CN110002876A - A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material - Google Patents

A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material Download PDF

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CN110002876A
CN110002876A CN201910311322.0A CN201910311322A CN110002876A CN 110002876 A CN110002876 A CN 110002876A CN 201910311322 A CN201910311322 A CN 201910311322A CN 110002876 A CN110002876 A CN 110002876A
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sintered
sintering
powder
temperature
ultra low
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孙毅
张占鹏
黄旭初
袁鹏
瞿江林
胡宁
田金龙
徐京南
郑晶晶
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Changji Institute
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time

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Abstract

The present invention provides a kind of Cu2Se0.5S0.5The step of sintered at ultra low temperature method of thermoelectric material, belongs to ceramic of compact preparation technical field, this method includes: that (1) prepare being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution.(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, are then uniformly mixed the two with milling bar, are obtained mixture；(3) mixture that step (2) obtains is fitted into mold, then in 300 ~ 500Mpa, at room temperature 10 ~ 20min of precompressed, heating sintering is then carried out under the pressure of 300 ~ 500Mpa.The sintering method compared with the conventional sinterings method such as discharge plasma sintering, hot pressed sintering, have many advantages, such as energy loss it is low, it is highly-safe, be suitable for industrialized production, and the Cu prepared using method of the invention2Se0.5S0.5Thermoelectric ceramics consistency is high, thermoelectricity capability is excellent.

Description

A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material
Technical field
The invention belongs to ceramic of compact preparation technical fields, adulterate thermoelectricity material more specifically to a kind of copper sulfide selenium The sintered at ultra low temperature method of material.
Background technique
Ceramic material is with the excellent properties of its high temperature resistant, wear-resistant, electricity, mechanics, heat transfer etc., in every field All have a wide range of applications.Determine that a whether excellent important factor of ceramic performance is that sintering process.Currently used for Cu2Se0.5S0.5Sintering method be mainly hot pressed sintering, discharge plasma sintering.Both sintering methods are required at 500 DEG C Above to carry out, this not only needs to consume more energy, but also all produces limitation for many researchs.For example, ceramics-polymerization Object composite material.Ceramic-polymer Composite has a variety of design spaces, can improve material property and realize multi-functional set It is standby.However, the process window to differ widely between polymer and ceramics limits the full scope of required performance.If can be significantly The temperature for reducing sintering, then of this sort problem can be resolved.Sintered at ultra low temperature of the present invention can be Room temperature is to densifying powder at 200 DEG C, for Cu2Se0.5S0.5The research of composite function ceramics is highly beneficial, will significantly Reduce as different materials process window difference and caused by limit.
Summary of the invention
The object of the present invention is to provide a kind of sintered at ultra low temperature methods of copper sulfide selenium doped thermoelectric material.With routine Suppress Cu2Se0.5S0.5Powder is similar, uniaxial machinery power drive densification, but we are in Cu2Se0.5S0.5Liquid phase is added in powder Afterwards, facilitate to enhance the lubricity between particle, there is also pressure drives on the local scale of the sharp small face contact of particle The enhancing of dynamic solubility, this is conducive to the larger surface area of the filling in gap and particle sliding between powder granule.Continuing High pressure under press certain temperature so that hydrothermal solution reaction-filling intergranular pore, powder grain occur for the liquid phase for having dissolved powder Also continued propagation, final realize densify at such a temperature.
A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material, it is characterised in that: the step of this method includes:
(1) preparing being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution.It is mentioned herein micro at this Field belongs to common sense；
(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, then will with milling bar The two is uniformly mixed, and obtains mixture；
(3) mixture that step (2) obtains is fitted into mold, then in 300 ~ 500Mpa, at room temperature 10 ~ 20min of precompressed, so Heating sintering is carried out under the pressure of 300 ~ 500Mpa afterwards.The mold that High Voltage is able to bear in reality can be used in this. It is powder and mill under sintering process high temperature in order to prevent since mold common in existing other sintering methods is graphite jig Tool reaction, but just without considering this problem in the low-temperature sintering of the application.
In the step (1), precursor solution is deionized water.
In the step (2), Cu2Se0.5S0.5Powder is nanometer grade powder, the nanometer grade powder and precursor solution Mass ratio be 5:1.
In the step (3), the mold is chromium steel mold, and the diameter that the chromium steel mold is is 10 ~ 30mm, a height of 60 The chromium cylindrical steel mold of ~ 80mm.
In the step (3), the temperature program(me) that is sintered specifically: with heating rate: the heating speed of 5 ~ 20 DEG C/min Rate is directly raised to sintering temperature, and soaking time is 1 ~ 2 hour, furnace cooling later, unloading pressure after being cooled to room temperature.
Further, heating is specifically referred to from room temperature to sintering temperature in the step (3), and the sintering temperature is 200 ℃。
Or, heating specifically refers to be sintered at room temperature in the step (3).
Or, heating is specifically referred to from room temperature to sintering temperature in the step (3), the sintering temperature is less than 200 DEG C.
With existing Cu2Se0.5S0.5Sintering technology compare, the beneficial effects of the present invention are:
(1) due to the sintering temperature being greatly lowered, the energy consumption in sintering process is effectively reduced.
(2) sintered at ultra low temperature Cu2Se0.5S0.5, it is possible to prevente effectively from due to difference in the research of copper sulphur compound composite ceramics It is limited caused by substance process window is different.
Detailed description of the invention
Fig. 1 is the Cu being sintered using sintering method of the invention2Se0.5S0.5The XRD spectrum of thermoelectric ceramics.
Fig. 2 is the Cu being sintered using sintering method of the invention2Se0.5S0.5The SEM image of thermoelectric ceramics.
Fig. 3 is the Cu being sintered using sintering method of the invention2Se0.5S0.5The conductivity of thermoelectric ceramics varies with temperature song Line chart；
The Cu that Fig. 4 is sintered using the sintering method of the invention2Se0.5S0.5The Seebeck coefficient of thermoelectric ceramics varies with temperature song Line chart；
The Cu that Fig. 5 is sintered using sintering method of the invention2Se0.5S0.5The power factor of thermoelectric ceramics varies with temperature curve Figure.
The Cu that Fig. 6 is sintered using sintering method of the invention2Se0.5S0.5The thermal conductivity of thermoelectric ceramics varies with temperature curve Figure.
The Cu that Fig. 7 is sintered using sintering method of the invention2Se0.5S0.5The thermoelectric figure of merit ZT of thermoelectric ceramics is varied with temperature Curve graph.
Specific embodiment
Technological means of the invention, creation characteristic, achieving the goal is easy to understand with effect in order to make, below in conjunction with Technical solution of the present invention is clearly and completely described in the embodiment of the present invention.Cu as described herein2Se0.5S0.5Refer to and contains There is Cu2S and Cu2The mixture of Se.
Embodiment 1
(1) Cu of electronic balance weighing 1g is used2Se0.5S0.5Powder is put into Yan Portland, then using liquid-transfering gun measure 200 μ L go from Sub- water is mixed with powder.
(2) after completing step (1), milling bar milled mixtures repeatedly are used, it is ensured that powder is uniformly mixed with solution.
(3) after completing step (2), mixed uniformly ceramics precursor powder is put into chromium steel mold, then mold is placed Under press machine；First press pressure precompressed 10 minutes of 500Mpa at room temperature, then under conditions of keeping pressure constant with Temperature is risen to 200 DEG C by the heating rate of 10 DEG C/min；Finally (500Mpa, 200 DEG C) is sintered under conditions of the constant temperature and pressure 1.5 hour；Keep pressure constant after the completion of sintering, unloading pressure after furnace cooling obtains Cu2Se0.5S0.5Ceramics.
Embodiment 2
(1) Cu of electronic balance weighing 1g is used2Se0.5S0.5Powder is put into Yan Portland, then using liquid-transfering gun measure 200 μ L go from Sub- water is mixed with powder.
(2) after completing step (1), milling bar milled mixtures repeatedly are used, it is ensured that powder is uniformly mixed with solution.
(3) after completing step (2), mixed uniformly ceramics precursor powder is put into chromium steel mold, then mold is placed Under press machine；First press pressure precompressed 10 minutes of 500Mpa at room temperature, then under conditions of keeping pressure constant with Temperature is risen to 100 DEG C by the heating rate of 10 DEG C/min；Finally (500Mpa, 100 DEG C) is sintered under conditions of the constant temperature and pressure 1.5 hour；Keep pressure constant after the completion of sintering, unloading pressure after furnace cooling obtains Cu2Se0.5S0.5Ceramics.
Embodiment 3
(1) Cu of electronic balance weighing 1g is used2Se0.5S0.5Powder is put into Yan Portland, then using liquid-transfering gun measure 200 μ L go from Sub- water is mixed with powder.
(2) after completing step (1), milling bar milled mixtures repeatedly are used, it is ensured that powder is uniformly mixed with solution.
(3) after completing step (2), mixed uniformly ceramics precursor powder is put into chromium steel mold, then mold is placed Under press machine；First press pressure precompressed 10 minutes of 500Mpa at room temperature, then under conditions of keeping pressure constant with Temperature is risen to 50 DEG C by the heating rate of 10 DEG C/min；Finally (500Mpa, 50 DEG C) sintering 1.5 under conditions of the constant temperature and pressure Hour；Keep pressure constant after the completion of sintering, unloading pressure after furnace cooling obtains Cu2Se0.5S0.5Ceramics.
Embodiment 4
(1) Cu of electronic balance weighing 1g is used2Se0.5S0.5Powder is put into Yan Portland, then using liquid-transfering gun measure 200 μ L go from Sub- water is mixed with powder.
(2) after completing step (1), milling bar milled mixtures repeatedly are used, it is ensured that powder is uniformly mixed with solution.
(3) after completing step (2), mixed uniformly ceramics precursor powder is put into chromium steel mold, then mold is placed Under press machine；Pressure is directly risen into 500Mpa, (room temperature) pressure maintaining 2 hours, subsequent unloading pressure under conditions of not heating Obtain Cu2Se0.5S0.5Ceramics.
In order to further detect the Cu that the embodiment of the present invention 1~4 is sintered2Se0.5S0.5The performance of thermoelectric ceramics, Wo Menjin Go dependence test and analysis, particular content is as follows:
Include two-phase by the resulting sample of sintering known to the XRD spectrum of Fig. 1, respectively corresponds vitreous copper tetragonal crystal system Cu2S (PDF#72-1071) and manganosite rhombic system Cu2Se, with the raising of sintering temperature, crystal grain further growth, peak intensity has Enhanced.From in the SEM image of Fig. 2 it will be seen that under 4 sintering temperatures (a is room temperature, b is 50 DEG C, c is 100 DEG C, D be 200 DEG C) preparation sample it is all densified.Thermoelectricity capability test is carried out to the ceramics sample of four sintering temperatures.Fig. 3 For conductivity variation with temperature curve, the conductivity of sample has first to reduce as the temperature rises increases last reduction again again Variation；With the raising of sintering temperature, the conductivity of sample is gradually increased.Fig. 4 is that Seebeck coefficient varies with temperature curve, with Conductivity on the contrary, with sintering temperature raising, Seebeck coefficient gradually decreases.Fig. 5 is that power factor varies with temperature curve, The variation of power factor and numerical value are all very small in 373-673K low temperature range, rise rapidly after 673K, 200 DEG C of burnings The sample power factor of knot reaches 7.068 μ W/cmK of maximum value in 823K2.Fig. 6 is that thermal conductivity varies with temperature curve graph, institute There is the thermal conductivity of sample to gradually decrease as the temperature rises, the sample of 50 DEG C of sintering reaches minimum thermal conductivity 0.436 in 823K W·m-1·K-1.Fig. 7 is thermoelectric figure of merit ZT variation with temperature curve, in 373-673K temperature range, lower sintering temperature The ZT value of sample is higher than the sample of higher temperatures sintering；After temperature reaches 673K, the sample ZT value rapid increase of higher temperatures sintering, 200 DEG C sintering samples 823K obtain maximum ZT value, 0.868.By being analyzed above it is found that sintering method of the invention is made Standby Cu2Se0.5S0.5Ceramics sample has excellent thermoelectricity capability, can be used as thermoelectric material application.
In conclusion the beneficial effects of the present invention are:
(1) sintering temperature obtains the reduction (can also complete the densification to powder at room temperature) of high degree, for producing The saving of the energy has very great meaning in journey.
(2) sintered at ultra low temperature Cu2Se0.5S0.5, it is possible to prevente effectively from due to difference in the research of copper sulphur compound composite ceramics It is limited caused by substance process window is different.
Embodiment 5
A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material, it is characterised in that: the step of this method includes:
(1) preparing being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution.It is mentioned herein micro at this Field belongs to common sense；
(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, then will with milling bar The two is uniformly mixed, and obtains mixture；
(3) mixture that step (2) obtains is fitted into mold, then in 300 ~ 500Mpa, at room temperature 10 ~ 20min of precompressed, so Heating sintering is carried out under the pressure of 300 ~ 500Mpa afterwards.The mold that High Voltage is able to bear in reality can be used in this. It is powder and mill under sintering process high temperature in order to prevent since mold common in existing other sintering methods is graphite jig Tool reaction, but just without considering this problem in the low-temperature sintering of the application.
In the step (1), precursor solution is deionized water.
In the step (2), Cu2Se0.5S0.5Powder is nanometer grade powder, the nanometer grade powder and precursor solution Mass ratio be 5:1.
In the step (3), the mold is chromium steel mold, and the diameter that the chromium steel mold is is 10 ~ 30mm, a height of 60 The chromium cylindrical steel mold of ~ 80mm.
In the step (3), the temperature program(me) that is sintered specifically: with heating rate: the heating speed of 5 ~ 20 DEG C/min Rate is directly raised to sintering temperature, and soaking time is 1 ~ 2 hour, furnace cooling later, unloading pressure after being cooled to room temperature.
Further, heating is specifically referred to from room temperature to sintering temperature in the step (3), and the sintering temperature is 200 ℃。
Embodiment 6
A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material, it is characterised in that: the step of this method includes:
(1) preparing being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution.It is mentioned herein micro at this Field belongs to common sense；
(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, then will with milling bar The two is uniformly mixed, and obtains mixture；
(3) mixture that step (2) obtains is fitted into mold, then in 300 ~ 500Mpa, at room temperature 10 ~ 20min of precompressed, so Heating sintering is carried out under the pressure of 300 ~ 500Mpa afterwards.The mold that High Voltage is able to bear in reality can be used in this. It is powder and mill under sintering process high temperature in order to prevent since mold common in existing other sintering methods is graphite jig Tool reaction, but just without considering this problem in the low-temperature sintering of the application.
In the step (1), precursor solution is deionized water.
In the step (2), Cu2Se0.5S0.5Powder is nanometer grade powder, the nanometer grade powder and precursor solution Mass ratio be 5:1.
In the step (3), the mold is chromium steel mold, and the diameter that the chromium steel mold is is 10 ~ 30mm, a height of 60 The chromium cylindrical steel mold of ~ 80mm.
In the step (3), the temperature program(me) that is sintered specifically: with heating rate: the heating speed of 5 ~ 20 DEG C/min Rate is directly raised to sintering temperature, and soaking time is 1 ~ 2 hour, furnace cooling later, unloading pressure after being cooled to room temperature.
Further, heating specifically refers to be sintered at room temperature in the step (3).
Embodiment 7
A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material, it is characterised in that: the step of this method includes:
(1) preparing being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution.It is mentioned herein micro at this Field belongs to common sense；
(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, then will with milling bar The two is uniformly mixed, and obtains mixture；
(3) mixture that step (2) obtains is fitted into mold, then in 300 ~ 500Mpa, at room temperature 10 ~ 20min of precompressed, so Heating sintering is carried out under the pressure of 300 ~ 500Mpa afterwards.The mold that High Voltage is able to bear in reality can be used in this. It is powder and mill under sintering process high temperature in order to prevent since mold common in existing other sintering methods is graphite jig Tool reaction, but just without considering this problem in the low-temperature sintering of the application.
In the step (1), precursor solution is deionized water.
In the step (2), Cu2Se0.5S0.5Powder is nanometer grade powder, the nanometer grade powder and precursor solution Mass ratio be 5:1.
In the step (3), the mold is chromium steel mold, and the diameter that the chromium steel mold is is 10 ~ 30mm, a height of 60 The chromium cylindrical steel mold of ~ 80mm.
In the step (3), the temperature program(me) that is sintered specifically: with heating rate: the heating speed of 5 ~ 20 DEG C/min Rate is directly raised to sintering temperature, and soaking time is 1 ~ 2 hour, furnace cooling later, unloading pressure after being cooled to room temperature.
Further, heating is specifically referred to from room temperature to sintering temperature in the step (3), and the sintering temperature is less than 200℃。
Embodiment 8
A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material, it is characterised in that: the step of this method includes:
(1) preparing being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution.It is mentioned herein micro at this Field belongs to common sense；
(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, then will with milling bar The two is uniformly mixed, and obtains mixture；
(3) mixture that step (2) obtains is fitted into mold, then in 350Mpa, at room temperature precompressed 12min, is then existed Heating sintering is carried out under the pressure of 350Mpa.The mold that High Voltage is able to bear in reality can be used in this.Due to existing Common mold is graphite jig in other sintering methods, is that powder is reacted with grinding tool under sintering process high temperature in order to prevent, But just without considering this problem in the low-temperature sintering of the application.
In the step (1), precursor solution is deionized water.
In the step (2), Cu2Se0.5S0.5Powder is nanometer grade powder, the nanometer grade powder and precursor solution Mass ratio be 5:1.
In the step (3), the mold is chromium steel mold, and the diameter that the chromium steel mold is is 20mm, a height of 70mm Chromium cylindrical steel mold.
In the step (3), the temperature program(me) that is sintered specifically: with heating rate: the heating rate of 10 DEG C/min It is directly raised to sintering temperature, soaking time is 1.5 hours, furnace cooling later, unloading pressure after being cooled to room temperature.
Further, heating is specifically referred to from room temperature to sintering temperature in the step (3), and the sintering temperature is 200 ℃。
Disclosed above is only presently preferred embodiments of the present invention, and still, the embodiment of the present invention is not limited to this, Ren Heben What the technical staff in field can think variation should all fall into protection scope of the present invention.

Claims (8)

1. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material, it is characterised in that: the step of this method includes:
(1) preparing being capable of oligodynamical Cu2Se0.5S0.5The solution of powder is as precursor solution；
(2) by Cu2Se0.5S0.5Powder and precursor solution obtained in step (1) are all put into Yan Portland, then will with milling bar The two is uniformly mixed, and obtains mixture；
(3) mixture that step (2) obtains is fitted into mold, then in 300 ~ 500Mpa, at room temperature 10 ~ 20min of precompressed, so Heating sintering is carried out under the pressure of 300 ~ 500Mpa afterwards.
2. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: In the step (1), precursor solution is deionized water.
3. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: In the step (2), Cu2Se0.5S0.5Powder is nanometer grade powder, the mass ratio of the nanometer grade powder and precursor solution It is 5:1.
4. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: In the step (3), the mold is chromium steel mold, and the diameter that the chromium steel mold is is 10 ~ 30mm, a height of 60 ~ 80mm Chromium cylindrical steel mold.
5. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: Heating is specifically referred to from room temperature to sintering temperature in the step (3), and the sintering temperature is 200 DEG C.
6. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: Heating specifically refers to be sintered at room temperature in the step (3).
7. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: Heating is specifically referred to from room temperature to sintering temperature in the step (3), and the sintering temperature is less than 200 DEG C.
8. a kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material according to claim 1, it is characterised in that: In the step (3), the temperature program(me) that is sintered specifically: with heating rate: the heating rate of 5 ~ 20 DEG C/min directly rises To sintering temperature, soaking time is 1 ~ 2 hour, furnace cooling later, unloading pressure after being cooled to room temperature.
CN201910311322.0A 2019-04-18 2019-04-18 A kind of sintered at ultra low temperature method of copper sulfide selenium doped thermoelectric material Pending CN110002876A (en)

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Citations (5)

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