, abilities
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be the present invention's
Within protection domain.
Claims (7)
1. a kind of environmentally friendly sulfur family stannide thermoelectric material, which is characterized in that its chemical formula is Sn1.03-yMgyTe
(Cu2Te)x, wherein 0<X≤0.05,0<y≤0.12.
A kind of 2. environmentally friendly sulfur family stannide thermoelectric material according to claim 1, which is characterized in that its chemical formula
For Sn1.03-yMgyTe(Cu2Te)x, wherein x=0.03~0.05, y=0.1~0.12.
A kind of 3. preparation method of environmentally friendly sulfur family stannide thermoelectric material as described in claim 1, which is characterized in that packet
Include following steps：
(1) Vacuum Package：Chemical formula Sn is pressed with simple substance element S n, Mg, Cu, the Te of purity more than 99.99%1.03-yMgyTe
(Cu2Te)xIn stoichiometric ratio carry out dispensing, and Vacuum Package is in quartz ampoule, wherein 0<X≤0.05,0<y≤0.12；
(2) melting quenching：Quartz ampoule equipped with raw material is heated, raw material is made fully to be reacted in the molten state, is then quenched
Fire obtains ingot casting；
(3) annealing quenching：It by ingot casting obtained by step (2) again Vacuum Package in quartz ampoule, and heats, carries out high annealing,
Then quenching, obtains ingot casting；
(4) hot pressed sintering：The ingot casting grind into powder that step (3) is obtained carries out vacuum heating-press sintering, subsequent slow cooling
Obtained sheet block materials are the environmentally friendly sulfur family stannide thermoelectric material of target components；
Quartz ampoule from room temperature to 850~900 DEG C and is kept the temperature 6 small with 150~200 DEG C per hour of rate in step (2)
When, raw material is made adequately to be reacted in the molten state；
In step (3) with 150~200 DEG C per hour of rate by quartz ampoule from room temperature to 650~700 DEG C and keep the temperature 2~4
My god, it is heat-treated；
In step (4), ingot casting grind into powder is placed in graphite jig, using sensing heating, with 100~300 DEG C per minute
Rate be warming up to 650~700 DEG C, adjusting pressure is 60~80MPa, and constant temperature and pressure is handled 30 minutes, carries out vacuum hotpressing
Sintering, then cools down to room temperature with 50 DEG C per minute of rate, you can environmentally friendly sulfur family stannide thermoelectric material is made.
4. the preparation method of environmentally friendly sulfur family stannide thermoelectric material according to claim 3, which is characterized in that step
Suddenly in (2), by quartz ampoule with 200 DEG C per hour from room temperature to 850 DEG C.
5. the preparation method of environmentally friendly sulfur family stannide thermoelectric material according to claim 3, which is characterized in that step
Suddenly in (3), by quartz ampoule with 200 DEG C per hour from room temperature to 677 DEG C, and 3 days are kept the temperature, annealed.
6. the preparation method of environmentally friendly sulfur family stannide thermoelectric material according to claim 3, which is characterized in that step
Suddenly in (4), the temperature of sintering is 677 DEG C, and pressure used in sintering is 70MPa.
7. the preparation method of environmentally friendly sulfur family stannide thermoelectric material according to claim 3, which is characterized in that step
Suddenly the Absolute truth reciprocal of duty cycle of the vacuum described in (1), step (3) and step (4) is no more than 10-1Pa。
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| EP1921699A2 (en) * | 1998-09-18 | 2008-05-14 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| CN102630254A (en) * | 2009-11-25 | 2012-08-08 | Aqt太阳能公司 | Low melting point sputter targets for chalcogenide photovoltaic applications and methods of manufacturing the same |
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| WO2016178000A1 (en) * | 2015-05-02 | 2016-11-10 | Alpha Metals, Inc. | Lead-free solder alloy with low melting point |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1921699A2 (en) * | 1998-09-18 | 2008-05-14 | Canon Kabushiki Kaisha | Electrode material for anode of rechargeable lithium battery, electrode structural body using said electrode material, rechargeable lithium battery using said electrode structural body, process for producing said electrode structural body, and process for producing said rechargeable lithium battery |
| CN102630254A (en) * | 2009-11-25 | 2012-08-08 | Aqt太阳能公司 | Low melting point sputter targets for chalcogenide photovoltaic applications and methods of manufacturing the same |
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